JPH08217986A - Pigment composition - Google Patents

Abstract

PURPOSE: To increase the pigment concentration and improve the flowability by using a specified compound, an alkenylsuccinimide dispersant and an organic pigment as the constituents. CONSTITUTION: Benzoic acid, naphthoic acid, β-oxynaphthoic acid, phthalic acid, isophthalic acid or terephthalic acid and a 1-8C alkyl alcohol are esterified to give a compound having an acidic group such as a carboxyl or sulfonic group in the molecule and containing an aromatic ring in the molecular structure. 0.5-20wt.% of this compound is blended with 0.5-20wt.% dispersant comprising an alkenylsuccinimide of a molecular weight of 400 to 3,000 and 99-60wt.% organic pigment selected from pigments of phthalocyanie, quinacridone, azo, lake, anthracene, perylene, condensed azo, isoindolinone and dioxane.

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 more specifically, to provide a novel pigment composition useful as a pigment for printing ink, a pigment for gravure ink, a pigment for paint, etc. To do.

[0002]

2. Description of the Related Art Pigment dispersion technology has made remarkable progress in recent years, and in the coating industry and ink industry, a method of dispersing the pigment by increasing the pigment concentration as much as possible is more and more adopted for the purpose of streamlining the production. It became like. Along with this, the problem regarding the fluidity of the pigment dispersion at the time of dispersing or taking out the pigment has come to the forefront. In particular, organic pigments (particularly insoluble azo pigments) have a difficulty in fluidity and tend to be a dispersion exhibiting a plastic flow with a high yield value, and therefore various improvement measures have been taken.

First, (1) a method of providing a protective film (barrier) on the surface of the pigment with an amine-based treating agent, or (2) a polar group (-SO ₃ H, -COOH) during pigment synthesis. , Etc.) to introduce a small amount of a derivative of a diazo compound or a coupling component, which controls the crystal growth, and imparts an appropriate hydrophilicity to the pigment crystal surface to make an effort to modify the crystal surface. It is being appreciated. As an example of the former, there is known a method of applying a chain-like diamine as described in British Patent 1,096,362 (1967) to a pigment. Further, as the latter example, many methods described in JP-B-55-49087 and JP-B-58-25698 are presented.

[0004]

However, any of the pigments produced by these methods has high transparency when used in paints and inks, and the pigment particles become small, so that the fluidity efficiency is lowered and the pigment is not sufficiently treated. Often ineffective. In particular, in the use of inks and paints that require hiding power, they do not meet the purpose immediately. Also, a method of applying a chain diamine, that is, B.I. P. In the method according to the specification of 1,096,362, it has been pointed out that when the obtained pigment is used in a lithographic ink, the emulsification rate of the pigment becomes abnormally high, which causes an adverse effect of water loss during printing. . Other,
Apart from the pigment treatment, in the process of preparing the ink
There have been many studies in recent years to mix hyper dispersants (dispersants with outstanding performance) to make pigment dispersions with extremely high pigment concentration and high fluidity.

As a typical example of this hyper dispersant, so
There are various products under the trade name of lsperese (ICI), but these products have different effects depending on the pigments and applications used, and it is difficult to select these dispersants and it is too complicated. Further, as such a usage, an alkenyl succinimide dispersant is found in an example used for a carbon black ink, but these are limited to black ink containing asphalt. Furthermore,
When the above method was applied to an organic pigment, it was found that the obtained ink had a serious defect in printability.

That is, a pigment having a high concentration is mixed with a hyper dispersant and dispersed efficiently, and the resulting dispersion having excellent fluidity has an extremely high viscosity during the dilution process with a solvent during ink preparation. If you go down and press the machine,
Misting is likely to occur, and ink tends to adhere to the non-image area of the printing plate (greasing). Also, in the use in publishing gravure ink,
It is not preferable that the printed matter on the Henry paper shows the phenomenon of strike-through (print-through). Therefore, an object of the present invention is to provide a novel pigment composition which is useful for various applications such as a pigment for printing ink, a pigment for gravure ink, a pigment for paint and the like.

[0007]

The above object can be achieved by the present invention described below. That is, the present invention relates to a compound (I) having an acidic group such as carboxylic acid or sulfonic acid in the molecule and containing an aromatic ring in its constituent molecule, an alkenyl succinimide dispersant (II) and an organic pigment. And a pigment composition.

[0008]

By treating the organic pigment with the compound (I) and the dispersant (II), a novel pigment composition useful for various purposes, for example, a pigment for printing ink, a pigment for gravure ink, a pigment for paint, etc. Can be provided.

The operation of the present invention will be described in more detail.
First, the vehicle used for lithographic ink is usually rosin-modified phenolic resin or rosin-modified maleic acid resin,
Alternatively, rosin-modified alkyd resins and the like, all of which are resins having a certain acid value. In addition, for inks for light plastic packaging materials printed by the gravure method, inks using polyamide-digested cotton or alkyd-digested cotton as a vehicle have been used for a long time. Both of these polyamide and alkyd resins have a certain acid value.

The conditions for the pigments to be dispersed in these vehicles are as follows. The first condition is that the acid value, which is a characteristic of the vehicle, is not impaired. As a second condition, it is important to prevent the formation of a structure, which is a connection between particles, by preventing the crystals of the pigment particles from electrically repelling each other in these vehicles and preventing the dispersed particles from approaching each other. is there. The pigment composition of the present invention is set so as to sufficiently satisfy the first and second conditions. Of these, the first condition is that the compound (I) that constitutes the pigment composition of the present invention satisfies this condition, and the second condition is that the alkenyl succinimide of the dispersant (II) is used. A system dispersant corresponds to this.

The chemical structure of the alkenyl succinimide dispersant is R ₁ : alkenyl group R ₂ : aliphatic ester group R ₃ : aliphatic ester group, and the -CONR- imide group having basic properties shows good adsorption to a pigment having an acidic group. And shows C = in the structure of succinic acid after being adsorbed on the pigment crystal surface.
The O group acts as a strong polarity toward the outside to give an electric repulsion property to the pigment crystal surface.

On the other hand, the role of the compound (I) is that it is adsorbed on the surface of a non-polar pigment crystal and its free acidic group (C
OOH, SO ₃ H) facilitates adsorption of the imide group of the dispersant (II), whereby the composition of the compound (I) and the dispersant (II) complements each other on the pigment crystal surface. It is thought that it will fully function in the relationship of. or,
The alkenyl succinimide dispersant of the dispersant (II) is
Even when used alone, some good fluidity is obtained when using lithographic ink and gravure ink,
In this case, the alkenyl succinimide dispersant acts as a pigment aggregating agent, and as a result, the transparency and tinting strength of the pigment are impaired. In the present invention, by using this compound (I), it has been found that the effect of preventing this phenomenon is great.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The organic pigment applied in the present invention, an azo pigment, a phthalocyanine pigment, a quinacridone pigment, a perylene pigment, a condensed azo pigment,
Dyeing pigments, isoindolinone pigments, dioxazine pigments and the like can be mentioned, and the idea of the present invention can be applied to all organic pigments.

The compound (I) used in the present invention is
It refers to a compound having an aromatic ring and one or more carboxylic acid or sulfonic acid groups in the molecule, and includes derivatives obtained by modifying most of these acidic groups with alcohol or vegetable oil, but at least the molecule It is necessary to have one free acidic group in it.

More specifically, it is a compound obtained by the esterification reaction of benzoic acid, naphthoic acid, β-oxynaphthoic acid, or phthalic acid, isophthalic acid, or terephthalic acid with an alkyl alcohol having 1 to 8 carbon atoms. There
Alkyd resin that leaves free carboxyl group, further modified alkyd resin obtained by modifying vegetable oil or glycerin with phthalic acid described above, and free carboxyl group that is further polymerized by using pentaerythritol instead of glycerin. Includes alkyd resin and the like inside. Also included are compounds obtained by reacting acetoacet-2-carboxy-anilide, acetoacetanilide-4-sulfonic acid and the like with a diazo component.

Further, the alkenyl succinimide dispersant of the dispersant (II) means a chemical substance represented by the above formula (A), and the essential point in the production process thereof is an unsaturated bond or a functional group such as halogen. It is preferably produced by further reacting an alkenyl succinic anhydride obtained by the reaction of a polyolefin having a phthalic anhydride with phthalic anhydride. This polyolefin is a homopolymer or copolymer of an olefin having 2 to 5 carbon atoms and has a molecular weight of 400 to 3,0.
00.

Further, as the polyamine, the following formula Alkylene polyamines according to are preferred, where n is an integer of 10 or less, A and A ′ are hydrocarbon groups, hydrogen atoms,
It is an aminohydrocarbon group, and the alkylene group is preferably a lower alkylene group having a carbon number of 8 or less. Among these amines, particularly preferred are diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. . Examples of commercially available alkenyl succinimide dispersants represented by these include, for example, “OLOA-1200 manufactured by Chevron, USA” and “S-900 manufactured by Nidowin Cooper, USA”.

In order to treat the pigment with the compound (I) and the dispersant (II), usually, these are dissolved in a petroleum-based organic solvent, and the presence of a surfactant in the solution. Then, by pouring a large amount of water and stirring at high speed,
/ W type emulsion is prepared by injecting it into the pigment slurry to treat the pigment. Alternatively, if it is soluble in water, the compound (I) can be converted into a free acidic group as a sodium salt in water. It is also possible to dissolve or disperse the pigment to treat the pigment, and then acidify the pigment to adsorb the compound (I) onto the pigment surface.

Further, regarding the use ratio of the compound (I), the dispersant (II) and the organic pigment used in the present invention, earnest studies have been made on not only the dispersibility and fluidity but also the problem of printability. As a result of the examination, the weight ratio is 0.
Within the range of 5 to 20 / 0.5 to 20/99 to 60,
Particularly preferable results are obtained within the range of 2 to 10/2 to 10/94 to 80.

[0020]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified. Example 1 2-Methoxy-benzamino-5-N, N'-diethylamino-sulfonyl chloride (25.8 parts) was diazotized by a conventional method to obtain a diazonium salt. This is 2-
Hydroxyl-naphthalene-3-carboyl-5'-chloro-2 ', 4'-dimethoxyanilide (38 parts) was mixed and coupled with a base pickling agent prepared by a conventional method to obtain an unaged slurry of Pigment Red 5.

This was heated to 70 ° C., and 2.8 parts of a dry oil type alkyd resin (Beckosol 1307) and 2.8 parts of an alkenyl succinimide dispersant were added to xylol 8.
Dissolve in 4 parts to prepare an O / W type emulsion under 0.8 part of surfactant Neugen EA141 (Daiichi Kasei) and inject the emulsion into the pigment slurry to treat the pigment. . Furthermore, after boiling for 60 minutes,
Water was poured, and the mixture was filtered, washed with water, dried and pulverized by a conventional method to obtain 66 parts of Pigment Red 5 pigment.

This is then dried into a melamine-alkyd resin (Bekkosol 1307 / Super Beckamine J-8).
20 = solid ratio 2/1), 7.0 parts of pigment, 35 parts of the above resin and 8.0 parts of solvent are dispersed by a paint conditioner, and 30 parts of the above resin and 20 parts of the solvent are added to add 9 parts.
2 parts of normally dry red paint are obtained. When this paint was applied to coated paper with a 3 mil applicator and the hiding power was evaluated with a cryptometer, it had gloss and fluidity as compared with the pigment of Comparative Example 1 to which the present invention was not applied. It was confirmed that there was.

Table 1 Viscosity: B type viscometer used Gloss: Gloss meter (reflection angle 60 °) Beckol 1307: Dainippon Ink and Chemicals Super Beckamine J-820: Dainippon Ink and Chemicals

Example 2 100 parts of crude copper phthalocyanine was placed in a dry attritor and ground for 40 minutes. The resulting ground material 95
30 parts of butyl cellosolve and 200 parts of water are added to the parts, and the mixture is stirred at room temperature for 30 minutes. Further, the contents are heated to 90 ° C. and mixed by stirring for 4 hours. Then, the mixture is placed in a large amount of water and heat-treated with a 2% dilute sulfuric acid aqueous solution at 80 to 90 ° C. for 50 minutes.

Next, the obtained pigment cake is filtered and washed with water, peptized in 1,000 parts of water, and 3.0 parts of mono-sulfonated phthalocyanine is alkali-dissolved at room temperature and poured. Then, the temperature is raised to 60 ° C., and xylol emulsion liquid of alkenyl succinimide dispersant (5.0 parts of alkenyl succinimide dispersant is dissolved in 10 parts of xylol and 1.0 part of Neugen EA141 is added. And forcibly emulsify it in a large amount of water). According to a conventional method, this is filtered, washed with water, dried and ground to obtain 92 parts of the powdery pigment of the present invention.

Further, in order to confirm the performance of the pigment of Example 2, a simultaneous comparison test with that of the comparative example was conducted in the following manner. That is, 6.6 parts of pigment and 14 parts of sheet-fed offset varnish are mixed and kneaded with a three-roll mill to prepare a base ink. Then, the ink was adjusted to a printable tack with an incometer according to a conventional method and the fluidity was measured with a spread meter, and good results were obtained as shown in Table 2 below. Further, in order to judge the printability (mainly water-property) of the ink thus adjusted, a test was carried out with an offset 211 type printing machine manufactured by Gestettner. As the plate, a PS plate having the same pattern on the left and right was used, and the ink of the pigment using the comparative example and the ink using the pigment of Example 2 were simultaneously supplied, and the amount of dampening water supplied was increased or decreased for evaluation.

Table 2

Comparative Example 2-a is a pigment which is not treated with the monosulfonated phthalocyanine and alkenyl succinimide dispersant in Example 2, and Comparative Example 2-b is a monosulfonated phthalocyanine. Example 2
The pigment was treated by adding the same amount as the above, and the alkenyl succinimide dispersant was not used. Comparative Example 2
-C is a pigment of Comparative Example 2-b in the process of forming an ink, that is,
It is a mixture of an alkenyl succinimide dispersant and a varnish mixed with a phthalocyanine pigment treated only with mono-sulfonated phthalocyanine. that time,
The amount of the mixed alkenyl succinimide dispersant used was 20% based on the phthalocyanine pigment.

Example 3 17.4 parts of 3,3'-dichlorobenzidine are tetrazotized according to a conventional method to obtain a tetrazonium salt. On the other hand, 29.5 parts of acetoacetametaxylidide and 0.4 part of acetoacetanilidoparasulfonic acid are mixed and dissolved in the presence of an alkali to prepare a precipitating agent according to a conventional method. The two liquids were mixed and coupled to give a suspension of the resulting pigment,
An emulsion liquid prepared in the same manner as in Example 2 from 2.3 parts of the alkenyl succinimide dispersant and 3.4 parts of xylol is injected to treat the pigment.

After further heating and boiling for 30 minutes, 45 parts of PY-13 type pigment are obtained by filtration, washing with water, drying and pulverizing in accordance with a conventional method. In order to compare the performance of this pigment with the pigment of the comparative example, the pigment was tested in the same manner as in the ink test of Example 2, and as shown in Table 3 below, it was very fluid and had a high tinting strength. An ink was obtained.

Table 3

The fluidity, the coloring power, and the printability (suitability for water) were measured in the same manner as in Example 2. Here, Comparative Example 3-a is a pigment in which an alkenyl succinimide dispersant and acetoacetanilide-parasulfonic acid corresponding to the compound (I) are not introduced at all, and Comparative Example 3-b is an alkenyl amber. The acid imide dispersant was used in the same amount as in Example 3, but acetoacetanilide-parasulfonic acid was not introduced.
Comparative Example 3-c was based on a pigment in which the same amount of acetoacetanilide-parasulfonic acid was introduced in the same manner as in Example 3, and an alkenyl succinimide dispersant was added to the varnish in the process of forming an ink. It was tested by mixing 20% with the pigment.

Example 4 17.4 parts of 3,3'-dichlorobenzidine are tetrazotized by a conventional method to obtain a tetrazonium salt. On the other hand, 27.9 parts of acetoacetametaxylidide and benzoic acid 2.
3 parts are mixed and dissolved in the presence of an alkali to prepare a soaking agent. An emulsion prepared by the same method as in Example 1 was prepared by dissolving 2.3 parts of the alkenyl succinimide dispersant in 3.4 parts of xylol in the resulting pigment suspension. To treat the pigment. Then, the temperature is raised, and after boiling for 30 minutes, filtration is performed according to a conventional method,
It was washed with water, dried and crushed to obtain 42 parts of PY-14 pigment.

Next, in order to compare with the pigment of the comparative example, the pigment was dispersed in 90 parts of polyamide-digested cotton (solid ratio 2/1) varnish with a paint conditioner to prepare 85 parts of polyamide-digested cotton type varnish. I got ink. When this ink was used to draw down on coated paper and Mylar film with a # 3 bar coater, the hue was clearer and the density with an excellent gloss was obtained compared to the case of using the pigment of the comparative example. A printed matter having a feeling was obtained.

Table 4 Here, in Comparative Example 4-a, the compound (I) used in Example 4 was not used at all, and in Comparative Example 4-b, the alkenyl succinimide dispersant was used in Example 4.
The same amount was used, but benzoic acid was not used at all. Gloss: Gloss meter (reflection angle 60 °) Viscosity: B type viscometer (measured 1 day after dispersion)

Example 5 16 parts of methyl violet dye was added to warm water 200c at 90.degree.
Dissolve in c with stirring to prepare a dye solution. On the other hand, a precipitant is prepared by a conventional method by adding an appropriate amount of sodium secondary phosphate and sulfuric acid to 16 parts of sodium molybdate and 10 parts of sodium tungstate with respect to 200 cc of water in a separate tank. Next, this is poured into the above dye solution for lake formation to obtain a water-insoluble pigment suspension.

In another separate tank, 1.6 parts of xylol was placed, and 0.8 parts of a non-drying oil type alkyd resin (Beckosol J-522) and 0.8 part of an alkenyl succinimide dispersant were added to this. In addition, it was dissolved and the EA141 of 0.
4 parts are mixed, and 100 cc of hot water at 70 ° C. is added to the mixture to form an O / W type emulsion by high speed stirring, and the mixture is poured into the pigment suspension to treat the pigment.

The mixture is stirred at 90 ° C. for 30 minutes, poured into water to 70 ° C., filtered, washed with water, dried and pulverized by a conventional method to obtain a violet dye pigment suitable for oil gravure ink and flexo ink. . Further, in order to confirm the suitability of this pigment, a test was carried out using the same test method as in Example 4 to obtain an expanded product which was very fluid, glossy and had a feeling of density. . * Beccosol J-522: made by Dainippon Ink

Table 5

Example 6 Toluidine metasulfonic acid (18.7 parts) was diazotized by a conventional method to obtain a diazonium salt. On the other hand, 17.9 parts of β-oxynaphthoic acid and phthalic acid mono-ethyl ester 1.
0 part is mixed and dissolved in an alkaline solution to prepare a soaking solution.
Both solutions are mixed and coupled to obtain 43 parts of 4B Rubintoner (PR-57) dye. A rosin soap prepared by dissolving 8.6 parts of gum rosin in an alkaline solution was poured into the above dye solution, and then an aqueous solution of 17 parts of 75% calcium chloride was added to make a lake. 4B Rubintoner (PR- A pigment suspension of 57) is obtained.

On the other hand, 2.6 parts of the alkenyl succinimide dispersant and 0.3 part of EA141 were heated and mixed at 50 ° C., and 50 cc of the rosin soap (5% aqueous solution) was added thereto.
Is heated to 60 ° C. and mixed well. Then, 100 cc of warm water of 50 ° C. is poured into this and stirred at high speed to
A / W type emulsion is prepared, and the pigment is treated by injecting it into the pigment suspension of 4B Rubintoner. This pigment suspension is aged at 80 ° C. for 30 minutes, poured into water, filtered, washed with water, dried and pulverized according to a conventional method to obtain 4B Rubintoner (PR-, which is suitable as a pigment for publication gravure red ink).
57 parts of pigment 57) are obtained.

Further, 10 parts of this powder pigment, 45 parts of lime rosin and 45 parts of toluol are dispersed in a paint conditioner according to a conventional method to form an ink to obtain a publication gravure ink. Then, when compared with the pigment of the comparative example by the same method, it was confirmed that the pigment of the present invention had clear hue, fluidity and gloss. In addition, in the process of forming an ink, that is, when the pigment of the comparative example is dispersed by the above paint conditioner, 1% of the alkenyl succinimide dispersant is added to the powder pigment.
When mixed with varnish at a ratio of 5%, it has good fluidity and good gloss, but in the case of Henry paper, which has good ink absorption, strike-through (print-through) occurs,
A decrease in gloss and a lack of density can be seen.

Table 6

Examples 7 to 11 For quinacridone pigments, perylene pigments, isoinrinone pigments, condensed azo pigments and dioxazine pigments, the pigment suspensions before filtration of these pigments are treated in the same manner as in Example 1. When the same test as in Example 1 (paint test) was performed, it was confirmed that the pigment was glossy and fluid when compared with the pigment of Comparative Example (untreated product). The results are shown in Table 7 below.

Table 7

[0046]

INDUSTRIAL APPLICABILITY According to the present invention as described above, the organic pigment is treated with the compound (I) and the dispersant (II) to obtain various uses, for example, a pigment for printing ink, a pigment for gravure ink, and a paint. It is possible to provide a novel pigment composition which is useful as a pigment for use in the like.

Claims (4)

[Claims] 1. A compound having an acidic group such as carboxylic acid or sulfonic acid in the molecule and containing an aromatic ring in its constituent molecule, an alkenyl succinimide dispersant, and an organic pigment. A pigment composition. 2. The organic pigment is a phthalocyanine pigment, quinacridone pigment, azo pigment, dyeing pigment, anthracene pigment, perylene pigment, condensed azo pigment, isoindolinone pigment or dioxazine pigment. The pigment composition according to claim 1. 3. The pigment composition according to claim 1, which is for printing ink, publication gravure ink, packaging oil gravure ink, flexo ink or paint. 4. The weight ratio of the compound containing an aromatic ring, the alkenyl succinimide dispersant, and the organic pigment is 0.5 to.
The pigment composition according to claim 1, which is in a range of 20 parts / 0.5 to 20 parts / 99 to 60 parts.