JPH05117541A - Pigment composition and pigment dispersion - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a pigment dispersion in which the fluidity of a high concentration pigment dispersion and the critical temperature of fluidity are increased. A pigment derivative obtained by mixing 100 parts by weight of the pigment and a pigment derivative of the general formula (1) having a tertiary alkylamino group, for example, the formula (2), with a (poly) oxyalkylene alkyl ether sulfosuccinate sodium salt. A pigment composition comprising 0.1 to 30 parts by weight of a pigment dispersant comprising the compound, and a pigment dispersion prepared by dispersing the pigment composition in a dispersion vehicle. P- ^{_{[X- (CH 2) k -N (}} R 1, R 2) ] _m
(1) (P is azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, anthrapyrimidine, ansanthrone, indanthrone, flavanthrone, pyranthrone, perylene, perinone, thioindigo, (At least one organic dye residue selected from diketopyrrolopyrrole, isoindolinone, isoindoline, and quinophthalone)

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment composition and a pigment dispersion having excellent fluidity in a dispersion pigment vehicle having a high pigment concentration, and particularly excellent fluidity in a state of being heated during a dispersion process.

[0002]

2. Description of the Related Art In general, in order to exert a vivid color tone and high tinting strength in various coatings or ink compositions, it is necessary to miniaturize the pigment dispersion vehicle. In this dispersion step, dispersion is generally carried out at a high pigment concentration in order to improve production efficiency, and then various vehicles and solvents are mixed to prepare a printing ink or paint.

Generally, the fluidity of a dispersion having a high pigment concentration is temperature-dependent, and the fluidity improves as the temperature rises. Therefore, dispersion at high temperature is advantageous in terms of production efficiency. However, a dispersion having a high pigment concentration has a critical temperature, and when it exceeds a certain temperature, the dispersion loses fluidity, and even if it is heated, the fluidity does not increase, and on the contrary, a phenomenon occurs. This critical temperature is around 50 to 90 ° C., which is the same as the dispersion temperature during the dispersion process. Therefore, the dispersion of high pigment concentration above the critical temperature is not only a poor dispersion but also the removal from the disperser,
Transport becomes difficult, and a dispersion having a high pigment concentration cannot be obtained, which hinders improvement in production efficiency. This phenomenon remarkably appears in the high pigment concentration dispersion of the offset ink,
The same applies to gravure ink and paint. Further, if the pigment dispersion prepared as a product also has poor fluidity, it may cause deterioration in gloss and poor printability.

In order to solve various problems as described above, Japanese Patent Publication No. 58-28303 and Japanese Patent Publication No. 59-4 have been published so far.
As typified by JP-A No. 1172, fluidity is improved by a method of mixing a compound obtained by introducing a substituent such as a sulfonamide group or an aminomethyl group into a side chain with an organic pigment as a base skeleton. However, the offset ink has almost no effect because the organic solvent content is small. Further, JP-A-63-363 describes a method of mixing a compound obtained by introducing a substituent of a polymer resin into a side chain, but the effect of improving fluidity in a high pigment concentration dispersion is not described. It is sufficient and has no effect of raising the critical temperature. Furthermore, JP-A-2-305861 describes a method of mixing a compound obtained by introducing an alkylene oxide addition product of a phosphoric acid ester into a side chain, but the critical temperature does not change,
It has no effect on the fluidity at the dispersion process temperature.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a pigment dispersion in which the above-mentioned various drawbacks are improved and the fluidity of a high-concentration pigment dispersion and the critical temperature of fluidity are increased.

[0006]

According to the present invention, 100 parts by weight of a pigment and a pigment derivative represented by the following general formula (1) are mixed with (poly) oxyalkylene alkyl ether sulfosuccinate sodium salt. It relates to a pigment composition comprising 0.1 to 30 parts by weight of a pigment dispersant comprising the obtained compound. Equation (1) P- _{[X- (CH 2) k -N (} R 1, R 2) ] _m (wherein, P is an azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, anthrapyrimidine, At least one organic pigment selected from anthanthrone, indanthrone, flavanthrone, pyranthrone, perylene, perinone, thioindigo, diketopyrrolopyrrole, isoindolinone, isoindoline, quinophthalone A residue, X is a direct bond or a divalent bonding group, R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group,
Alternatively, R ¹ and R ² each represent a heterocycle which may contain a nitrogen atom or an oxygen atom, k is an integer of 1 to 4, and m is an integer of 1 to 4, respectively. )

The pigments of the present invention include phthalocyanine pigments, insoluble azo pigments, disazo pigments, azo lakes, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavans. There are organic pigments such as threon pigment, perylene pigment, perinone pigment, and thioindigo pigment, and inorganic pigments such as carbon black.

The pigment derivative represented by the formula (1) of the present invention is disclosed in JP-A-51-34235, JP-B-58-28303, and JP-B-59-4.
0172, JP-A-58-167654, JP-A-59-168070, JP-B-63-20869, JP-B-58-28303, JP-B1-34268 and JP-B1-34269. Is known,
Organic dyes include azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, anthrapyrimidine, ansanthrone, indanthrone, flavanthrone, pyranthrone, perylene, perinone, thioindigo, diketopyrrolo. It is at least one selected from pyrrole-based, isoindolinone-based, isoindoline-based, and quinophthalone-based. X may be a direct bond or a divalent linking group. The divalent linking group _{-CH 2 NH -, - SO 2} NH -, - CH 2
_{NHCO -, - CH 2 NHCOCH 2} NH -, - CON
H- and the like are preferable. The following are specific examples of the pigment derivative.

P-CH ₂ N (CH ₃ ) ₂ P-CH ₂ N (C ₂ H ₅ ) ₂ P-CH ₂ N (C ₃ H ₇ ) ₂ P-CH ₂ N (C ₄ H ₉ ) ₂

[Chemical 1]

[Chemical 2] _{P-CH 2 NH (CH 2} ) 2 N (C 2 H 5) 2 P-CH 2 NH (CH 2) 3 N (CH 3) 2 P-CH 2 NH (CH 2) 3 N (C 2 H 5 _{) 2 P-CH 2 NH (} CH 2) 4 N (C 2 H 5) 2 P-SO 2 NH (CH 2) 2 N (CH 3) 2 P-SO 2 NH (CH 2) 2 N (C 2 _{H 5) 2 P-SO 2} NH (CH 2) 3 N (CH 3) 2 P-SO 2 NH (CH 2) 3 N (C 2 H 5) 2 P-SO 2 NH (CH 2) 3 N ( C ₄ H ₉ ) ₂

[Chemical 3]

[Chemical 4]

[Chemical 5] _{P-CH 2 NHCO (CH 2} ) 2 N (CH 3) 2 P-CH 2 NHCO (CH 2) 2 N (C 2 H 5) 2 P-CH 2 NHCO (CH 2) 3 N (CH 3) 2 _{P-CH 2 NHCO (CH 2} ) 3 N (C 2 H 5) 2 P-CH 2 NHCOCH 2 NH (CH 2) 2 N (C
_{H 3) 2 P-CH 2} NHCOCH 2 NH (CH 2) 3 N (C
_{H 3) 2 P-CH 2} NHCOCH 2 NH (CH 2) 3 N (C 2 H
₅ ) ₂ P-CH ₂ NHCOCH ₂ NH (CH ₂ ) ₃ N (C ₄ H
_{9) 2 P-CH 2 CONHCH} 2 N (CH 3) 2 P-CH 2 CONH (CH 2) 2 N (CH 3) 2 P-CH 2 CONH (CH 2) 3 N (CH 3) 2 P-CH ₂ CONH (CH ₂ ) ₄ N (CH ₃ ) ₂ The pigment derivative may be a 2 to 4 substituent.

The (poly) oxyalkylene alkyl ether sulfosuccinate sodium salt of the present invention is represented by the following general formula (2). Equation ^{(2) R 3 O (R} 4 O) n OC-CH (CH 2 COONa) -SO 3 Na ( wherein, R ³ is an alkyl group or an alkylaryl group having 8 to 22 carbon atoms, R ⁴ is the number of carbon atoms 2 or 3 alkylene groups may be used alone or mixed, and n is an integer of 1 to 30, preferably an integer of 2 to 20.)

In the pigment dispersant of the present invention, a pigment derivative is made into an acidic aqueous solution with a mineral acid such as acetic acid, hydrochloric acid or sulfuric acid, preferably acetic acid, and then sodium salt of polyoxyalkylene alkyl ether sulfosuccinate is added and mixed, Stir and adjust by salt formation reaction. The salt-forming reaction is instantly completed at a reaction temperature of 0 to 100 ° C. After the salt formation reaction is completed, p
A pigment dispersant paste is obtained by adjusting H to around neutral, and filtering and washing with water. The pigment dispersant may be used in the form of paste as it is, or may be used in the form of powder by drying and pulverizing.

The amount of the (poly) oxyalkylene alkyl ether sulfosuccinate sodium salt added to the pigment derivative is 40 to 100 parts by weight of the pigment derivative.
150 parts is preferred. If it is less than 40 parts by weight, only the effect of the pigment derivative can be obtained, and the effect of the pigment dispersant according to the present invention cannot be obtained. If more than 150 parts by weight (poly)
Not only the effect of the pigment dispersant according to the present invention cannot be obtained because the sodium salt of oxyalkylene alkyl ether sulfosuccinate becomes excessive, but also the interfacial tension of the pigment dispersion is lowered, and thus the printability with an offset ink is reduced. The composition of the pigment dispersant to the pigment is pigment 10
0.1 to 30 parts by weight is preferable with respect to 0 parts by weight. 0.
If it is less than 1 part by weight, the effect of the pigment dispersant according to the present invention cannot be obtained, and if it is used in excess of 30 parts by weight, the effect of the used amount cannot be obtained and the coloring power is lowered, which is not preferable.

As a method for preparing the pigment composition, the desired effect can be obtained by simply mixing the pigment powder and the powder of the pigment dispersant of the present invention. However, kneaders, roll mills, attritors, supermills, various types, etc. Mechanically mixing with a pulverizer or the like, or adding a solution containing the pigment dispersant of the present invention to a suspension system of pigment water or an organic solvent to deposit the pigment dispersant on the pigment surface, an organic solvent or sulfuric acid. Even better results can be obtained by performing a close mixing method such as co-dissolving the pigment and the pigment dispersant in a solvent having a strong dissolving power such as and coprecipitating with a poor solvent such as water.

As a method for preparing a pigment dispersion, a pigment composition is dispersed in a dispersion vehicle or the like at a high pigment concentration, and then various vehicles and solvents are mixed to prepare a printing ink or paint. By using a dissolver, a high speed mixer, a homomixer, a sand mill, a roll mill, an attritor, a kneader or the like as a disperser, the pigment can be well dispersed. In the dispersion method, the powdery pigment composition is used for dispersion, but the drying step may be omitted and the pastey pigment composition may be directly dispersed by flushing.

In the present invention, the above pigment dispersion is applied and includes a paint and a printing ink. The offset ink comprises 3 to 40% by weight of the pigment composition of the present invention, 45 to 97% by weight of the vehicle for offset ink, and 0 to 20% by weight of other auxiliary agents and extender pigments. The vehicle for offset ink is rosin-modified phenol. Resin, petroleum resin, alkyd resin, or these dry oil modified resins, etc.
50% by weight and vegetable oil such as linseed oil, tung oil, soybean oil 0
~ 30% by weight, solvent such as n-paraffin, isoparaffin, aromatech, naphthene, α-olefin 10
It is composed of 60% by weight.

The coating composition comprises 3 to 40% by weight of the pigment composition of the present invention, 97 to 55% by weight of the vehicle for coating, and 0 to 30% by weight of other auxiliary agents and extender pigments. The vehicle resin for coating is an acrylic resin, Alkyd resin, epoxy resin, chlorinated rubber resin, vinyl chloride resin, silicone resin, fluororesin, polyurethane resin, polyester resin, melamine resin, urea resin or a mixture thereof 20 to 80% by weight
And a solvent such as hydrocarbon, alcohol, ketone, ether alcohol, ether or ester in an amount of 10 to 60% by weight.

In the gravure ink, the pigment composition of the present invention is 3 to 40% by weight, and the vehicle for gravure ink is 60 to 97.
The gravure ink vehicle comprises rosin such as gum rosin and lime rosin, maleic acid resin, polyamide resin, vinyl resin, nitrocellulose, ethylene-vinyl acetate Consists of 10 to 50% by weight of a resin mixture such as polymerized resin, polyurethane resin, polyester resin, alkyd resin, gilsonite, dammar and shellac, and 30 to 80% by weight of a solvent such as hydrocarbon, alcohol, ketone, ether alcohol, ether and ester. It is a thing.

[0018]

The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. Production Examples 1 to 13 Table 1 shows production examples of the pigment dispersant according to the present invention. As the pigment dispersant, 100 parts of the pigment derivative was dissolved in 1000 parts of 5% acetic acid aqueous solution, and sodium salt of polyoxyalkylene alkyl ether sulfosuccinate was added at room temperature to carry out a salt forming reaction. After the addition, the pH was adjusted to 7 and the slurry was added dropwise to the filter paper to confirm that the reaction was complete because there was no bleed, and the slurry was heated to 70 ° C., stirred for 30 minutes, filtered, washed with water, and dried. Then, a pigment dispersant was obtained. The pigment composition was produced by mixing a pigment with a pigment dispersant having an organic dye residue having a structure similar to that of the pigment.

[0019]

[Table 1]

Examples 1 to 6 and Comparative Examples 1 to 4 Table 2 shows Examples and Comparative Examples of the pigment composition according to the present invention and the high pigment concentration dispersion (base ink) in the offset ink. In the pigment dispersion, a base ink was prepared by dispersing an offset ink having the following composition using a sand mill until the particle diameter became 10 μm or less. Blended pigment composition 15 parts Rosin-modified phenolic resin varnish 35 parts Flowability was evaluated using a spread meter at a flow rate (60 seconds value (diameter)) and slope (100 seconds value-10 seconds value) in measurement at 80 ° C. I went in search of. The larger the number, the better the fluidity.

[0021]

[Table 2]

As is clear from Table 2, the fluidity of the pigment dispersion having a high pigment concentration as the base ink is superior to that of the comparative example in the pigment composition or the pigment dispersion according to the present invention. ..

FIG. 1 shows Example 1 (◯) and Comparative Example 1 (Δ),
The effect of temperature on the fluidity of the high pigment concentration dispersion of Comparative Example 2 (□) is shown. As is clear from FIG. 1, the critical temperature of Comparative Examples 1 and 2 is 60 ° C., and the slope is remarkably lowered at higher temperatures, but in Example 1, the slope is increased even at 80 ° C. and the critical temperature is recognized. In other words, it shows excellent fluidity.

Examples 7 to 15 Table 3 shows examples of high pigment concentration dispersions (base paints) in paints of pigment compositions and pigment dispersions according to the present invention. The pigment dispersion was prepared by dispersing a paint having the following composition using a sand mill until the particle diameter became 10 μm or less, and adjusting the base of the baking type paint. Blended pigment composition 30 parts Alkyd resin varnish 25 parts Xylene 45 parts The fluidity was evaluated using a B-type viscometer at 6 rpm value and TI value (6 rpm value / 60 rpm value) at 60 ° C.
I went in search of. The smaller the number, the better the fluidity.

[0025]

[Table 3]

As is clear from Table 3, the fluidity of the pigment dispersion having a high pigment concentration as the base paint is superior to the comparative example in the pigment composition or the pigment dispersion according to the present invention. ..

Examples 16 to 18 Table 4 shows examples of the high pigment concentration dispersion (base ink) in the gravure ink of the pigment composition and the pigment dispersion according to the present invention. For the pigment dispersion, a gravure ink having the following composition was dispersed using a sand mill until the particle diameter became 10 μm or less, to prepare a base ink. Blended pigment composition 30 parts Nitrocellulose varnish 20 parts Ethyl acetate 50 parts The fluidity was evaluated using a B-type viscometer at 6 rpm value and TI value (6 rpm value / 60 rpm value) measured at 60 ° C.
I went in search of. The smaller the number, the better the fluidity.

[0028]

[Table 4]

As is clear from Table 4, the fluidity of the pigment dispersion having a high pigment concentration as the base ink is superior to that of the comparative example in the pigment composition or the pigment dispersion according to the present invention. ..

[0030]

INDUSTRIAL APPLICABILITY The pigment composition according to the present invention and the pigment dispersion using the same are compared with the case where the pigment is used alone or the conventional pigment derivative is blended and used.
It shows good fluidity in pigment dispersions with high pigment concentrations. In particular, the offset ink has excellent fluidity at high temperatures, and by increasing the critical temperature, it exhibits an excellent effect of improving production efficiency.

[0031]

[Brief description of drawings]

FIG. 1 is a graph showing the influence of temperature on the fluidity of a high pigment concentration dispersion.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C09B 67/20 K 7306-4H C09C 3/08 PBU 6904-4J PBV 6904-4J 3/10 PCD 6904-4J

Claims (2)

[Claims] 1. A pigment dispersant comprising 100 parts by weight of a pigment and a compound obtained by mixing a pigment derivative represented by the following general formula (1) with a sodium salt of (poly) oxyalkylene alkyl ether sulfosuccinate. 0.
A pigment composition comprising 1 to 30 parts by weight. Equation (1) P- _{[X- (CH 2) k -N (} R 1, R 2) ] _m (wherein, P is an azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, anthrapyrimidine, At least one organic pigment selected from anthanthrone, indanthrone, flavanthrone, pyranthrone, perylene, perinone, thioindigo, diketopyrrolopyrrole, isoindolinone, isoindoline, quinophthalone A residue, X is a direct bond or a divalent bonding group, R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group,
Alternatively, R ¹ and R ² each represent a heterocycle which may contain a nitrogen atom or an oxygen atom, k is an integer of 1 to 4, and m is an integer of 1 to 4, respectively. ) 2. A pigment dispersion comprising the pigment composition of claim 1 and a dispersion vehicle.