JP2906833B2 - Pigment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is suitable for use, especially non-agglomerated,
C. excellent in crystal stability and fluidity. I. Pigment Red 177 and a derivative thereof.

[0002] I. Pigment Red 177 (4,
4'-Diamino-1,1'-dianthraquinonyl) is a practically useful red pigment having a vivid color tone and high coloring power, and is frequently used for coloring high-molecular organic materials. However, when dispersed in non-aqueous vehicles such as offset inks, gravure inks, and paints, it is difficult to obtain a stable dispersion, which causes various problems that have a significant effect on manufacturing operations and the value of the resulting product. What happens often happens. For example, C.I. I. Dispersions containing Pigment Red 177 often exhibit high viscosities, which can be difficult to use, as well as difficult to transport, as well as worse, take away from the disperser of the product, during storage, or even worse, during storage.

[0003] When different kinds of pigments are used in a mixture, color unevenness and a remarkable decrease in tinting strength may appear in a colored product due to phenomena such as color separation and sedimentation due to aggregation. Further, with respect to the surface of the coated film of the colored product, a state defect such as a decrease in gloss and a leveling defect may occur. In non-aqueous vehicles such as offset inks, gravure inks and paints, C.I.
I. Pigment Red 177 crystal particles,
Since the form is changed to a stable state, the commercial value may be impaired due to a significant change in hue, a decrease in coloring power, generation of coarse particles, and the like in the developed product.

In order to solve these problems, many proposals have been made mainly on copper phthalocyanine pigments and quinacridone pigments. When the contents are classified by technical methods, they are roughly divided into the following two. The first law is US
As disclosed in P3370971 and US Pat. No. 2,965,511, the surface of pigment particles is coated with a colorless compound such as silicon oxide, aluminum oxide and tertiary butyl benzoic acid. The second law is Japanese Patent Publication No. 41-
A compound obtained by introducing a substituent such as a sulfone group, a sulfonamide group, an aminomethyl group, or a phthalimidomethyl group into a side chain using an organic pigment as a parent skeleton, as represented by US Pat. No. 2,466 and US Pat. No. 2,761,865, is mixed. Is the way.

The second method has remarkable effects on the non-aggregation property and crystal stability of the pigment in the non-aqueous vehicle as compared with the first method, and is judged from the easiness of production of the pigment composition. This is a very advantageous method. JP-A-63-172
772 discloses, in particular, C.I. I. Pigment Red 177
To improve the rheological properties of C.I. I. A second method of mixing a sulfonated derivative of Pigment Red 177 has been proposed, but this pigment is not sufficiently satisfactory in quality.

[0006]

The present invention relates to C.I. I. Pigment Red 177 ameliorates the various disadvantages described above and provides a pigment composition that provides good agglomeration resistance, crystal growth resistance and stability, and dispersion fluidity to a wide range of non-aqueous vehicles. Things.

[0007]

The above object is achieved by the present invention described below. That is, C.I. I. Pigment Red 177 (100 parts by weight) and 0.3 to 30 parts by weight of a compound of the formula (2). Equation (1)

Embedded image Equation (2)

Embedded image (Wherein, R ₁ and R _2;. Hydrogen atom, a substituted or unsubstituted alkyl group, a nitrogen in a cycloalkyl group or R _1, R _2, may form a heterocyclic ring containing an oxygen or sulfur atom R ₃ A hydrogen atom or a lower alkyl group k; an integer 1 or 2 l; an integer 2 or 3 m; an integer 0 or 1 n; an integer 1 or 2)

Various methods are available for obtaining the pigment derivative represented by the formula (2), but the following method is industrially advantageous. That is, in polyphosphoric acid or concentrated sulfuric acid, C.I. I.
Pigment Red 177 is reacted with paraformaldehyde and monochloroacetic acid amide or monochloroacetic acid alkylamide or 3-chloropropionic acid amide or an alkylamide thereof to obtain a compound represented by the formula (3). This is a method of reacting an amino compound. Equation (3)

Embedded image (Wherein R ₃ , k and n are the same as described above)

Typical examples of the primary or secondary amine include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine and n-hexylamine. Octylamine, 2-ethylhexylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, di-
n-butylamine, diisobutylamine, N-methylhexylamine, di-n-octylamine, di- (2-ethylhexyl) -amine, 2-hydroxymethylaminoethanol, diethanolamine, 3-aminopropanol, 2-aminopropanol, 3 -Methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-
(2-ethylhexyloxy) propylamine, 3-lauryloxypropylamine, piperidine, 2-pipecholine, 4-pipecholine, 2,4-lupetidine, 2,6-lupetidine, 3-piperidinemethanol, N-aminopiperidine, N -Amino-4-pipecholine, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine,
N-methylhomopiperidine, N-methylpiperazine, 1
-Amino-4-cyclopentylpiperazine, 1-cyclopentylpiperazine, morpholine, thiomorpholine, dimethylaminoethylamine, ethylaminoethylamine, diethylaminoethylamine, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine,
2-hydroxyethylaminopropylamine, laurylaminopropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-
Aminopropyl piperidine, N-aminopropyl-2-
Pipecoline, N-aminopropylmorpholine and the like.

The reaction between the compound represented by the formula (3) and the above-mentioned amino compound is carried out, for example, in the presence of an excess of the amino compound at 60 to 150 ° C. in water or an inert solvent. The amino component introduced into the side chain shows a strong affinity for an anionic portion such as a carboxyl group of the resin component contained in the vehicle, and C.I. I. Pigment Red 177 is considered to contribute to improvement in dispersibility.

The C.I. of the pigment derivative represented by the formula (2) according to the present invention. I. Pigment Red 177 is added in an amount of 0.1 parts by weight based on 100 parts by weight of indanthrone blue pigment.
3 to 30 parts by weight are preferred. If the amount is less than 0.3 part by weight, the effect is reduced, and if the amount is more than 30 parts by weight, the effect of the amount used is not obtained, and there is a possibility that the various resistance of the colored material after use as a pigment composition may be deteriorated. . Most preferred is 2 to 15 parts by weight.

As a method for preparing the pigment composition, C.I. I.
Pigment Red 177 powder and the pigment derivative powder represented by the formula (2) may be mixed with each other to obtain the desired effect. However, mechanical mixing may be performed by a kneader, a roll mill, an attritor, a super mill, various pulverizers, or the like. Or mix
C. I. A solution containing a pigment derivative is added to a suspension of Pigment Red 177 in water or an organic solvent, and the pigment derivative is deposited on the surface of the pigment, or an indanthrone blue pigment and a pigment derivative are added to a solvent having a strong dissolving power such as sulfuric acid. Can be obtained by performing a close mixing method such as co-dissolution and co-precipitation with a poor solvent such as water.

[0013]

The pigment composition of the present invention has a crystal transition even in an aromatic solvent at room temperature or at 160 ° C.
No growth is observed and no change in hue and tinting strength. C.I. I. Pigment Red 177, compared to the case where Pigment Red 177 is used alone, shows good dispersibility in non-aqueous vehicles such as paints and gravure inks, and shows good fluidity because it does not cause aggregation. No color separation or sedimentation of the pigment occurs even when used in combination with the pigment. Therefore, it is possible to obtain a beautiful colored polymer having good gloss of a printed material or a coating film.

[0014]

The synthesis of a representative compound represented by the formula (2) will be outlined below as a production example. In addition, in an example, a part shows a weight part. Production Example 1 Chromophtal Red A2B in 98 parts of 98% sulfuric acid
11 parts of (CI Pigment Red 177) are added at 30 ° C. or lower and stirred to dissolve. Subsequently, 9.5 parts of monochloroacetic acid amide and 4 parts of paraformaldehyde were added at 30 ° C. or lower, and the mixture was stirred at 25 ° C. for 2 hours.
After stirring for 4 hours, the mixture was poured into ice water, filtered and washed with water to give C.I. having the following chemical structure (a). I. Pigment Red 177 derivative in water was obtained. Dry some,
When the number of substituents was determined by chlorine analysis and weighing, 1.5 were introduced per molecule. (A)

Embedded image The above water paste was reslurried in 400 parts of water, 7 parts of diethylamine was added, and the mixture was stirred at 70 ° C. for 2 hours.
After washing with water and drying, C.I. having the following chemical structure (b): I.
Pigment Red 177 derivative was obtained as a red powder. It readily dissolved in dilute acetic acid. (B)

Embedded image

Preparation Example 2 The same reaction as in Preparation Example 1 was carried out except that diethylamine of Preparation Example 1 was replaced with 10 parts of 2-pipecholine, and the following chemical structure (c)
Having C.I. I. Pigment Red 177 derivative was obtained as a red powder. It readily dissolved in dilute acetic acid. (C)

Embedded image

Preparation Example 3 The same reaction as in Preparation Example 1 was carried out except that diethylamine of Preparation Example 1 was changed to 10 parts of dimethylaminopropylamine, and C.I. having the following chemical structural formula (d) was obtained. I. Pigment Red 1
A red powder of the 77 derivative was obtained. It readily dissolved in dilute acetic acid. (D)

Embedded image

Production Example 4 The diethylamine of Production Example 1 was replaced with cyclohexylamine 10
The reaction was carried out in the same manner as in Production Example 1 except that C.I. I. Pigment Red 177 derivative was obtained as a red powder. It readily dissolved in dilute acetic acid. (E)

Embedded image

Production Example 5 Chromium phthalate red A2B (CI pigment red 177) 11 was added to 100 parts of polyphosphoric acid heated to 80 ° C.
Then, 95 parts of monochloroacetic amide and 4 parts of paraformaldehyde are added, and the mixture is stirred at 110 ° C. for 5 hours. Pour into water, filter and wash, then 400
Then, add 8 parts of diethylaminoethylamine and heat to reflux for 2 hours. After cooling, the mixture was filtered, washed with water and dried to obtain C.I. having the following chemical structure (f). I. Pigment Red 1
A red powder of the 77 derivative was obtained. It readily dissolved in dilute acetic acid. (F)

Embedded image

Production Example 6 Monochloroacetic acid amide of Production Example 5 was replaced with 12.6 parts of monochloroacetic acid methylamide, and the same reaction as in Production Example 5 was carried out. I. Pigment Red 177 derivative was obtained as a red powder. It readily dissolved in dilute acetic acid. (G)

Embedded image

Production Example 7 Monochloroacetic acid amide of Production Example 5 was replaced with 12.6 parts of β-chloropropionic acid chloride, and the same reaction as in Production Example 5 was carried out. I. Pigment Red 177 derivative was obtained as a red powder. It readily dissolved in dilute acetic acid. (H)

Embedded image Hereinafter, an example and a comparative example will be described. In addition, the chemical structure of each compound shown by the alphabet corresponds to that shown in Production Examples.

Examples 1 to 9 An alkyd melamine resin varnish for baking paint was prepared according to the formula (1)
C. I. Pigment Red 177 (Chromophthal Red A2B manufactured by Ciba-Geigy) alone, and a pigment composition of the present invention in which each compound shown in Production Examples 1 to 7 was mixed with Chromophthal Red A2B, and the pigment content was 6% by weight. , And dispersed by a ball mill to prepare a paint. Table 1 shows the results of measuring the viscosity immediately after the removal and storage for one month.

[Table 1]

The alkyd melamine paints using the pigment compositions according to Examples 1 to 9 are more excellent in fluidity and crystal stability than the comparative examples, and the hue is beautiful and the coloring strength is large in the coating film. Was excellent in gloss. Further, the storage stability was excellent with little increase in viscosity.

The dispersion stability will be compared with the examples of color separation stability, which is particularly problematic in application. The paints shown in Examples of Table 1 were cut with a base paint of titanium oxide prepared in advance with an alkyd melamine resin varnish so that the ratio of pigment to titanium oxide became 1/10, to obtain a light-colored paint. This light-colored paint was further diluted with xylene, and Ford Cup No. 4 for 20 seconds (25 ° C)
Table 2 shows the results of observation of changes in the glass wall surface after injection into a test tube. Table 2 cites the paint of Example 1 as an example, but the paints of Examples 2 to 9 also show the same behavior as the examples,
The pigment compositions according to the invention have shown excellent results.

[Table 2]

Example 10 A cyclized rubber varnish for gravure was prepared using C.I. I. Pigment Red 177 (Chromophthal Red A3B manufactured by Ciba-Geigy) alone, and a pigment composition of the present invention in which each compound shown in Production Examples 1 to 7 was mixed with Chromophthal Red A3B, and the pigment content was 10% by weight. Gravure ink was prepared by dispersing with a bead mill. When the fluidity was compared with a B-type viscometer, the one according to the present invention was remarkably excellent. In addition, excellent results were obtained in the effects on the clarity, transparency, coloring power, and gloss of the color tone of the printed matter printed with the gravure ink.

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein the C.I. I. Pigment Red 177 (100 parts by weight) and 0.3 to 30 parts by weight of a compound of the formula (2). Formula (1) Formula (2) (Wherein, R ₁ and R _2;. Hydrogen atom, a substituted or unsubstituted alkyl group, a nitrogen in a cycloalkyl group or R _1, R _2, may form a heterocyclic ring containing an oxygen or sulfur atom R ₃ A hydrogen atom or a lower alkyl group k; an integer 1 or 2 l; an integer 2 or 3 m; an integer 0 or 1 n; an integer 1 or 2)