JPH0252659B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a pigment composition that is suitable for use, particularly excellent in non-aggregation and non-crystallinity. In general, practically useful pigments that exhibit vivid color tones and high tinting power in various coating compositions are composed of fine particles. However, the 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 are important for manufacturing operations and for the value of the resulting product. This often results in various problems that have an impact. For example, dispersions containing pigments made of fine particles often have a high viscosity, making it difficult to remove the product from the dispersion machine and transport it, and even worse, it may gel during storage and use. It can be difficult. Furthermore, when different types of pigments are mixed and used, phenomena such as color separation due to aggregation and sedimentation may appear in the developed product as color unevenness or a significant decrease in coloring power. Furthermore, the surface of the paint film of the developed product may suffer from poor conditions such as reduced gloss and poor leveling. Further, although not directly related to pigment dispersion, some organic pigments experience a phenomenon that involves a change in the crystalline state of the pigment. In other words, in non-aqueous vehicles such as offset inks, gravure inks, and coatings, pigment crystal particles, which are energetically unstable, change their size and morphology and shift to a stable state, resulting in a noticeable hue in the developed product. Product value may be impaired due to changes in color, decrease in coloring power, generation of coarse particles, etc. The present inventors have developed an offset ink as described above,
We conducted studies to solve various problems that occur in non-aqueous vehicles for gravure inks and paints,
We have invented a method for producing a pigment composition that is excellent in practical use. That is, quinacridone pigments, azo pigments,
Aluminum organic pigments represented by the following general formulas () to () are added to 100 parts by weight of one or more organic pigments selected from isoindolinone pigments, flavanthrone pigments, threne pigments, and perylene pigments. A pigment composition characterized by comprising 0.5 to 30 parts by weight of salt. General formula () Q(-A-COOH) _n In the formula, Q: a residue of an organic dye, A: a direct bond or a divalent bonding group, m: an integer from 1 to 4. More specifically, it can be exemplified by the following general formula. Q(−COOH) _n () In formulas () to (), Q is the same as in formula (), and X is a halogen atom, a nitro group, a hydroxyl group,
p represents a carboxyl group, and p represents an integer of 0 to 4. Examples include pigments or dyes such as benzimidazolone dyes, quinacridone dyes, azo dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, or dianthraquinolyl dyes. By converting the above-mentioned organic dye containing a carboxyl group into a salt with a water-soluble aluminum compound such as aluminum chloride or aluminum sulfate and adding a characteristic group -COO ^- Al ⁺ 1/3 to the end, an organic dye can be formed. It shows a remarkable effect on non-aggregation in mixed systems with pigments. The organic dye represented by the general formula () can be obtained, for example, by diazotizing a base having a carboxyl group according to a conventional method and coupling it with a coupler such as naphthols or acetanilides. Alternatively, it may be an organic pigment itself having a carboxyl group. The compound represented by the general formula () can be produced by a known method of phthalimidomethylating an organic pigment or dye and then hydrolyzing the phthalimidomethylated organic pigment or dye. For example, the organic dye represented by the general formula () can be prepared by combining excess trimellitic anhydride and p
- It is obtained by diazotizing the base () obtained by reacting phenylene diamine and coupling it with a coupler according to a conventional method. It can also be obtained by a dehydration reaction between an organic pigment having an amino group and trimellitic anhydride. The organic dye represented by the general formula () is, for example,
It is obtained by condensing excess terephthalic acid dichloride and p-phenylenediamine by a dehydrochloric acid reaction, followed by hydrolysis, diazotizing the obtained base (2) by a conventional method, and coupling it with a coupler. Further, it can be obtained by condensing an excess organic pigment having an amino group with terephthalic acid dichloride by dehydrochlorination reaction, followed by hydrolysis. The organic pigments in the present invention include, for example, quinacridone pigments, azo pigments, dioxazine pigments, anthrapyrimidine pigments, isoindolinone pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, and perinone pigments. , perylene pigments, etc. The organic pigment and the organic pigment represented by Q in the general formula () do not necessarily have to be the same; for example, even in a mixed system of an aluminum salt of a quinacridone pigment having a carboxyl group and an azo pigment, significant non-aggregation occurs. shows the effect. In the present invention, the mixing ratio of the organic pigment and the organic pigment-based aluminum salt having a carboxyl group is suitably 0.5 to 30 parts by weight, preferably 5 to 20 parts by weight per 100 parts by weight. If the aluminum salt of the organic dye having a carboxyl group is too small, the non-aggregation effect will not be improved, and if it is too large, it will have a negative effect on resistance such as water resistance and solvent resistance. In addition, according to research by the present inventors, organic pigments with carboxyl groups made into salts using other metals such as calcium, zinc, barium, etc., instead of aluminum, do not contain aluminum even when mixed with organic pigments other than phthalocyanine. It has been confirmed that it is significantly less effective than salt. The second invention of the present application relates to an organic pigment composition whose non-aggregation property is further improved by adding an aluminum salt of an organic pigment having a carboxyl group and an aluminum salt of benzoic acid or a derivative thereof as a mixed salt. Here, the amount of the aluminum salt of the organic dye is 0.5 to 30 parts by weight, and the amount of the aluminum salt of benzoic acid or its derivative is 0.5 to 40 parts by weight. Each aluminum salt shall be calculated as -COO ^- Al.1/3. Examples of the benzoic acid derivatives include nitrobenzoic acid, aminobenzoic acid, salicylbenzoic acid, aminosalicylbenzoic acid, terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, and pyromellitic acid. In the present invention, in order to form a mixed salt of an aluminum salt of an organic dye having a carboxyl group and an aluminum salt of benzoic acid or its derivative, for example,
A slurry is prepared by well dispersing the sodium salt of an organic dye having a carboxyl group and the sodium salt of benzoic acid or its derivative, and an aqueous solution of an aluminum salt such as aluminum chloride or aluminum sulfate is added to the slurry. The organic pigment composition of the present invention thus obtained not only does not grow crystals in aromatic solvents and does not cause changes in tinting power or hue, but also has significantly improved non-aggregation properties, and can be used in nitrocellulose lacquers, aminoalkyd baking paints, etc. When used in alkyd resin paints, acrylic resin paints, etc., titanium dioxide,
Even in paints mixed with other pigments such as Bengara and Carbon Black, there is no color separation, no aggregation, and no decrease in coloring power. Moreover, printed matter with a coated film having extremely excellent surface gloss can be obtained. A mixture of benzoic acid or a derivative thereof with an aluminum salt, or an aluminum salt of a colorless or slightly colored organic compound having 4 to 17 carbon atoms and having a carboxyl group may be mixed and dispersed and blended in a predetermined ratio. . Example 1 In a container equipped with a stirrer, 100 parts by weight (dry weight) of unsubstituted α-type quinacridone press cake and an average of about 2 N-(2-carboxy-5-nitrobenzoyl) having the following structure (a) were added. Add 15 parts by weight (dry weight) of quinacridone press cake substituted with aminomethyl groups, add water to make a slurry of about 4000 parts by weight, and add aqueous sodium hydroxide solution.
Adjust the pH to 9.5, raise the temperature to 50°C, and stir for 1 hour. After adding 10.1 parts by weight of hydrated aluminum sulfate (8% by weight based on ₃ minutes of Al ₂ O), the pH was adjusted to 6, filtered, washed with water, and dried at 100°C to form a powder. The viscosity of a paint prepared by dispersing 5 parts of this pigment composition and 95 parts of alkyd melamine varnish in a ball mill at 25°C during kneading and after being left for one month was measured using a BM type viscometer, and the structural viscosity was as follows. does not indicate. In addition, the paint obtained in this way,
A coating film with significantly superior surface gloss can be obtained.

[Table] Furthermore, a light color paint containing 2 parts of a white paint prepared by dispersing 25 parts of rutile titanium dioxide and 75 parts of alkylated melamine varnish in a ball mill and 1 part of the above red paint was diluted with xylol, and its viscosity was adjusted to the food cup No.
4 for 20 seconds, and the mixture was placed in a test tube and observed while standing, but no color separation, flocculation, or sedimentation was observed even after one month. At the same time, similar tests were conducted in Example 1 using di[N-(2-carboxy-5-nitrobenzoyl)aminomethyl]quinacridone without a metal-insoluble salt and with calcium, zinc, or barium salts. However, in all cases, coagulation and sedimentation occurred within 2 days. Example 2 In a container equipped with a stirrer, 100 parts by weight (dry weight) of 2,9-dichloroquinacridone presscake and an average of about 2 N-(2-carboxy-5-nitro- Add 15 parts by weight (dry weight) of quinacridone press cake substituted with benzoyl)aminomethyl group, add water to make a slurry of about 4000 parts by weight, and add 18.8 parts by weight of benzoic acid and 8.1 parts by weight of sodium hydroxide. In addition, the pH was adjusted to 9.5, stirred at 80-85℃ for 1 hour, and left to cool to 50℃.
This was added with hydrated aluminum sulfate (Al ₂ O for ₃ minutes at 8
After adding 49.4 parts by weight (% by weight) and adjusting the pH to 4.5,
Filter, wash with water, and dry at 100℃ to form a powder. The viscosity of a paint prepared by dispersing 5 parts of the pigment composition thus obtained and 95 parts of acrylic melamine varnish in a ball mill at 25°C during kneading and after being left for one month was measured using a BM type viscometer, and the results are as follows. , showed no structural viscosity.

[Table] White paint 2 in which 25 parts of rutile titanium dioxide and 75 parts of acrylic melamine varnish are further dispersed in a ball mill.
Dilute a light colored paint containing 1 part of red paint and 1 part of the above red paint with xylol, and check its viscosity with food cup No. 4.
The reaction time was adjusted to 20 seconds, and the mixture was placed in a test tube and observed while standing still, but no color separation, flocculation, or sedimentation was observed even after one month. At the same time, as a pigment composition for comparison with this
2.9-Add water to 100 parts by weight (dry weight) of dichloroquinacridone press cake to make a slurry of 4000 parts by weight, and make 93.8 parts by weight of benzoic acid and sodium hydroxide.
After adding 32.3 parts by weight and adjusting the pH to 9.5, it was stirred at 80-85℃ for 1 hour. To this, 196.1 parts by weight of hydrated aluminum sulfate was added, the pH was adjusted to 4.5, filtered and washed with water, and heated at 100℃. The dried version showed color separation and agglomeration in similar paint tests. Furthermore, for comparison, water was added to 100 parts by weight (dry weight) of the 2.9-dichloroquinacridone press cake and 10 parts by weight (dry weight) of the quinacridone-monosulfonic acid press cake to make a 4,000 parts by weight slurry as a pigment composition. 80 after adding 9.4 parts by weight of acid and 4.3 parts by weight of sodium hydroxide to adjust the pH to 9.5.
After stirring at ~85°C for 1 hour, 26.2 parts of hydrated aluminum sulfate was added to adjust the pH to 4.5, and filtered.
Those washed with water and dried at 100°C caused color separation and agglomeration in similar tests. Example 3 In Example 1, a benzimidazolone azo compound having the following structure (c) was used instead of the unsubstituted α-quinacridone presscake, and N-(2-carboxy-5 - Hydrated aluminum sulfate according to Example 1, using a benzimidazolone azo compound having a carboxyl group having the following structure (d) instead of the quinacridone presscake having a nitrobenzoyl) aminomethyl group.
Pigments prepared with 11.5 parts did not cause color separation agglomeration in similar paint tests. Example 4 Put 100 parts by weight (dry weight) of perylene having the following structure (e) and 15 parts by weight (dry weight) of perylene dye having the following structure (f) into a container equipped with a stirrer, and add water. Add 18.8 parts by weight of benzoic acid and 7.7 parts by weight of sodium hydroxide to make a slurry of approximately 4,000 parts by weight, adjust the pH to 9.5, stir at 80 to 85°C for 1 hour, and leave to cool to 50°C. To this was added 46.8 parts by weight of hydrated aluminum sulfate (8% by weight as Al ₂ O ₃ minutes), the pH was adjusted to 4.5, filtered and washed with water, and dried at 100°C to form a powder. The viscosity of a paint prepared by dispersing 5 parts of the pigment composition thus obtained and 95 parts of alkyd melamine varnish in a ball mill at 25°C during kneading and after being left for one month using a BM type viscometer is as follows. It showed no structural viscosity.

[Table] In addition, a light color paint containing 2 parts of a white paint prepared by dispersing 25 parts of rutile titanium dioxide and 75 parts of alkyd melamine varnish in a ball mill and 1 part of the above blue paint was diluted with xylol and its viscosity was measured using a food cup No. 4. After adjusting the time to 20 seconds, the sample was placed in a test tube and observed, but no color separation, flocculation, or sedimentation was observed even after one month. Furthermore, in tests using gravure ink using nitrocellulose, no decrease in density due to aggregation was observed, and prints with significantly superior gloss could be obtained. At the same time, for comparison, water was added to 100 parts by weight (dry weight) of perylene (e) as a pigment composition.
A slurry of 4000 parts by weight was added with 93.8 parts by weight of benzoic acid and 32.3 parts by weight of sodium hydroxide, adjusted to pH 9.5, stirred at 80 to 85°C for 1 hour, and 196.2 parts by weight of hydrated aluminum sulfate was added to the slurry to adjust the pH to 4. After adjusting the temperature to .5, filtering, washing with water, and drying at 100°C caused color separation and aggregation in the same paint test. Furthermore, for comparison, 100 parts by weight (dry weight) of perylene (e) and the following structure (g) were used as a pigment composition.
Water was added to 10 parts by weight (dry weight) of an azo dye having
Add parts by weight and 4.4 parts by weight of sodium hydroxide, and adjust the pH
After adjusting the pH to 9.5 and stirring at 80 to 85℃ for 1 hour, adding 26.5 parts of hydrated aluminum sulfate to adjust the pH to 4.5, filtering and washing with water and drying at 100℃. Color separation and aggregation occurred in the paint test. Example 5 In Example 4, the same amount (dry weight) of dianthraquinonyl having the following structure (h) was substituted for perylene having the structure (f), and 19.1 weight by weight of p-nitrobenzoic acid was substituted for benzoic acid. 1 part by weight, add 6.6 parts by weight of sodium hydroxide to adjust the pH to 9.5, and raise the pH to 80~
Stir at 85°C for 1 hour. Add 40.2 parts by weight of hydrated aluminum sulfate and adjust the pH to 4.5.
Wash with water and dry at 100℃ to form a powder. The pigment composition thus obtained did not cause color separation and agglomeration in similar paint tests. Furthermore, offset inks made of various rosin-modified resins exhibited good fluidity and did not increase in viscosity over time. The gloss of the printed matter was also extremely good. Note that dianthraquinonyl (h) can be obtained by dehydrating 4,4'-diamino-1,1'-dianthraquinonyl and trimellitic anhydride in an organic solvent according to a conventional method. Example 6 In Example 4, the same amount (dry weight) of an azo compound having the following structure (i) was used instead of perylene having the structure (f), and 19.1 parts by weight of p-nitrobenzoic acid was used instead of benzoic acid. using sodium hydroxide
Add 6.6 parts by weight to adjust the pH to 9.5, and heat at 80 to 85℃.
Stir for an hour. Hydrated aluminum sulfate 40.2
After adding parts by weight and adjusting the pH to 4.5, filter and wash with water, and dry at 100°C to form a powder. The pigment composition thus obtained did not cause color separation and agglomeration in similar paint tests. Furthermore, in tests with gravure ink using polyamide resin, no sedimentation or decrease in concentration due to aggregation was observed. Example 7 In Example 4, flavanthrone having the following structure (j) was used instead of perylene in (e), and a disazo compound having the following structure (k) was used in place of perylene having the structure in (f). No color-coding agglomeration occurred in similar paint tests. Furthermore, the pigment composition thus obtained did not cause color separation and aggregation in tests with nitrocellulose lacquer and gravure ink. Example 8 In Example 4, in place of perylene in (e), isoyledrinone having the following structure (l) was used, and in place of perylene having the structure in (f), anthraquinone having the following structure (m) was used. also did not cause color-coding agglomeration in similar paint tests. Incidentally, anthraquinone (m) can be obtained by reacting α-acinoanthrquinone and excess terephthalic acid dichloride according to a conventional method, and then hydrolyzing the reaction mixture. The same effect can be obtained by using a threne compound having the following structure (o) in place of perylene in (e) in Example 4, and using a phthalocyanine having the following structure (p) in place of perylene having the structure in (f). No color aggregation occurred in the paint test.

Claims (1)

[Scope of Claims] 1. The following for 100 parts by weight of one or more organic pigments selected from quinacridone pigments, azo pigments, isoindolinone pigments, flavanthrone pigments, thren pigments, and perylene pigments. General formula ()
- Aluminum salt of organic dye represented by ()
A pigment composition comprising 0.5 to 30 parts by weight. Q(−COOH) _n () (In the formula, Q represents a residue of a benzimidazolone dye, a quinacridone dye, an azo dye, an anthraquinone dye, a perylene dye, a phthalocyanine dye, or a dianthraquinolyl dye, and
represents a halogen atom, a nitro group, a hydroxyl group, or a carboxyl group, and m and p each independently represent an integer of 0 to 4. ) 2 The following general formula () is applied to 100 parts by weight of one or more organic pigments selected from quinacridone pigments, azo pigments, isoindolinone pigments, flavanthrone pigments, threne pigments, and perylene pigments.
- Aluminum salt of organic dye represented by ()
1. A pigment composition comprising a mixed salt of 0.5 to 30 parts by weight and 0.5 to 40 parts by weight of an aluminum salt of benzoic acid or a derivative thereof. Q(−COOH) _n () (In the formula, Q represents a residue of a benzimidazolone dye, a quinacridone dye, an azo dye, an anthraquinone dye, a perylene dye, a phthalocyanine dye, or a dianthraquinolyl dye, and
represents a halogen atom, a nitro group, a hydroxyl group, or a carboxyl group, and m and p each independently represent an integer of 0 to 4. )