JP2987072B2 - Pigment composition - Google Patents

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 particularly, to a novel pigment composition which is useful as a pigment for printing ink, a pigment for gravure ink, a pigment for paint, and the like. I do.

[0002]

2. Description of the Related Art In recent years, remarkable progress has been made in the technique of dispersing pigments, and in the paint industry and the ink industry, a method of dispersing a pigment by increasing the pigment concentration as much as possible to streamline production has been increasingly adopted. It became like. Along with this, a problem concerning the fluidity of the pigment dispersion at the time of dispersing or taking out the pigment has been greatly surfaced. In particular, organic pigments (particularly, insoluble azo pigments) are difficult to flow, and tend to be dispersions exhibiting plastic flow with a high yield value, so various measures have been taken.

First, (1) a method of providing a protective film (barrier) on the pigment surface with an amine-based treating agent or the like; and (2) a polar group (—SO ₃ H, —COOH) By introducing a small amount of a diazo or coupling component derivative having a), crystal growth is controlled and efforts are made to modify the crystal surface by imparting appropriate hydrophilicity to the pigment crystal surface. Have been done. As an example of the former, a method of applying a chain-type diamine to a pigment as described in British Patent 1,096,362 (1967) is known. Further, as the latter example, many methods described in JP-B-55-49087 and JP-B-58-25698 have been proposed.

[0004]

However, all of the pigments produced by these methods have high transparency when used in paints and inks, and reduce the efficiency of fluidity due to the small pigment particles. In most cases, it does not work. In particular, the use of inks and paints that require concealment does not respond to the purpose. Also, a method of applying a chain type diamine, that is, B.I. P. It has been pointed out that in the method disclosed in Japanese Patent No. 1,096,362, when the obtained pigment is used for a lithographic ink, the emulsification ratio of the pigment becomes abnormally high, and the problem of water loss during printing occurs. . Others
Separately from the pigment treatment, during the process of preparing the ink
Recently, many studies have been made to mix hyper dispersants (dispersants with outstanding performance) to produce pigment dispersions with extremely high pigment concentration and high fluidity.

[0005] As a typical example of this hyper dispersant, so
Although there are various products under the trade name of lsperese (ICI), these products have different effects depending on the pigments and applications to be used, and have a drawback that the selection of these dispersants is difficult and too complicated. As an example of such a use, an alkenyl succinimide dispersant is found in an example used for 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 resulting ink had serious defects in printability.

That is, a high-concentration pigment is mixed with a hyper dispersant and dispersed efficiently, and the resulting dispersion having excellent fluidity has an extremely high viscosity in the course of dilution with a solvent during ink preparation. If you go down and press it,
Misting is likely to occur, and ink tends to adhere (grease) to the non-image area of the printing plate. Also, for use in publishing gravure inks,
What is printed on Henry paper, in which the phenomenon of strikethrough (print-through) is observed, is also not preferred. Accordingly, an object of the present invention is to provide a novel pigment composition useful as a pigment for printing ink, a pigment for gravure ink, a pigment for paint, and the like, for various uses.

[0007]

The above objects are achieved by the present invention described below. That is, the present invention relates to benzoic acid, naphtho,
Eic acid, β-oxynaphthoic acid; phthalic acid, isophthalic acid
Or terephthalic acid and an alkyl alcohol having 1 to 8 carbon atoms
Alkyd resin obtained by an ester reaction with
Modified alkyl obtained by modifying vegetable oil or glycerin with phthalic acid
Resin; use pentaerythritol instead of glycerin
Alkyd resin with high molecular weight; acetoaceto-2
-Carboxy-anilide or acetoacetanilide
-4-sulfonic acid and the diazo component
Consisting of compounds and monosulfonated phthalocyanines
At least one aromatic ring in the constituent molecule selected from
Compounds having a number of acidic groups Ri Do from (I) an alkenyl succinimide dispersant (II) and organic pigments, the above compounds
A pigment composition which has been treated with (I) and a dispersant (II) .

[0008]

[Function] By treating an organic pigment with a compound (I) and a dispersant (II), a novel pigment composition useful as a pigment for printing inks, a pigment for gravure inks, a pigment for paints, etc. is obtained. Can be provided.

The operation of the present invention will be described in more detail.
First, the vehicles used for lithographic inks are usually rosin-modified phenolic resins or rosin-modified maleic resins,
Alternatively, it is a rosin-modified alkyd resin or the like, and these are resins having a certain acid value. Further, as an ink for a plastic light packaging material printed by a gravure method, an ink using a polyamide-digested cotton or an alkyd-digested cotton as a vehicle has been used for a long time. Both of these polyamide and alkyd resins are resins that retain an acid value to some extent.

Therefore, preferable pigment conditions for dispersing in these vehicles are as follows. The first condition is that the acid value, which is the 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 mutually repelling each other in these vehicles and preventing the dispersion 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. Among them, the first condition is that the compound (I) constituting 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 a imide group of —CONR— having basic properties is favorably adsorbed on a pigment having an acidic group. After adsorbing to the pigment crystal surface, C =
The O group acts to the outside with a strong polarity to provide electrical repulsion to the pigment crystal surface.

On the other hand, the role of compound (I) is that the compound (I) is adsorbed on the surface of
OOH, SO ₃ H) to facilitate the adsorption of the imide group of the dispersant (II), whereby the compound (I) and the dispersant (I
The composition with (I) is considered to function sufficiently on the surface of the pigment crystal in a mutually complementary relationship. Also, dispersant (II)
The alkenyl succinimide dispersant of the present invention can provide a certain degree of good fluidity in the use of a lithographic ink and a gravure ink even when used alone, but in this case, the alkenyl succinimide dispersant is As a result, the transparency and coloring power of the pigment are impaired. In the present invention, it has been found that the use of this compound (I) has a great effect of preventing this phenomenon.

[0013]

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

The compound (I) used in the present invention is
A compound having an aromatic ring and one or more carboxylic acid or sulfonic acid groups in the molecule, including derivatives in which most of these acidic groups have been modified with alcohol or vegetable oil, etc. It is necessary to have one free acidic group in it.

[0015] Then, more specifically, benzoic acid, naphthoic acid, obtained by esterification reaction of β-oxy naphthoic acid, or phthalic acid or isophthalic acid or Tele phthalic acid and alkyl alcohol having 1 to 8 carbon atoms Alkyd resin remaining free carboxyl groups, further modified alkyd resin obtained by modifying vegetable oil or glycerin with the above-mentioned phthalic acid, and free carboxyl groups further increased in molecular weight using pentaerythritol instead of glycerin Alkyd resin or the like having in the molecule. Also included are compounds obtained by the reaction of a diazo component with acetoaceto-2-carboxy-anilide or acetoacetanilide-4-sulfonic acid , and such compounds are described in Example 3.
Are formed at the same time as the pigment is synthesized.

The alkenyl succinimide dispersant of the dispersant (II) refers to a chemical substance represented by the above formula (A), and its essential point in the production method is a functional group such as an unsaturated bond or a halogen. The alkenyl succinic anhydride obtained by the reaction of a polyolefin having the formula (II) and phthalic anhydride is preferably further reacted with a polyamine. The 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.

The polyamine is represented by the following formula: Wherein n is an integer of 10 or less, A and A ′ are a hydrocarbon group, a hydrogen atom,
An amino hydrocarbon group, and an alkylene group is preferably a lower alkylene group having 8 or less carbon atoms. Among these amines, particularly preferred are diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. . Commercially available alkenyl succinimide dispersants represented by these include, for example, "OLOA-1200 manufactured by Chevron Corporation of the United States" and "S-900 manufactured by Nido Win Cooper, Inc."

When treating the pigment with the compound (I) and the dispersant (II), these are usually dissolved in a petroleum organic solvent, and the solution is dissolved in the presence of a surfactant in the solution. Then, pour a large amount of water and stir at high speed.
The pigment is treated by injecting it into a / W type emulsion and injecting it into a pigment slurry. Alternatively, when the compound is soluble in water, compound (I) is converted into a free acid group as a sodium salt and added to water. It is also possible to dissolve or disperse the pigment to treat it and then acidify it to adsorb the compound (I) on the pigment surface.

Further, as for the ratio of the compound (I), the dispersant (II) and the organic pigment used in the present invention, not only the dispersibility and fluidity but also the printability problem have been intensively studied. As a result of the examination, the weight ratio of each was 0.1.
In the range of 5-20 / 0.5-20 / 99-60,
Particularly preferred results are obtained within the range of 2 to 10/2 to 10/94 to 80.

[0020]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the description, parts and% are based on weight unless otherwise specified. Example 1 2-Methoxy-benzamino-5-N, N'-diethylamino-sulfonyl chloride (25.8 parts) is diazotized in a conventional manner to obtain a diazonium salt. This is
An unripened slurry of Pigment Red 5 is obtained by mixing and coupling with a dipstick prepared from 38 parts of hydroxy-naphthalene-3-carboyl-5'-chloro-2 ', 4'-dimethoxyanilide according to a conventional method.

The temperature was raised to 70 ° C., and 2.8 parts of a drying oil-type alkyd resin (Beccosol 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. . After boiling for 60 minutes,
Water was injected and filtered, washed with water, dried and pulverized according to a conventional method to obtain 66 parts of Pigment Red 5 pigment.

This was washed with a melamine-alkyd resin (Beccosol 1307 / Super Beckamine J-8).
20 = solids ratio 2/1), 7.0 parts of the pigment, 35 parts of the above resin and 8.0 parts of the solvent were dispersed by a paint conditioner, and 30 parts of the above resin and 20 parts of the solvent were added to obtain 9 parts.
Two parts of a normally dry red paint are obtained. The paint was spread on coated paper with a 3 mil applicator, and the hiding power was determined with a cryptometer. As compared with the pigment of Comparative Example 1 to which the present invention was not applied, the paint had gloss and flowability. It was confirmed that there was.

Table 1 Viscosity: Using a B-type viscometer Gloss: Gloss meter (reflection angle: 60 °) Veccosol 1307: manufactured by Dainippon Ink and Chemicals Super Beckamine J-820: manufactured by Dainippon Ink and Chemicals

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

Next, the mixture is filtered and washed with water, and the obtained pigment cake is peptized with 1,000 parts of water, and 3.0 parts of mono-sulfonated phthalocyanine is dissolved in alkali at room temperature and poured therein. Then, the temperature was raised to 60 ° C., and a xylol emulsion liquid of an alkenyl succinimide dispersant (5.0 parts of an alkenyl succinimide dispersant was dissolved in 10 parts of xylol, and 1.0 part of Neugen EA141 was added. Emulsified liquid in a large amount of water. This is filtered, washed with water, dried and pulverized according to a conventional method 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 carried out in the following manner. That is, 6.6 parts of the pigment and 14 parts of the sheet-fed offset varnish are mixed, and the mixture is kneaded with three rolls to prepare a base ink. Next, 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. Good results were obtained as shown in Table 2 below. Further, in order to judge the printing suitability (mainly the water running suitability) of the adjusted ink, a test was performed using an offset 211 type printing machine manufactured by Gästedner. For the plate, a PS plate having the same pattern as the left and right plates was used, and the pigment ink using the comparative example and the ink using the pigment of Example 2 were simultaneously supplied, and the supply amount of the dampening solution was increased and decreased.

Table 2

Here, Comparative Example 2-a is a pigment which was not treated at all with the monosulfonated phthalocyanine and alkenyl succinimide dispersant in Example 2, and Comparative Example 2-b was a monosulfonated phthalocyanine. Example 2
The pigment was treated by adding the same amount as described 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 making ink, that is,
An alkenyl succinimide-based dispersant was mixed with a varnish and used with a phthalocyanine pigment treated only with a mono-sulfonated phthalocyanine. that time,
The mixed alkenyl succinimide dispersant was used in an amount of 20% based on the phthalocyanine pigment.

Example 3 A tetrazonium salt is obtained by subjecting 17.4 parts of 3,3'-dichlorobenzidine to tetrazotization according to a conventional method. Separately, 29.5 parts of acetoacetomethaxylide and 0.4 part of acetoacetoanilide parasulfonic acid are mixed and dissolved in the presence of an alkali, and a dipstick is prepared according to a conventional method. Both liquids are mixed and coupled, and the resulting pigment suspension is
An emulsion 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 the temperature is further raised and the mixture is boiled for 30 minutes, it is filtered, washed with water, dried and pulverized according to a conventional method to obtain 45 parts of a PY-13 type pigment. 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. As shown in Table 3 below, it was very fluid and had high coloring power. An ink was obtained.

Table 3

The measurement of fluidity, coloring power, and printability (suitability for water circulation) was carried out in the same manner as in Example 2. Here, Comparative Example 3-a is a alkenyl succinimide-based dispersant and a pigment to which no acetoacetanilide-parasulfonic acid corresponding to Compound (I) is introduced, and Comparative Example 3-b is alkenyl succinimide. An acid imide-based 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 only acetoacetanilide-parasulfonic acid was introduced in the same amount as in Example 3, and an alkenyl succinimide-based dispersant was added to the varnish during the ink formation. The pigment was mixed and tested to be 20% with respect to the pigment.

Example 4 17.4 parts of 3,3'-dichlorobenzidine are tetrazotized according to a conventional method to obtain a tetrazonium salt. On the other hand, 27.9 parts of acetoacetomethaxlide and benzoic acid.2.
3 parts are mixed and dissolved in the presence of an alkali to prepare a dipstick. Both liquids were mixed and coupled, and 2.3 parts of an alkenyl succinimide dispersant was dissolved in 3.4 parts of xylol in the resulting pigment suspension. To treat the pigment. Then, the temperature was raised and boiling was performed for 30 minutes, followed by filtration according to a conventional method.
Washing, drying and pulverization gave 42 parts of a pigment of PY-14.

Next, for comparison with the pigment of the comparative example, the pigment was dispersed in 90 parts of a polyamide-digested cotton (solid ratio: 2/1) varnish with a paint conditioner, and 85 parts of a polyamide-digested cotton type varnish was dispersed. An ink was obtained. When this ink was used to draw down on coated paper and mylar film with a # 3 bar coater, the hue was clearer than when the pigment of Comparative Example was used, and the density was excellent. A printed matter with 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-based dispersant was used in Example 4.
Although the same amount was used, benzoic acid was not used at all. Gloss: Gloss meter (reflection angle 60 °) Viscosity: B-type viscometer (measured one day after dispersion)

Example 5 Methyl violet dye (16 parts) was heated at 90 ° C. in hot water (200 c).
The mixture is stirred and dissolved in c to prepare a dye solution. On the other hand, a precipitant is prepared by adding an appropriate amount of second sodium phosphate and sulfuric acid to 16 parts of sodium molybdate and 10 parts of sodium tungstate per 200 cc of water in a separate tank, according to a conventional method. This is then poured into the previous dye solution and laked to form a water-insoluble pigment suspension.

In another separate vessel, 1.6 parts of xylol was placed, and 0.8 parts of a non-drying oil-type alkyd resin (Beccosol J-522) and 0.8 parts of an alkenyl succinimide dispersant were added thereto. In addition, it was dissolved,
4 parts were mixed, and 100 cc of hot water at 70 ° C. was added thereto, and the mixture was stirred at a high speed to form an O / W emulsion, which was then injected into the pigment suspension to treat the pigment.

The mixture is stirred at 90 ° C. for 30 minutes, poured into water and heated to 70 ° C., and then filtered, washed with water, dried and pulverized in a conventional manner to obtain a violet dye pigment suitable for oil-based gravure ink and flexographic ink. . Further, in order to confirm the suitability of this pigment, a test was conducted by making it into an ink by the same test method as in Example 4. As a result, an extremely colored, glossy and densely colored product was obtained. . * Veccosol J-522: manufactured by Dainippon Ink.

Table 5

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

On the other hand, 2.6 parts of an alkenyl succinimide dispersant and 0.3 part of EA141 were mixed by heating at 50 ° C., and 50 cc of the above-mentioned rosin soap (5% aqueous solution) was added thereto.
Is heated to 60 ° C. and added well to mix. Then, 100 cc of warm water of 50 ° C. is poured into the mixture, and the mixture is stirred at a high speed.
A / W emulsion is prepared and injected into the 4B Rubin Toner pigment suspension to treat the pigment. This pigment suspension was aged at 80 ° C. for 30 minutes, poured into water, filtered, washed with water, dried and pulverized according to a conventional method to obtain a 4B Rubin Toner (PR-PR) suitable as a pigment for gravure red ink for publication.
57) of 53 parts of the pigment are obtained.

Further, 10 parts of this powder pigment, 45 parts of lime rosin and 45 parts of toluene are dispersed by a paint conditioner according to a conventional method to form an ink to obtain a gravure ink for publication. Then, when the pigment of the present invention was compared with the pigment of Comparative Example by the same method, it was confirmed that the pigment of the present invention had a clear hue, had fluidity, and was glossy. Further, in the process of ink formation, that is, when the pigment of Comparative Example is dispersed by the above-mentioned paint conditioner, an alkenyl succinimide-based dispersant is added to this powder pigment in an amount of 1%.
A varnish mixed at a ratio of 5% has good fluidity and gloss, but in the case of Henry paper with good ink absorption, print-through occurs.
There is a decrease in gloss and a lack of density.

Table 6

Examples 7 to 11 For quinacridone pigments, perylene pigments, isoinlinone pigments, condensed azo pigments and dioxazine pigments, the same treatment as in Example 1 was carried out on the pigment suspension before filtration of these pigments. When the same test (paint test) as in Example 1 was performed, it was confirmed that the pigment had gloss and fluidity when compared with the pigment of the comparative example (untreated product). The results are shown in Table 7 below.

Table 7

[0046]

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, pigments for printing inks, pigments for gravure inks, and paints. It is possible to provide a novel pigment composition useful as a pigment for use.

Continuation of the front page (56) References JP-A-6-256698 (JP, A) JP-A-2-70766 (JP, A) JP-A-61-126176 (JP, A) JP-A-59-96175 (JP, A) , A) JP-A-61-141794 (JP, A) JP-A-6-16987 (JP, A) JP-B-41-2466 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C09B 67/20 C09D 7/12 C09D 11/02 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] (1) benzoic acid, naphthoic acid, β-oxynaphtho
Eic acid; phthalic acid, isophthalic acid or terephthalic acid and carbon
By an ester reaction with an alkyl alcohol of 1 to 8
Alkyd resin obtained with phthalic acid
Modified alkyd resin modified from lyserine; glycerin
Instead of pentaerythritol
Kid resin; acetoaceto-2-carboxy-anilai
Or acetoacetanilide-4-sulfonic acid and dia
Compound and monosulfo obtained by reaction with azo component
A compound (I) having an aromatic ring and at least one acidic group in a constituent molecule selected from the group consisting of phthalocyanine halides, an alkenyl succinimide dispersant (II), and an organic pigment. Tona is, organic pigments aforementioned compound (I) and dispersants
And (II) . 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 used for printing inks, gravure inks for printing, oil-based gravure inks for packaging, flexographic inks or paints. 4. The weight ratio of the compound containing an aromatic ring, the alkenyl succinimide-based dispersant and the organic pigment is from 0.5 to 0.5.
The pigment composition according to any one of claims 1 to 3, wherein the amount is in the range of 20 parts / 0.5 to 20 parts / 99 to 60 parts.