JPH0157149B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel pigment composition, which is characterized by good fluidity, storage stability, and coating gloss when used in water-based printing inks, water-based paints, and other water-based pigment compositions. can be significantly improved. In recent years, due to issues such as air pollution caused by organic solvents contained in oil-based printing inks or paints, occupational health and disaster prevention issues, and resource conservation considerations,
Water-based printing inks or paints are becoming the dominant trend in the industry. For pigments for water-based printing inks or paints, as for oil-based printing inks or paints, fluidity, storage stability, and film gloss of the ink or paint are particularly important suitability, and these properties are important. In order to impart this, it has been proposed to modify pigments with various processing agents or additives, such as surfactants, resins such as rosin, urea, thiourea, etc. Some pigments, such as dioxazine and phthalocyanine pigments, have relatively good suitability as pigments for water-based printing inks and paints without modification, but most pigments When fluidity is improved, coating film gloss is lost, and conversely, when gloss is improved, fluidity and storage stability are impaired. This tendency is caused by oil-based printing ink,
This is also seen in pigments for paints, but it is even more significant in water-based printing inks and paints, and pigments that have been surface-treated with surfactants and resins such as rosin have problems with gloss, fluidity, and storage. It has been extremely difficult to obtain pigments that have both stability. As a result of extensive research, the present inventors discovered that biuret and the urea or thiourea derivative compound represented by the general formula () or () exhibit excellent effects as a pigment treatment agent, and completed the present invention. I came to the conclusion. Biuret, general formula for 100 parts by weight of organic pigment (In the formula, R ₁ and R ₂ are hydrogen atoms, lower alkyl groups,
Represents a carbamide group or a phenyl group. ) or the general formula (In the formula, n represents an integer of 2 to 4.) A pigment composition containing 0.1 to 20 parts by weight of the compound represented by the following is provided. The pigment composition of the present invention can be used as a water-based printing ink, paint, colored coating agent for textiles or non-woven fabrics,
When used as a coloring agent for paper, etc., it exhibits much better fluidity and storage stability than pigments that have been subjected to conventionally known treatments, and provides good paint film gloss. It is known that the biuret used in the present invention can be easily obtained by heating urea, which is industrially produced in large quantities. In addition, hydantoin represented by the general formula () or its substituted product at the 5-position, such as U.S. Patent No.
No. 2717252, No. 2717253, No. 2732400, British Patent No. 630139, Special Publication No. 29-2074, No. 29-
No. 2075, No. 1071, J.Am.Chem.Soc. No. 70
Volume No. 1450, Volume 64, Page 2082, Chem. Ber. No. 83
Vol. 265, J.Prakt.Chem. Vol. 140, No. 291, J.Prakt.Chem. Vol. 141, No. 5, Can.J.Research B Vol. 24, No. 301
Produced by heating a mixture of a carbonyl compound, sodium cyanide, and ammonium carbonate in a solvent such as ethanol-water, or by heating cyanohydrin together with ammonium carbonate in aqueous ethanol, as described on page 1 and elsewhere. This reaction is generally called “Bu¨cherer”.
known as a reaction. Examples of compounds represented by the general formula () include hydantoin, 5-methylhydantoin, 5,5-dimethylhydantoin,
5-ethyl-5-methylhydantoin, 5-methyl-5-phenylhydantoin, 5-phenylhydantoin, 5,5-diphenylhydantoin,
Allantoin [in the general formula (), R ₁ = H, R ₂ = NH-CONH ₂ ]
Not synthesized by Bu¨cherer reaction, Org.Syn.Coll
It can be synthesized by oxidation of uric acid with alkaline potassium permanganate as described on page 23 of vol., or by the condensation reaction of dichloroacetic acid and urea as described in U.S. Pat. No. 2,158,098. I can do it. 5-(2-hydroxyethyl)-1,4,5,6-tetrahydro-1,3, represented by general formula ()
The 5-triazine-2(1H)-thione compound is
It is novel in itself, and is useful not only as a processing agent for the pigment of the present invention but also as an intermediate in the synthesis of pharmaceuticals and agricultural chemicals. Examples of compounds represented by the general formula () include: 5-(2-hydroxyethyl)-1,4,
5,6-tetrahydro-1,3,5-triazine-2(1H)-thione 5-(2-hydroxypropyl)-1,4,
5,6-tetrahydro-1,3,5-triazine-2(1H)-thione 5-(2-hydroxybutyl)-1,4,
Examples include 5,6-tetrahydro-1,3,5-triazine-2(1H)-thione, but these compounds can be synthesized extremely easily and with good yield from alkanolamines, formaldehyde, and thiourea. I can do it. The amount of the pigment treatment agent used in the composition of the present invention is 0.1 to 20 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the pigment, and if it is less than 0.1 part by weight, a sufficient effect cannot be obtained. If the amount exceeds 20 parts by weight, the physical properties of the coating film tend to deteriorate. The pigment treatment agent can be added to the pigment by adding it directly to the pigment powder and mixing, or by adding it to a wet paste of the pigment, mixing it, then drying and pulverizing it, or adding it to the pigment composition in the desired amount. Any method can be used as long as it is uniformly blended, and it may be added at the time of pigment production. Although it is not clear why the compound added to the pigment in the present invention exhibits an excellent effect of preventing thickening over time or structural viscosity, it is possible that the pigment and the polymer in the aqueous vehicle, or the pigment and water or alcohol, etc. This is presumed to be due to its extremely strong effect as a so-called "hydrogen bond breaker" that blocks interaction with polar solvent molecules. Examples of organic pigments to which the present invention is applied include phthalocyanine-based, quinacridone-based, indigo-based, indathrene-based, perylene-based, monoazo-based,
Examples include organic pigments such as disazo, isoindolinone, and dioxazine, but azo pigments are especially effective, and disazo pigments give particularly favorable results. Furthermore, when applied to pigments that have been treated with resins such as surfactants and rosins to impart gloss properties, they exhibit excellent performance as water-based printing ink pigments. Examples of the water-soluble resin of the vehicle used when the pigment composition of the present invention is used for water-based printing ink include styrene-maleic acid, acrylic, styrene-sierac, alkyd, melamine, and epoxy ester. Examples include resins that can be diluted with water or water-soluble polar solvents such as ethanol and isopropyl alcohol. The present invention will be explained in more detail below with reference to synthesis examples of the pigment treatment agent used in the present invention and examples of the present invention, but the gist and scope of the present invention will not be limited by these examples. It is not something that will be done. In addition, all parts in use mean parts by weight. (1) Synthesis example of 5-methylhydantoin [general formula ()] 250.8 g of ammonium carbonate is mixed with 100 g of ethanol.
ml and 100 ml of water, and 53.3 g of 98% lactonitrile was added dropwise over 2 hours while stirring while maintaining the temperature at 15 to 20°C. After the dropwise addition was completed, the mixture was stirred at 20 to 25°C for 2 hours and 30 minutes, then the temperature was raised to 60°C, and the mixture was heated and stirred for 4 hours. The resulting reaction solution was concentrated to half under reduced pressure, 15 g of 35% hydrochloric acid was added, and the temperature was raised to 90°C for 30
The mixture was heated and stirred for a minute. Next, the mixture was cooled to 5°C with stirring, and the precipitated crystals were filtered, dried, and recrystallized from methanol to obtain 59.0 g of white crystalline 5-methylhydantoin with a melting point of 144-45°C. The yield was 70.3%. (2) 5-(2-hydroxypropyl)-1,4,
Synthesis example of 5,6-tetrahydro-1,3,5-triazine-2(1H)-thione [general formula ()] 35% formalin 89.0g (1.04mol) and thiourea
While mixing and stirring 38.1g (0.50mol), 37.6g (0.50mol) of isopropanolamine and 1,4-
A mixed solution with 50 ml of dioxane was gradually added dropwise over a period of 1 hour at 0 to 5°C. 20-25 minutes after completion of dripping
The mixture was stirred at ℃ for 1 hour and further heated under reflux for 2 hours.
As the resulting reaction solution was cooled, a large amount of crystals were precipitated, and upon cooling to 0° C., the precipitated crystals were separated and dried to obtain 68.2 g of first crystals of the target product. Melting point (decomposition point) is 150-152℃, yield is 78.3
It was %. Concentrate the mother liquor further to obtain a second crystal
Obtained 10.5g. Next, the first crystal was purified by recrystallization from a 50% aqueous ethanol solution. The melting point (decomposition point) was 153-155°C, and the results of elemental analysis were as follows. Elemental analysis C ₆ H ₁₃ N ₃ As OS Calculated values C: 41.36%, H: 7.52%, N: 24.12% Actual values C: 40.85%, H: 7.72%, N: 23.85% (3) 5-(2- hydroxyethyl)-1,4,5,
6-tetrahydro-1,3,5-triazine-
Synthesis example of 2(1H)-thione [general formula ()] A mixture of 30.54 g (0.50 mol) of monoethanolamine and 50 ml of 1,4-dioxane was stirred into a mixture of 89.0 g (1.04 mol) of 35% formalin and 38.1 g (0.50 mol) of thiourea cooled to 0 to 5°C. The mixture was added dropwise at the same temperature over a period of 1 hour. After standing overnight at room temperature, the mixture was heated under reflux for 2 hours, and then evaporated to dryness under reduced pressure. The remaining solid was purified by recrystallization from methanol to obtain 58.6 g of white crystals.
Melting point (decomposition point) is 149.5-150.5℃, yield is 72.7
%, and the results of elemental analysis were as follows. Elemental analysis C ₅ H ₁₁ N ₃ OS Calculated values C: 37.25%, H: 6.88%, N: 26.06% Actual values C: 36.98%, H: 6.80%, N: 26.02% Example 1 Tetrazotization using a known method CIPigment treated with HLB14 poly(oxyethylene) alkyl ether type surfactant after coupling and coupling
Yellow 14 was filtered, washed with water and dried, and 5 parts of Biuret were added to 100 parts of this pigment, thoroughly mixed and pulverized to obtain a pigment composition of the present invention. 25 parts of the obtained pigment composition, 45 parts of styrene maleic acid resin (nonvolatile content 28%, PH8.5, Gardner method viscosity P), and 30 parts of water were mixed, and 100 parts of glass beads with a diameter of 3 mm were added to form a paint condenser. Shake and disperse for 90 minutes in an issuer to create an ink base.
60 parts of this ink base, 30 parts of styrenated Sierra Tsuk emulsion (47% non-volatile content, PH8.5) and 5 parts of water.
1 part and stir well to obtain a water-based printing ink.
The obtained aqueous printing ink had particularly excellent fluidity and storage stability, and had good gloss without deterioration. Comparative Examples 1 to 3 Conventionally known pigment compositions were obtained in exactly the same manner as in Example 1 except that the following compounds were used in place of biuret or the addition was omitted, and then water-based printing inks were obtained in the same manner. . The resulting aqueous printing ink had good gloss but was poor in fluidity and storage stability. Comparative Example 1 Urea 5 parts Comparative Example 2 Thiourea 5 parts Comparative Example 3 Not added The viscosity, thixotropic index and gloss of the water-based inks obtained in Example 1 and Comparative Examples 1 to 3 are shown in Table 1. . The viscosity is the value measured by a B-type viscometer at 20℃ immediately after ink preparation and after being left at 20℃ for 720 hours, and the thixotropic index is a B-type viscometer.
The value is the viscosity at 6 rpm divided by the viscosity at 60 rpm, and the gloss is the value measured with a gloss meter after applying ink on kraft paper with a 0.15 mm percoater.

[Table] Example 2 5 parts of biuret were added to 100 parts of β-type phthalocyanine blue, thoroughly mixed and pulverized to obtain a pigment composition of the present invention. 18.1 parts of the obtained pigment composition, 37.5 parts of varnish for water-based ink (water-based acrylic resin manufactured by SC Johnson),
Mix 5.0 parts of water and 8.5 parts of ethanol, add 150 parts of steel beads with a diameter of 3 mm, and thoroughly shake and disperse for 60 minutes with a paint conditioner to create an ink base. Add 35 parts of this ink base to 35 parts of the water-based ink. 15 parts of varnish was added and mixed uniformly to obtain a water-based printing ink with excellent fluidity. Comparative Example 4 A conventionally known pigment was obtained in exactly the same manner as in Example 2, except that the addition of biuret was omitted, and then a water-based printing ink was obtained in the same manner. The resulting water-based printing ink had poor fluidity. The viscosity and thixotropic index of the aqueous printing inks obtained in Example 2 and Comparative Example 4 are shown in Table 2.

[Table] Examples 3 to 8 CIPigment which was tetrazotized and coupled by a known method and treated with a poly(oxyethylene) alkyl ether type surfactant of HLB10.
Yellow 14 was filtered, washed with water and dried, and 5 or 10 parts of the following compound was added to 100 parts of this pigment, thoroughly mixed and ground to obtain a pigment composition of the present invention.

[Table] Next, water-based printing inks were obtained from these pigment compositions in the same manner as in Example 1. All of the obtained aqueous printing inks had particularly excellent fluidity and storage stability, and also had good gloss. Comparative Example 5 A conventionally known pigment was obtained in exactly the same manner as in Example 3, except that the addition of 5,5-dimethylhydantoin was omitted, and then a water-based printing ink was obtained in the same manner. The resulting water-based printing ink was poor in fluidity, storage stability, and gloss. The viscosity, thixotropic index and gloss of the aqueous printing inks obtained in Examples 3 to 8 and Comparative Example 5 are shown in Table 3. The viscosity is a value measured using a B-type viscometer at 20°C immediately after preparation and after being left at 40°C for 120 hours.

[Table] Examples 9 to 14 and Comparative Example 6 23 parts of the pigment composition obtained in Examples 3 to 8 and Comparative Example 5, 50 parts of water-based ink varnish (water-based acrylic resin manufactured by SC Johnson), 10 parts of water, ethanol
Mix 17 parts, add 150 parts of steel holes with a diameter of 3 mm, and shake and disperse for 90 minutes with a paint conditioner to create an ink base, and add 30 parts of the water-based ink varnish to 70 parts of this ink base. A water-based printing ink was obtained by uniformly mixing. The ink bases and water-based printing inks obtained in Examples 9 to 14 had excellent fluidity, but those of Comparative Example 6 had poor fluidity. The compounds used in Examples 9 to 14 and Comparative Example 6 and their usage amounts are as follows.

【table】

Table 4 shows the viscosity and thixotropic index of the ink bases and water-based printing inks obtained in Examples 9 to 10 and Comparative Example 6.

【table】

[Table] Examples 15 to 16 5 parts of the following compound were added to 100 parts of β-type phthalocyanine blue, thoroughly mixed and pulverized to obtain a pigment composition of the present invention. Example 15 5-Methylhydantoin Example 16 Hydantoin Then, in exactly the same manner as in Example 9, a water-based printing ink was obtained. The obtained water-based printing ink had excellent fluidity. Comparative Example 7 Example 16 except that the addition of hydantoin was omitted.
A conventionally known pigment was obtained in exactly the same manner as above, and then a water-based printing ink was obtained in the same manner. The resulting water-based printing ink had poor fluidity. Table 5 shows the viscosity and thixotropic index of the aqueous printing inks obtained in Examples 15-16 and Comparative Example 7.

[Table] Examples 17-18 and Comparative Example 8 CIPigment treated with HLB poly(oxyethylene) alkyl ether type surfactant
CI treated similarly instead of yellow14
A pigment composition was obtained in exactly the same manner as in Example 9, except that Pigment orange 16 was used and the amount of 5,5-dimethylhydantoin added was changed to 10, 5, and 0 parts.
An ink base was obtained in the same manner except that the time was 60 minutes, and a water-based printing ink was obtained in the same manner. The fluidity and storage stability of the obtained ink base and aqueous printing ink tended to be better as the amount of 5,5-dimethylhydantoin added was larger, and the gloss was the same. The amount of 5,5-dimethylhydantoin used in Examples 17 and 18 and Comparative Example 8 is as follows. Example 17 10 parts Example 18 5 parts Comparative example 8 Not added The viscosity and thixotropic index of the ink bases obtained in Examples 17 to 18 and Comparative Example 8 are shown in Table 6, and the viscosity of the water-based printing ink is shown in Table 6. , thixotropic index, and gloss are shown in Table 7. The storage conditions for ink base and water-based printing ink are 20
°C for 96 hours and 168 hours, respectively.

【table】

[Table] Examples 19-20 A pigment composition was obtained in exactly the same manner as in Example 9, except that the following compound obtained in the above synthesis example was used in place of 5,5-dimethylhydantoin, and then aqueous printing was carried out in the same manner. Got the ink. The obtained water-based printing ink had excellent fluidity. Example 19 5-(2-hydroxypropyl)-1,4,5,
6-tetrahydro-1,3,5-triazine-2
(1H)-thione Example 20 5-(2-hydroxyethyl)-1,4,5,6
-tetrahydro-1,3,5-triazine-2
(1H)-thione The viscosity and thixotropic index of the aqueous printing inks obtained in Examples 19-20 and Comparative Example 6 are shown in Table 8.

[Table] Example 21 5-(2-hydroxyethyl)-1, obtained in the above synthesis example, in place of 5-methylhydantoin
Example 15 except using 4,5,6-tetrahydro-1,3,5-triazine-2(1H)-thione
A pigment composition was obtained in exactly the same manner as above, and then a water-based ink was obtained in the same manner. The viscosity and thixotropic index of the aqueous printing inks obtained in Example 21 and Example 7 are shown in Table 9.

【table】

Claims (1)

[Claims] 1 Based on 100 parts by weight of organic pigment, Biuret, general formula (In the formula, R ₁ and R ₂ are hydrogen atoms, lower alkyl groups,
Represents a carbamide group or a phenyl group. ) or the general formula (In the formula, n represents an integer of 2 to 4.) A pigment composition containing 0.1 to 20 parts by weight of the compound shown below.