JPH039961A - Pigment composition and dispersion of pigment - Google Patents

Abstract

PURPOSE:To obtain a pigment compsn. with excellent non aggregating and flow properties by incorporating each a specified amt. of diketopyrrolopyrrole pigment and a specified quinacridone deriv. CONSTITUTION:A composition comprising 100 pts.wt. diketopyrrolopyrrole pigment (e.g. a compd. of formula I) and 3-30 pts.wt. quinacridone deriv. of formula II [wherein Q is a quinacridone residue; n is 1-10; R3 and R4 are each a (substd.) alkyl, an aryl or a (substd.) N, O or S-contg. heterocyclic ring (except for piperazine); p is 1-4].

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a diketopyrrolopyrrole pigment composition that is suitable for use, particularly excellent in non-agglomeration and fluidity, and a dispersion method.

(Prior Art) Practically useful pigments that exhibit clear color tone and high coloring power in various coating or ink compositions generally consist of fine particles. However, fine particles of pigments make it difficult to obtain stable dispersions when dispersed in non-aqueous vehicles such as offset inks, gravure inks and paints, which has a significant impact on manufacturing operations and the value of the resulting products. It is known to cause various problems.

For example, dispersions containing pigments consisting of fine particles often exhibit high viscosities that make it difficult to remove the product from the disperser.

Not only is transportation difficult, but in worse cases, gelation may occur during storage, making it difficult to use. Furthermore, when different types of pigments are mixed and used, color separation due to agglomeration or decrease in sedimentation may result in color unevenness or a significant decrease in coloring power in the spread product. Furthermore, the gloss of the paint film surface of the color exhibit decreases.

Condition defects such as poor leveling may occur.

In addition, although not directly related to the dispersion of pigments, some organic pigments exhibit a decrease accompanied by changes in the crystalline state of the pigments; i.e., they are energetically unstable in non-aqueous vehicles such as offset inks, gravure inks, and paints. Since the crystal particles of the pigment change their size and shape and shift to a stable state, the product value may be impaired due to significant changes in hue, decrease in coloring power, generation of coarse particles, etc. in the developed product.

In order to solve the various problems mentioned above, many proposals have been made so far, centering on copper phthalocyanine and quinacridone pigments.

The content can be broadly divided into the following two categories based on technical methods.

Act 1 is USP 3370971 and USP 29655
As seen in Publication No. 11, the surface of pigment particles is coated with a colorless compound such as silicon oxide, aluminum oxide, and tertiary butylbenzoic acid.

The second method is Japanese Patent Publication No. 41-2466 and USP2B
As typified by Japanese Patent No. 55403, this is a method of mixing a compound obtained by using an organic pigment as a parent skeleton and introducing substituents such as a sulfone group, a sulfonamide group, an aminomethyl group, or a phthalimidomethyl group into the side chain.

Compared to the first method, the second method has a significantly greater effect on pigment disaggregation, crystal stability, etc. in a non-aqueous vehicle, and is also very advantageous judging from the ease of manufacturing the pigment composition. It's a method.

Currently, very few compounds are known that are effective against diketopyrrolopyrrole pigments.

For diketopyrrolopyrrole pigments, JP-A-62-2
A composition disclosed in Japanese Patent No. 95966 is known. In the field of pigments, the question is whether two dispersion aids are effective or not.

Although it will not be known until further experimentation is carried out, the combined use of phthalimidomethyl derivatives of quinacridone is not necessarily effective.

(Problems to be Solved by the Invention) The present invention provides a stable dispersion with excellent non-aggregation properties and fluidity when producing off-cent inks, gravure inks, paints, etc. made of diketopyrrolopyrrole pigments. The present invention provides a pigment composition and a method for dispersing the pigment.

[Structure of the invention]

(Means for Solving the Problems) The present invention provides 0.0 parts by weight of a quinacridone derivative represented by formula CI) per 100 parts by weight of a diketopyrrolopyrrole pigment.
The present invention relates to a pigment composition and dispersion method using 3 to 30 parts by weight.

Diketopyrrolopyrrole pigments are compounds of formula (II). These compounds are described in U.S. Pat.
．． No. 685, European Patent Application Publication No. 133.1
No. 56 or Japanese Patent Publication No. 11(A) No. 61-12
0861.61-183363.62-149759 and the like.

B (The symbols in the formula are the same as above.) The two quinacridone derivatives according to the present invention are of the formula (I)
This is a compound represented by

(The symbols in the formula are the same as above.) The compound represented by formula (I) can be obtained by first chloroalkylating a quinacridone compound by a conventional method, then reacting the obtained chloroalkylquinacridone with an amine. Can be manufactured. The solvent used for the reaction between chloroalkylquinacridone and amines is water, methanol, or ethanol.

Propyl alcohol, isopropyl alcohol, acetone, dioxane, N,N-dimethylformamide, N-
General organic solvents such as methyl-2-pyrrolidine, dimethyl sulfoxide, cyclohexane, toluene, and xylene can be used, but it is also possible to use the amines as the two reaction components as they are as a solvent. In addition, sodium hydroxide, sodium carbonate,
Basic compounds such as potassium hydroxide, potassium carbonate, triethylamine, pyridine, and p-dimethylaminopyridine may also be used in combination.

In addition, examples of amines include dimethylamine,
Diethylamine, N-ethylisopropylamine, N-
Ethylpropylamine, N-methylbutylamine, N-
Methylisobutylamine, N-butylethylamine,
N-tart-butylethylamine.

Diisopropylamine, dipropylamine, N-5eC
-butylpropylamine, dibutylamine, di-5ec
-butylamine, diisobutylamine, N-isobutyl-3eC-butylamine, cyamylamine.

Diisoamylamine 2 Diallylamine, di(2-ethylhexyl)amine, dioctylamine, N-methyloctadecylamine, didecylamine, diallylamine,
N-ethyl-1,2-dimethylpropylamine, N-methylhexylamine, 2-hydroxymethylaminoethanol, dioleylamine.

Distearylamine, piperidine, 2-pipecoline.

3-pipecoline, 4-pipecoline, 2,4-rubetidine, 2,6-lupetidine, 3,5-rubetidine.

Examples include 3-piperidine methanol, pipecolic acid, isonipecotic acid, methyl isonicopetate, ethyl isonicopetate, 2-pyheridine ethanol, pyrrolidine, and 3-hydroxypyrrolidine.

The quinacridone derivative obtained in the present invention is blended into the diketopyrrolohyrol pigment based on 100 parts by weight of the pigment.
0.3 to 30 parts by weight is preferred. If it is less than 0.3 parts by weight, the effect of the pigment dispersant obtained in the present invention cannot be obtained, and even if it is more than 30 parts by weight, the effect of the amount used cannot be obtained.

There are 9 methods for using the quinacridone derivatives according to the present invention, for example, as follows.

1. A pigment composition obtained by pre-mixing a pigment and a quinacridone derivative is added to a non-aqueous vehicle and dispersed.

2. The pigment and the quinacridone derivative are separately dispersed in advance in a non-aqueous vehicle, and the resulting dispersion is mixed.

3. The pigment and the quinacridone derivative are separately dispersed in advance in a non-aqueous vehicle, and the resulting dispersion is mixed.

In this case, the quinacridone derivative may be dispersed using only a solvent.

4. After dispersing the pigment in a non-aqueous vehicle or the like, a quinacridone derivative is added to the resulting dispersion.

etc., and any of these can achieve the desired effect.

As for the preparation method of the pigment composition shown in 1 above, the desired effect can be sufficiently obtained by simply mixing the pigment powder and the powder of the quinacridone derivative related to the present invention.

Kniter, roll, attritor, super mill.

The quinacridone derivative is deposited on the surface of the pigment by mechanically mixing it with various types of pulverizers, or by adding a solution containing the quinacridone derivative according to the present invention to a suspension system of the pigment in water or an organic solvent. Even better results can be obtained by performing an intimate mixing method such as co-dissolving the pigment and quinacridone derivative in a strong solvent and co-precipitating with a poor solvent such as water.

Further, as shown in 2 to 4 above. In the use of pigments and quinacridone derivatives, dispersion of the pigment or quinacridone derivative in a non-aqueous vehicle or solvent.

Good dispersion of the pigment can be achieved by using a daysilver, high-speed mixer, homomixer, kneader, roll mill, sand mill, attritor, etc. as a dispersion machine for these mixing operations.

Vehicles used include lime rosin varnish, gravure ink such as polyamide resin face or vinyl chloride resin face, nitrocellulose lacquer, air-drying or baking paint of amino alkyd resin.

Acrylic lacquer and amino acrylic resin baking are paints.

There are non-aqueous vehicles such as urethane resin paints.

〔Effect of the invention〕

According to the present invention, compared to the case where a diketopyrrolopyrrole pigment is used alone, the dispersion exhibits good fluidity such as lower viscosity and lower structural viscosity, and at the same time, problems such as color separation and crystal changes are avoided. Therefore, it is possible to obtain a beautiful product with good gloss of the printed matter or coating film.

In particular, one quinacridone i-form related to the present invention.

It has an extremely excellent dispersion effect not only in oil-modified amino alkyd resin paints but also in oil-free alkyd resin paints.

The use of quinacridone derivatives according to the present invention is not limited to non-aqueous vehicles, but also other printing inks and paints,
Even when it comes to coloring plastics.

A colored product with excellent dispersion effect and 2 coloring power can be obtained.

The outline of the method for synthesizing quinacridone i-isomer according to the present invention is shown below as a production example.
” means “parts by weight” or “% by weight”, and the numbers of the quinacridone derivatives correspond to the abbreviations shown in Table-1.

[Production Example 1] A compound represented by the formula (I
It was dispersed into several departments. Next, 56 parts of diethylamine was added to give 7
The temperature was raised to 0°C, and stirring was performed at the same temperature for 5 hours. The precipitate was filtered, washed with water, and dried at 70°C to obtain pigment dispersant (1) 5.
I got 8 copies.

[Production Example 2] The compound represented by formula (IV) was chloromethylated by a conventional method, and 50 parts of the obtained compound was dispersed in 1000 parts of water. Next, 40 parts of piperidine was added, the temperature was raised to 100°C, and stirring was performed at the same temperature for 3 hours. The precipitate was filtered, washed with water, and dried at 70°C to obtain 54 parts of pigment dispersant (8).

The pigment dispersant according to the present invention can be synthesized by the same method as in Production Examples 1 and 2. Some examples are shown in Table 1.

Note that "Ql" in Table 2-1 represents the skeletal structure of the compound represented by formula (II[), and rQ2J represents the skeletal structure of the compound represented by formula (rV).

Table-1 Structures and abbreviations of quinacridone derivatives
1 to 1 to 2 cH2N (CH2CH=CH2)2 Incidentally, quinacridone derivative 12 shows a comparative example.

In order to evaluate the dispersion effect of the quinacridone derivative obtained in the present invention, 5% of the quinacridone derivative was added to the diketopyrrolopyrrole pigment represented by the following formula (V) to prepare a paint with the following formulation. did.

Formulation (1) Pigment 9.5 parts Pigment dispersant 0.5 parts Alkyd resin face (60% non-volatile content) 26.4 parts Melamine resin face (50% non-volatile content) 13.6 parts Thinner 20 parts (xylene/
n-Butanol-8/2) Mixing phase added after dispersion
48.3 parts (alkyd/melamine-773
(Solid content)) Blend (2) Pigment: 9.5 parts Pigment dispersant: 0.5 parts Oil-free polyester resin face 26.4 parts (non-volatile content: 60%) Melamine resin-based varnish (non-volatile content: 50%) 13.6 parts Mixing face to be added after 20 parts Swazol 48.3 parts (alkyd/melamine = 7/3 (solid content)) Place the above mixture in a container, add a steel ball and disperse with a paint shaker, Created paint. These paints
A comparison was made with a paint to which no pigment dispersant was added (a paint in which no pigment dispersant was added in the above formulation and the pigment was 10 parts) according to the evaluation method below. Table 2 shows an example of the results. In addition.

The numbers of the pigment dispersants in Table-2 correspond to the abbreviations shown in Table-1.

Evaluation method (1) The viscosity of the obtained paint was determined by measuring it with a B-type viscometer (measurement temperature: 25°C). The evaluation was made by relative comparison with a paint without the addition of a pigment dispersant, and those with lower viscosity were evaluated as good.

○: Good Δ: Fairly good ×: Poor Evaluation method (2) The obtained paint has a final paint viscosity of 23 in Ford Cup 4.
After temporarily spraying the tin plate with an air spray gun and baking it, the overall sharpness of the coated surface was evaluated visually and by measuring 20° gloss with a gloss meter.

0, f Δ: Good ×: Poor When the viscosity of these paints was measured using the same viscometer after being left for one week, almost no increase in viscosity was observed. In addition, a 1/10 cut light color paint was made using white paint adjusted with titanium white, the viscosity was adjusted to 23 seconds using Ford Cup 4, and the state of agglomeration was observed in a test tube. No separation or sedimentation was observed.

Furthermore, the pigments to which the three pigment dispersants according to the present invention were added showed good dispersibility without causing aggregation even in nitrocellulose lacquers, acrylic resin paints, and gravure inks.

(1) (2) 1990 model month 1

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a diketopyrrolopyrrole pigment and 0.0 parts by weight of a quinacridone derivative represented by the following general formula (I). A pigment composition comprising 3 to 30 parts by weight. Formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Q represents a quinacridone residue, and n is 1 to 10
R_3R_4 each independently represents an optionally substituted saturated or unsaturated alkyl group or aryl group, or R_3, R_4 represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom; (Except when the heterocycle is a piperazine ring.)
, P represents an integer from 1 to 4. 2. The pigment composition according to claim 1, wherein the diketopyrrolopyrrole pigment is one or a mixture of two or more compounds having different structures represented by formula (II). Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents an oxygen or sulfur atom, and A and B may be the same or different from each other. , represents a cycloalkyl, aryl or carbocyclic or heterocyclic aromatic residue;
R_1 and R_2 represent a hydrogen atom, an unsubstituted or substituted alkyl residue, and an alkenyl, alkynyl, aralkyl, cycloalkyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl, alkoxycarbonyl, aryl, alkanoyl or aroyl group. 3. A method for dispersing the diketopyrrolopyrrole pigment in a vehicle, which comprises using 0.3 to 30 parts by weight of the quinacridone derivative according to claim 1 per 100 parts by weight of the diketopyrrolopyrrole pigment.