JPS6239182B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to pigment or dye compositions in the form of powder-free, easily dispersible granules and to processes for their production. It is known to produce pigment granules by a process consisting of stirring an aqueous dispersion of a pigment and a solution of a water-insoluble organic carrier in a water-immiscible organic liquid. However, in the known process the product contains some solvent and it is necessary to remove the organic solvent from the product by distillation. The inventors have found a method in which the product is obtained directly and solvent-free. According to the invention, an aqueous dispersion of a pigment or dye and aniline, N-ethylaniline, N-butylaniline, N-cyclohexylaniline, N.N.
-diethylaniline, N-hydroxyethyl-N
-Cyclohexylaniline, N/N-dimethyl-
3-Methylaniline, N・N-dipropylaniline, N-ethyl-2-methylaniline, N・N-
dibutylaniline, 2,5-dimethylaniline,
An amine compound selected from the group consisting of methianthranilate, N/N-dimethylbenzylamine, di-isobutylamine, n-octylamine, a primary amine having 6 to 12 carbon atoms, and 2-ethylhexylamine. The amine compound is brought into contact with the amine compound under stirring at a pH range where the compound is insoluble in water or higher, while maintaining the temperature above the melting point of the amine compound,
and production of a pigment or dye composition in the form of powder-free, easily dispersible granules, characterized in that the pH is lowered to below 7 to make the amine compound water-soluble, and the resulting granules are recovered. A method is provided. Among the amine compounds, those mentioned as primary amines having 6 to 12 carbon atoms are, for example, cyclohexylamine or Primene 81R.
(a branched chain synthetic aliphatic amine with 12 carbon atoms from Rohm and Haas). The amount of amine compound used is usually 0.1 to 2 parts by weight, preferably 0.3 parts by weight per part of pigment or dye.
and 0.6 parts by weight. The method may be carried out in the presence of an organic carrier. The organic carrier can be an organic compound that is soluble in the amine, or at least softened by the amine, and is insoluble in water or can be made insoluble in water over the entire PH range used in the process. When the ratio of pigment or dye to carrier is high, for example 90:10 or more, the carrier can be liquid. If the proportion of pigment is lower, it is preferable to use compounds with a melting point above 40° C. as carriers. Suitable carriers are, for example, alkyl-, aryl-, aralkyl- or cycloalkyl-carboxylic acids or polyacids and alkyl-, aryl-,
Carboxylic acid esters derived from aralkyl- or cycloalkyl-mono- or poly-hydroxy compounds, such as the fatty acid esters cetyl palmitate, glycerol tristearate,
Glycerin monostearate, glycerin tripalmitate, glycerin trioleate, ethylene glycol dilaurate, ethylene glycol distearate, diethylene glycol distearate, or the benzoic acid esters ethylene glycol dibenzoate, neopentyl glycol dibenzoate, trimethylolethanetri benzoate, trimethylolpropane tribenzoate or the dicarboxylic acid esters dibenzyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate and similar esters of adipic, sebacic or azelaic acid; amides from the above carboxylic acids and ammonia; or alkylaryl-,
aralkyl- or cycloalkyl-mono- or polyamides such as stearamide, oleamide, palmitamide, N-alkyl-stearamide or -oleamide, ethylenebisstearamide;
Phosphate esters such as triphenyl or tricresyl phosphate, resins such as hydrocarbon resins,
xylene formaldehyde resins, coumaron, coumaron-indene and ketone resins; vinyl polymers such as polyvinyl chloride and vinyl chloride copolymers, acrylate and methacrylate polymers and copolymers, polyvinyl acetate and vinyl acetate copolymers; Styrene homo- and copolymers; polyolefins such as polyethylene, polypropylene and polyisobutylene; water-insoluble fatty alcohols such as cetyl alcohol and stearyl alcohol; fatty amines which do not give water-soluble salts such as didodecylamine and distearylmonomethylamine;
Fatty oxazolines include water-insoluble carboxylic acids, such as fatty acids having 12 or more carbon atoms, such as lauric acid, stearic acid, behenic acid, and rosin derivatives, such as uddrozine or its hydrogenated or disproportionated derivatives. These acids may be added to the pigment as aqueous solutions of their alkali metal or ammonium salts. In this case, the process is preferably carried out in the presence of a water-soluble inorganic salt, such as sodium chloride or calcium chloride. These acids are applied as their soluble salts,
and water-insoluble carriers, particularly the applicant's pending application.
It can also be combined with sorbitan esters as defined in specification No. 48061/77. Such a combination provides granules that are extremely useful for coloring polyvinyl chloride. The weight ratio of pigment or dye to carrier is 33.3:
It can be up to 66.7, preferably from 95.5 to 50:50, more preferably from 90:10 to 60:40. When the process is carried out in the presence of an organic carrier, the amount of amine compound used is such as to form a solution of the carrier, or at least to soften the carrier. When using a high ratio of pigment to carrier, or when using a carrier that is less soluble in the amine compound, a higher proportion of the amine compound is required for satisfactory granule formation. Pigments and dyes that can be used are preferably insoluble in water and have a pH range required for the production and isolation of the granules.
It is stable within the range. Suitable pigments are azo, azomethine, anthraquinone, phthalocyanine, nitro, perinone, perylene, dioxazine, thioindigo, isoindolinone, quinacridone, azo or azomethine metal salt or complex. Mixtures of pigments may also be used. Water-insoluble dyes are, for example, organic solvent-soluble azo and phthalocyanine dyes. These dyes can also be used as mixtures and mixed with pigments. The organic carrier may be dissolved or dispersed in the amine and added together with the amine compound, or both may be added before heating or at any point during the heating process. The carrier may also be added in the form of a liquid dispersion, for example an aqueous dispersion of a polymer or resin such as polyvinyl chloride, vinyl chloride copolymer or low molecular weight (oxidized) polyethylene. As well as pure pigments or dyes can be used, ready-made pigment preparations, i.e. pigments as well as e.g.
It is also possible to use formulations containing 90% by weight of carrier, preferably 10 to 40% by weight. Preferably, protective colloids are added to the mixture to aid in the formation of granules and in the production of granules with a more uniform particle size distribution. When used, it is preferably mixed with an aqueous slurry of pigment or an aqueous dispersion of amine compound before contacting the pigment with the amine compound. Suitable protective colloids include cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose,
Includes polyvinyl alcohol, polyethylene oxide, polypropylene oxide, copolymers of ethylene oxide and propylene oxide, adducts of ethylene oxide or propylene oxide, polyvinylpyrrolidone and copolymers thereof, or mixtures of these compounds. Preferred compounds are of the hydroxyethyl cellulose type, exemplified by Natrosol from the Hercules Powder Company. The amount of protective colloid can be up to 15% by weight, but preferably up to 5% by weight, relative to the pigment. The process can be carried out at a temperature selected such that the support is at least softened in the amine derivative, but preferably dissolved in the amine derivative. The mixture is initially formulated at or adjusted to a pH range at which the amine compound is insoluble in water. The mixture is stirred at least until the pigment has migrated from the aqueous phase to the organic phase. Provide sufficient agitation to keep the droplets (or granules) in suspension.
The size of the granules is controlled to some extent by the stirring speed. Increased agitation and swirling causes a reduction in granule size. Strong vortices and therefore small size coarse bodies are discussed in our pending application.
Obtained by using the improved mixing-emulsifying machine described in No. 48061/77. The granules have a diameter of 0.1 to 5 mm, but preferably 0.5 to 2 mm.
Can be mm. Processing times can vary depending on the pigment used and the properties desired in the product. For example, certain pigments, particularly azo pigments, are susceptible to crystal growth when kept in contact with aniline compounds, and the degree of growth depends on the contact time and temperature. The increase in crystal size gives pigments with high opacity. In these cases, the contact time of the pigment and the amine compound can therefore be increased if the product requires good opacity and improved rheological properties in the application system. On the other hand, when using pigments of this type, if a product with good transparency is required, the processing time can be shortened to a time sufficient for the pigment to migrate into the organic phase. in this case,
Addition of a carrier promotes rapid granulation formation, which further reduces processing time. Amine selection also affects transparency. Aliphatic amines have less of a crystallizing effect than aromatic amines and therefore provide more transparent compositions. In the case of pigments that exhibit little or no tendency to crystal growth in the process of the present invention, there is no benefit in extending the contact time of the pigment and amine compound beyond that required to form particulates. Nor. In such cases, particulate formation is considerably facilitated by the use of carriers. In these cases, granule formation is achieved through the use of dissolved inorganic salts during the contacting step.
further encouraged. Particularly representative of such pigments are those that have been treated with a crystallization-promoting solvent in a previous step, such as halogenated copper phthalocyanine (green). The PH of the mixture is then lowered below the PH at which the amine compound is completely water-soluble. This is usually achieved by adding an acid that forms a water-soluble salt with the amine compound.
Below, it is preferably lowered to 5 or less. Preferably the acids are hydrochloric acid and acetic acid. The amine compound thereby dissolves in the water as a salt, leaving the pigment granules and, if used, the organic carrier in suspension. For example, the temperature of the mixture may be increased or decreased as necessary to promote dissolution and as desired for handling or product performance reasons. The granules are then recovered by sieving, washing and drying. Granules too small to be collected are filtered out and reused in the next batch. To recover the solvent, the pH of the liquid is raised, usually to 7 or higher, for example 10. This makes the solvent insoluble, separates it from the water, and can be recovered and reused, for example by decantation. The aniline derivative may be further purified by steam distillation if necessary. The granulation method of the present invention can also be combined with a method of solvent treatment of pigments to improve the properties of pigments that are known to be improved by solvent treatment.
Solvent treatment can be carried out before or during the granulation step. For example, phthalocyanine as a highly aggregated α/β crystalline mixture produced by dry milling is deagglomerated using an amine compound as a solvent in a solvent treatment step and substantially β -Can be transformed into shapes. The resulting granules, especially those with a diameter of 1 mm or less,
initially and during storage by adding small amounts, e.g. up to 2% by weight, of finely divided inorganic or modified inorganic materials commonly used to improve free-flow properties, such as finely divided silica or silicates. Easy flowability can be improved. These materials can be conveniently added to the granulate by simple mixing. Particularly advantageous materials of this kind are finely divided silicas whose surface has been modified with organic groups, such as, for example, Aerosil R972 from Degutusa. The products according to the invention can be used for coloring any system, such as surface coating media such as paints and inks, or plastics. The carrier used is
It is usually selected to be compatible with the system being colored. This product, when formulated into an application system,
Color the material by liberating the pigment from the granules. Next, the present invention will be explained with reference to examples. In the examples, "parts" are parts by weight unless otherwise specified. Example 1 C. from 30 (w/w)% aqueous press cake
Eye Pigment Yellow 93 (CIPigment
Yellow 93) was stirred with 600 parts of water containing 0.5 part of hydroxyethyl cellulose for 10 minutes at room temperature. Add 13 parts by volume of diethylaniline and adjust the pH.
Raised to 10.0. Sorbitan Tristearate 1.5
and 3.0 parts of dicyclohexyl phthalate were added and the temperature was raised to 85°C. After stirring for an additional 30 minutes at 85°C, 5N hydrochloric acid was added to lower the pH to 1.0. Stirring was continued for a further 60 minutes, and the granules thus formed were filtered by passing the treated mixture through a BS60 mesh sieve.
The samples were washed alternately with water at 0.degree. C. and water at room temperature until no chloride was detected. 40 in air circulation dryer
The granules dried at °C gave bright yellow films when incorporated into polyvinyl chloride and polyethylene. Example 2 The procedure of Example 1 was repeated using 3.0 parts of a hydrocarbon resin (Hercules A80) instead of 3.0 parts of dicyclohexyl phthalate. Obtained similar results. Example 3 The operation of Example 2 was repeated except that 19 parts by volume of diethylaniline was used as the solvent. Obtained similar results. Example 4 Hydroxyethyl cellulose was added to 18.0 parts of CI Pigment Yellow 13 in 600 parts of water, obtained by a conventional acetate buffered aqueous coupling method.
0.36 part was added. The pH was raised to 10.0 by adding 2N sodium hydroxide solution, and 2.4 parts of sorbitan tristearate and 10 parts by volume of diethylaniline were added. The temperature was raised to 85°C and held for 30 minutes, then 9.6 parts of Hercules A80 were added.
After stirring for an additional 30 minutes, the pH was lowered to 1.0, and after stirring for an additional 4 hours, the product was separated as in Example 1. A satisfactory dispersion was obtained when the product was incorporated into a thin lithographic ink. Example 5 0.2 parts of hydroxyethylcellulose was dissolved in 200 parts of water. Add 18 parts of CI Pigment Blue 15.3 slurried in 120 parts of water to 18 parts of CI Pigment Blue in 200 parts of water.
It was added along with 3.7 parts of a salt made from Direct Blue 86 and Rosin Amine D. 10 parts of diethylaniline was added to this mixture, and the pH was adjusted to 10.0 by adding 2N sodium hydroxide solution. temperature 85
℃ and held at this temperature for 30 minutes. 20 parts of a melt of Hercules A80 (hydrocarbon resin from Hercules Powder Company) and cetyl alcohol in a ratio of 2:1 are added and after a further 60 minutes,
The pH was lowered to 1.0 by adding 5N hydrochloric acid. Stirring was continued for an additional 60 minutes, and the resulting granules were collected in the same manner as in Example 1. The colored granules thus produced could be easily dispersed in the gravure printing medium. Example 6 0.2 part of hydroxyethyl cellulose was dissolved in 200 parts of water, and copper phthalocyanine (previously triturated with 12 (w/w)% calcium chloride in 150 parts of water to obtain an α/β ratio of 60:40) was added. CI Direct Blue 86 and monomethyl in 27 parts (27 parts) and 300 parts water.
7.5 parts of a salt made from di-(hydrogenated tallow) amine was added. 10 parts of diethylaniline were added and the PH of the mixture was then raised to 10.0 as in Example 5, after which the same loadings and procedures as in Example 5 were applied. The colored granules thus produced could be easily dispersed in the gravure printing medium. Example 7 Pigment - 2 parts of hydroxyethylcellulose were added to an aqueous slurry of 13-100 parts of CI Pigment Yellow with stirring. The temperature was raised to 80°C and the pH was adjusted to 10 by adding 2N sodium hydroxide solution. A solution of 20 parts of dicyclohexyl phthalate in 50 parts of diethylaniline was then added and the mixture was stirred until the pigment had migrated from the aqueous phase to the organic phase. Next, hydrochloric acid was added to adjust the pH to 1. Stirring was continued for an additional 15 minutes at pH 1. Next, 120 parts of the pigment composition were removed by sieving (60 meshes) and washed first with water + acid (PH3) and then with water alone. The product was dried at 60°C. The resulting powder-free composition was successfully formulated into lithographic varnishes. Example 8 CI Pigment Blue in 800 parts of water with a pH of 10
15.3 Add 40 parts of an aqueous slurry to this with stirring.
20 (w/w). 10 parts of low molecular weight polyethylene oxide in the form of a % emulsion were added. Then 0.2 part of hydroxyethylcellulose was added and the mixture was stirred at 85°C on a high power mixer. The high power mixer was removed and a paddle stirrer was inserted. 20 parts of diethylaniline were added and the mixture was held for 30 minutes. Next 2
Hydrochloric acid was added at ~3 minutes to adjust the pH to 1 and the mixture was stirred for an additional 30 minutes. The resulting granules were sieved onto a 60 mesh (BS) sieve, washed with dilute acid and then with water, and dried at 60° C., yielding 50 parts of a product dispersible in polyethylene. Example 9 10 parts of Staybelite resin (hydrogenated uddrosine) and 50% aqueous potassium hydroxide solution
22.5 parts were stirred at high speed in 100 parts of water at 50° C. using a cavitation mixer until a particle-free dispersion was formed (approximately 20 minutes). In a separate container, 15 parts _of dicyclohexyl phthalate are heated and dissolved in 30 parts _of diethylaniline, and a compound of the following average formula: CuPc[ _-SO3NCH3 ( _C12H25 ) ₂ ] ₂ is prepared. 10 parts (as described in Example 6 of our pending Application No. 18736/76) were added under stirring to form a grain-free paste at 50-60°C. This paste was added to the stavelite resin dispersion along with an additional 10 parts of diethylaniline and stirred at high speed until a solid blue emulsion was obtained (approximately 15 minutes). 92 parts of blister copper phthalocyanine and 8 parts of phthalimide were mixed in a ball mill, and 55% of the copper phthalocyanine was
- Milled to crystalline form. 97.8 parts of this mixture (corresponding to 90 parts of copper phthalocyanine) were stirred in 200 parts of water at 50° C. until complete wetting. The blue emulsion was poured into the wet pigment under high speed stirring and stirred for 30 minutes with external cooling as necessary to maintain the temperature of the mixture between 50 and 55°C. The high speed stirrer was replaced with a paddle type stirrer. Approximately 150 r.p.
5 parts of calcium chloride in 500 parts of water while stirring at m.
1 part and 71 parts of concentrated hydrochloric acid were added over 5 minutes. After stirring for an additional 30 minutes, the resulting pigment components were isolated, washed with warm water until free of salts and acids, and incubated at 50-60°C.
It was dried. 120.8 parts of powder-free small granules with excellent rheological properties and tinting strength in toluene-based gravure printing inks were obtained. Example 10 20 parts of β-form copper phthalocyanine pigment and Synperonic NX (nonylphenol)
(0.3 parts of ethylene oxide condensate) was stirred in 500 parts of water until the pigment was completely wetted. The pH was raised to 11 with dilute sodium hydroxide solution, 0.5 part of hydroxyethylcellulose was added, and the temperature was raised to 50°C. 5 parts of coumaron-indene resin (Escores 11028) were heated and dissolved in 10 parts of diethylaniline. This solution was added to the pigment slurry with stirring at about 150 rpm using a paddle stirrer, and the mixture was stirred at 50° C. for 30 minutes. While maintaining stirring, hydrochloric acid was added over 5 minutes to lower the pH to 1. After stirring for an additional 30 minutes, the resulting pigment composition was collected by pouring the mixture onto a 100 mesh sieve, washing with hot water until free of salts and acids, and drying at 50-55°C. 22.3 parts of uniformly sized spherical particles with a diameter of about 1 mm suitable for the preparation of lithographic ink were obtained. Example 11 48.9 parts of the milled copper phthalocyanine mixture of Example 9 containing 45 parts of copper phthalocyanine were stirred under reflux for 5 hours in 250 parts of an isopropanol-water azeotrope. 250 parts of water were added and the isopropanol-water azeotrope was removed by distillation. Another 250 parts of water was added and the temperature was lowered to 50°C. 12.5 parts of the hydrocarbon resin Hercules A80 were heated and dissolved in 25 parts of diethylaniline, and this was added to the pigment slurry with stirring. After 15 minutes, 5 parts of the copper phthalocyanine sulfonic acid-tallow amine compound of Example 6 was added,
This mixture was stirred for an additional 15 minutes. In this mixture,
Acidification was achieved by adding 30 ml of concentrated hydrochloric acid in 30 ml of water. The resulting pigment composition was collected on a 60 mesh sieve (BS), washed with hot water and dried at 50-55°C. 58.2 parts of spherical particles, 78% of which were within the range of 0.21-0.32 mm in diameter, were obtained. Examples 12-18 To 20 parts of CI Pigment Yellow 17 in the form of an aqueous slurry from the azo coupling process, 0.2 parts of hydroxyethyl cellulose was added. temperature
The temperature was raised to 80°C and the pH was adjusted to 10. Next, 10 parts of alkylaniline and various amounts of diisooctyl phthalate (DiOP) as shown in Table 1 were added. This mixture was stirred for 20 minutes. During this time, beads with a diameter of 1 to 2 mm were produced. Next, adjust the pH to ~1 with hydrochloric acid,
Stirring was continued for 5 minutes. The beads were then filtered, washed and dried at 50°C. The product was uniformly sized granules that gave a clear yellow film when incorporated into plasticized polyvinyl chloride.

Table: Examples 19-23 To 20 parts of CI Pigment Yellow 17 in the form of an aqueous slurry from the azo coupling process, 0.2 parts of hydroxyethylcellulose (Natrosol 250HR) was added. temperature 80
℃ and add 2N sodium hydroxide solution to adjust the pH.
was adjusted to 10. 10 parts of N.N-diethylaniline and 2 parts of the carrier shown in Table 2 were added. This mixture was stirred for 60 minutes. During this time, 1-2 mm granules were formed. Next, adjust the pH to 1 with hydrochloric acid and stir for 5 minutes.
Lasted for minutes. The granules were then filtered, washed free of salt, and dried at 50°C. The product gave a printing ink concentrate when dispersed in Lithoglara ink.

Table: Example 24 20 parts of CI Pigment Yellow 17 in the form of an aqueous slurry from the azo coupling process and hydroxyethylcellulose (Natrozol 250HR)
0.2 part was adjusted to pH 10 with 2N sodium hydroxide solution. To this pigment slurry was added an aqueous potassium salt solution of 2 parts of hydrogenated uddrozine (stabelite resin). After stirring for 10 minutes, 1 part of calcium chloride dihydrate in 10 parts of water was added and the temperature was raised to 85°C.
Next, add 10 parts of N/N-diethylaniline and heat at 85°C.
Stirring was continued for 1 hour. Adjust the pH to 1 with hydrochloric acid,
The granules were filtered out. This was then washed and dried. The product was easily dispersed in the lithographic varnish. Example 25 Hydroxyethyl cellulose (Natrozol 250HR) 0.2 was added to the pigment slurry used in Example 24.
1 part, 2 parts of stearic acid and calcium chloride dihydrate
Added 0.6 parts. Adjust the pH with 2N sodium hydroxide solution
10, the temperature was raised to 85°C, and 10 parts of N·N-diethylaniline was added. After stirring for 1 hour, the pH was adjusted to 1 with 5N hydrochloric acid, and the granules were filtered out. This was then washed and dried. The product could be dispersed in polyvinyl chloride. Example 26 An aqueous slurry of 100 parts CI Pigment Yellow 13 produced in a conventional azo coupling process and hydroxyethyl cellulose (Natrosol
250HR) were stirred at 15°C for 20 minutes. Adjust the pH of the slurry to 10 with 2N sodium hydroxide solution, add 10 parts of dioctyl phthalate and 100 parts of diethylaniline.
of the mixture was added. Continue stirring at 15℃ for 90 minutes.
The granule formation was completed. Hydrochloric acid was added to adjust the pH to 1, and the granules (100 parts) separated and collected on a 60 mesh sieve were washed and dried at 50°C. The product could be dispersed in lithographic ink media. Example 27 20 parts of CI Pigment Green 7 in the form of a 30 (w/w)% presscake were dispersed in 600 parts of water in which 30 parts of sodium acetate and 10 parts of sodium chloride were dissolved. After raising the temperature to 85°C, 10 parts of N·N-diethylaniline was added and stirring was continued at 85°C for 2 hours. The pH was then lowered to slightly below 1 with 5N hydrochloric acid. 20 parts of granules remained on the 60B.S. mesh sieve.
The inorganic salts and acid were carefully washed away and dried at 55°C. The resulting non-dusting particulates could be dispersed in the lithographic ink medium. Example 28 16 parts of CI Pigment Green 7 in the form of a 30 (w/w)% presscake were dispersed in 300 parts of water. To this dispersion, 3 parts of hydrogenated uddrodine (stavelite resin) was added as an aqueous solution of its potassium salt. This mixture was stirred for 2 hours and then hydroxyethylcellulose (Natrozol 250HR)
0.2 parts and 3 parts of sorbitan tristearate (Span 65) were added. This mixture with a pH of 9 was heated to 85°C, and the pH was adjusted to 6 with 5N hydrochloric acid.
Then, 24 parts of sodium acetate, 8 parts of sodium chloride, and 16 parts of N.N-diethylaniline were added. The mixture was stirred at 85° C. for 5 minutes, then the pH was adjusted to slightly below 1 with 5N hydrochloric acid. The resulting granules were passed through a 60B.S. mesh sieve, washed until free of inorganic salts and acids, and dried at 55°C. Product (22
part) could be dispersed in plasticized polyvinyl chloride. Examples 29-34 A series of bisarylamide azo pigments shown in Table 3 were prepared by conventional azo coupling methods. Hydroxyethyl cellulose (Natrozol
After adjusting the pH to 10 with 2N sodium hydroxide solution, 10 parts of N·N-diethylaniline was added. The temperature was raised to 85°C and stirring continued at this temperature for 2 hours. The pH was then adjusted to slightly below 1 with 5N hydrochloric acid, the granular product was washed free of inorganic salts and acid, and isolated by drying at 60°C.
The product was dispersed in lithographic oil based ink medium.

Table Example 35 20 parts of CI Pigment Yellow 13 in the form of a 5% (w/w) aqueous slurry prepared by the conventional aqueous azo coupling method and 0.2 parts of hydroxyethylcellulose (Natrozol 250HR) at pH 6.
Heated to 85°C. Next, N・N-diethylaniline
10 parts were added and stirring continued for an additional 30 minutes. The pH was adjusted to slightly below 1 with 5N hydrochloric acid and the granular product was filtered, washed free of inorganic salts and acid, and dried at 55°C. The properties of this product were similar to those of Example 29. Example 36 100 parts of an aqueous slurry of CI Pigment Yellow 13 prepared in the same manner as in Example 35 was adjusted to pH 11 with 2N sodium hydroxide solution, and 1 part of hydroethyl cellulose (Natrozol 250HR) and 30 parts of hydrogenated utudolozine were added. An aqueous solution of potassium salt was added. This mixture was heated to 85 °C and at this temperature 15
It was held for a minute. Next, the pH was adjusted to 6.2, and 50 parts of N.N-diethylaniline was added. Stirring was continued for 15 minutes, then the pH was lowered to just below 1 with 5N hydrochloric acid.
Uniform spherical particles were recovered by filtering, washing until free of inorganic salts and acids, and drying at 55°C. The resulting granules gave prints of excellent gloss when dispersed in a lithographic oil-based ink medium. Example 37 A similar product with similar properties was obtained by applying the amounts and procedure of Example 36, except that the amount of hydrogenated uddrodine was reduced to 10 parts. Example 38 CI Pigment Yellow 13 of 5 (w/
w) 20 parts of the % aqueous suspension were adjusted to pH 10 with 2N potassium hydroxide solution. An aqueous potassium salt solution of 0.2 parts of hydroxyethylcellulose (Natrozol 250HR) and 2 parts of hydrogenated uddrozine (stavelite resin) was added and the mixture was heated to 85°C. Then 10 parts of N.N-diethylaniline were added and the mixture was stirred at 85° C. for 1 hour, and the pH was adjusted to slightly below 1 with 5N hydrochloric acid. The resulting spherical particles were filtered, washed until inorganic salts were removed, and dried at 50°C. This product could be dispersed in lithographic oil-based inks and had greater clarity than the product of Example 37. Example 39 Example 37 except that the amount of utudolozin is increased to 6 parts
A product with appearance and performance similar to that of Example 12 was obtained. Example 40 5 (w/w)% aqueous slurry of CI Pigment Yellow 13 prepared as in Example 9 20
1 part and 0.2 parts of hydroxyethyl cellulose (Natrozol 250MR) with 2N sodium hydroxide solution.
Adjusted to 10. 20 parts of N.N-diethylaniline and 2 parts of dioctyl phthalate were added and the mixture was stirred at 20°C for 45 minutes. Next, adjust the pH to 1 with 5N hydrochloric acid.
Adjusted it slightly lower. The granular composition was isolated by filtering, washing until free of inorganic salts and acids, and drying at 55°C. The resulting particulate product could be dispersed in lithographic ink. Example 41 CI Pigment Yellow 74 20 parts 5 (w/
w) % slurry and 0.2 part of hydroxyethyl cellulose (Natrozol 250HR) were adjusted to pH 10 with 2N sodium hydroxide solution. Next, an aqueous potassium salt solution of 2 parts of hydrogenated uddrodine (stavelite resin) was added, the temperature was raised to 85°C, and 10 parts of N·N-diethylaniline was added. Continue stirring at 85°C for 2 hours, adjust the pH to slightly below 1 with 5N hydrochloric acid, filter the product over a 60B.S. mesh sieve, wash until free of inorganic salts and acids, and dry at 55°C. and isolated. The resulting generally spherical particles could be dispersed in lithographic inks or decorative paints. In the case of the latter application, highly desirable opaque coatings were obtained. Example 42 Thirty parts of CI Pigment Yellow 83 as a 5% (w/w) aqueous slurry prepared by the conventional aqueous azo coupling method was adjusted to pH 7 with 2N potassium hydroxide solution and treated with hydrogenated utudolozine (stabe). 3 parts of Wright's resin) were added as an aqueous solution of its potassium salt. Then add 0.3 parts of hydroxyethyl cellulose (Natrozol 250MR), heat this PH10 slurry to 85°C, maintain at 85°C for 10 minutes, then
The pH was adjusted to 6 with 5N hydrochloric acid. Next, 30 parts of N·N-diethylaniline was added, and stirring was continued for an additional 10 minutes at 85°C. Next, adjust the pH to below 1 with 5N hydrochloric acid,
The granules were passed through a 60B.S. mesh sieve, washed free of inorganic salts and acids, and dried at 60°C. The resulting product could be dispersed in oil-based inks, giving very clear ink films. Excellent rheological properties were obtained in the nitrocellulose binder-alcohol solvent liquid ink, and the resulting films exhibited excellent gloss and brightness. Example 43 Aqueous slurry of 30 parts CI Pigment Yellow 83 prepared as in Example 42 and hydroxyethylcellulose (Natrozol 250MR)
0.3 part was adjusted to pH 7 and heated to 85°C. While stirring, add 30 parts of N-N-diethylaniline and heat to 85°C.
The contact continued for 3 hours. Next, the pH was adjusted to slightly below 1 with 5N hydrochloric acid, and the roughly spherical granules were
It was isolated by passing through a 60B.S. mesh sieve, washing until inorganic salts and acids were removed, and drying at 60°C. The dried granules were free-flowing and resistant to pressure. When formulated in a lithographic ink, it gave a slightly more opaque film than the product of Example 42. The nitrocellulose binder-alcohol solvent ink is still Example 42.
It gave a film with similar good rheological properties and excellent gloss. Example 44 A mixture of 30 parts of an aqueous slurry of CI Pigment Yellow 83 produced in the same manner as in Example 42 and 0.2 parts of hydroxyethyl cellulose (Natrozol 250HR) was adjusted to pH 11, and N-N-diethylaniline was added.
Added 15 parts. The temperature was increased to 95°C and maintained at this temperature for 6 hours with stirring. Next, adjust the pH to 0.5 with 5N hydrochloric acid.
lowered to The product was then passed through a 60 B.S. mesh sieve, washed free of inorganic salts and acids, dried at 55°C and collected. The obtained product has an average diameter of 0.5
- They were approximately spherical particles with a diameter of 1 mm. Example 45 The same formulation and stirring conditions as in Example 44 were applied except that hydroxyethylcellulose was omitted, and granules with a diameter of 3 to 5 mm were obtained. Example 46 5 (w/
w) 15 parts of CI Pigment Red 38 in the form of a % aqueous slurry were added to 400 parts of water and the pH was raised to 6.3.
0.2 part of hydroxyethyl cellulose was added and heating was started. When the temperature reached 70°C, 15 parts of N.N-diethylaniline was added and the temperature was raised to 80°C. After further stirring at 80℃ for 3 hours, 10N hydrochloric acid was added.
The PH was lowered to slightly below 1.0 and the product was isolated and dried as in Example 45. The resulting spherical particles could be easily dispersed in lithographic ink medium. Example 47 18 parts of β-copper phthalocyanine pigment and bis-cetyloxysulfanilide of copper phthalocyanine (the process for its preparation is described in our pending application No. 50054/
76) in the form of a 10% (w/w) aqueous slurry were dispersed in 500 parts of water in which 40 parts of sodium chloride were dissolved. Add hydroxyethylcellulose (Natrozol 250HR) to this dispersion.
0.2 part was added, and heating was started while stirring. 70℃
Then, 5 parts of dicyclohexyl phthalate dissolved in 15 parts of N.N-diethylaniline was added, and the temperature was increased.
Stirring was continued for 2 hours at 80°C. The pH was then lowered to slightly below 1.0 with 10N hydrochloric acid. The resulting granules were separated by filtration, washed free of chloride, and dried at 40° C. in an air circulation dryer. The product could be dispersed in lithographic and graphia printing media. Example 48 200 parts of the aqueous pigment slurry of Example 47 was added to 500 parts of water in which 20 parts of sodium chloride had been dissolved. To this dispersion, 0.5 parts of a primary fat (tallow) amine [Crodamine IT from Crodagh] was added as an acetate aqueous solution, 1.5 parts of hydrogenated utudolozine (stavelite resin) was added as a potassium salt aqueous solution, and 0.1 part of hydroxyethyl cellulose was added. Added a section. Heating was started, 15 parts of N.N-diethylaniline was added at 70°C, the temperature was raised to 80°C, and stirring was continued for an additional 80 minutes. The pH was lowered in the same manner as in Example 21, and the product consisting of roughly spherical particles was separated on a BS60 mesh sieve, washed in the same manner as in Example 47 until no chloride ions were observed, and dried at 40°C. Example 49 27 parts of copper fucrocyanine, previously milled to an α/β ratio of 60:40, and 30 parts of sodium chloride were dispersed in 700 parts of water. 0.1 part of hydroxyethyl cellulose was added and heating was started. When the temperature reached 70°C, a secondary fat (coconut oil) amine (Armeen from Armor Hess) was dissolved in 11.2 parts of N-N-diethylaniline.
2C] 1.5 parts was added. The temperature was raised to 80°C and one hour after the addition of diethylaniline, 6 parts of hydrogenated utudolozine (stavelite resin) was added as an aqueous solution of its potassium salt. Next, copper phthalocyanine bis-cetyloxysulfanilide 3 of Example 21
Added a section. After stirring for another 15 minutes, adjust the pH with 10N hydrochloric acid.
The temperature was lowered slightly below 1.0, and the roughly spherical granules produced were separated in the same manner as in Example 28. The granules thus obtained were easily dispersible in lithographic ink medium. Example 50 30 parts of copper phthalocyanine and 30 parts of sodium chloride, previously milled to an α/β ratio of 55:40, were dispersed in 700 parts of water and 0.1 part of hydroxyethylcellulose was added. Heating was started, and 7.5 parts of hydrogenated utudolozine (stavelite resin) was added as an aqueous potassium salt solution. N・N-diethylaniline at 75℃
15 parts were added and the mixture was stirred for a further 2 hours at 80°C. The pH was lowered in the same manner as in Example 47, and the resulting granules were separated and dried in the same manner as in Example 48.
The product was easily dispersible in lithographic ink media. Example 51 81.0 parts of the pigment of Example 24, 90 parts of sodium chloride, and 9.0 parts of copper phthalocyanine bis-cetyloxysulfanilide of Example 47 were dispersed in 1500 parts of water. Heating was started and 2.25 parts of primary fat (tallow) amine (Crodamine IT from Croda) was added as an acetate aqueous solution and 20.25 parts of hydrogenated utudolozine (stavelite resin) was added as a potassium salt aqueous solution. Stirring was continued for 1 hour, and 70 parts of N.N-diethylaniline was added to the slurry at 80°C. After another 15 minutes, the pH was lowered in the same manner as in Example 27, and the resulting granules were separated and dried in the same manner as in Example 48. The product was easily dispersible in lithographic and gravure printing ink media. Example 52 24 parts of CI Pigment Orange 34 in the form of a 5% (w/w) aqueous slurry obtained by conventional acetate buffered aqueous coupling are dispersed in 100 parts of water;
2N potassium hydroxide solution was added to raise the pH to 7.0. 12 parts of N.N-diethylaniline were added and the temperature was raised to 80°C over 45 minutes. After stirring for an additional 15 minutes at 80°C,
10N hydrochloric acid was added to lower the pH to just below 1.0.
The produced granules were filtered in the same manner as in Example 47, washed until chloride was removed, and dried.
The resulting granules having a diameter of 0.5-4 mm were easily dispersible in lithographic ink medium. Example 53 120 parts of CI Pigment Orange 34 in the form of a 5% (w/w) aqueous slurry obtained by conventional acetate buffered aqueous coupling are added to 500 parts of water;
2N sodium hydroxide solution was added to raise the pH to 8.0. Add 0.6 parts of hydroxyethyl cellulose,
Heating started. When the temperature reaches 60℃, N・N
- Add 120 parts of diethylaniline and reduce the temperature.
The temperature was raised to 80℃. After stirring at 80°C for 2 hours, 10N hydrochloric acid was added to lower the pH to slightly below 1.0, and the product was separated and dried in the same manner as in Example 48. Obtained diameter
The 0.3-1mm spherical particles are suitable for lithography, ink,
It was easily dispersible in the medium. Example 54 5(w/
w) 15 parts of CI Pigment Red 3 in the form of a % aqueous slurry were dispersed in 400 parts of water and the pH was raised to 8.0 by adding 2N aqueous sodium hydroxide solution. 0.3 part of hydroxyethylcellulose was added and heating was started. When the temperature reached 80°C, 10 parts of N.N-diethylaniline were added and the mixture was stirred at 80°C for a further 2 hours. Next, 10N hydrochloric acid was added to lower the pH to 1.0, and the product was separated and dried in the same manner as in Example 47. The resulting granules were easily dispersible in lithographic ink medium. Examples 55-60 The procedure of Example 36 was repeated, except that N.N-diethylaniline was replaced with an equivalent amount of the amine listed in Table 4. The appearance and performance of the product was similar to that of Example 36.

Table Examples 61-69 20 parts of the pigments listed in Table 5 and hydroxyethylcellulose (Natrozol 250HR) in the form of an aqueous slurry obtained by the conventional azo coupling method.
0.2 part was heated to 85°C at pH 8. A solution of 5 parts of organic carrier in 15 parts of the appropriate amine shown in Table 5 was added and the mixture was stirred at 85°C for 1 hour. Then PH
was adjusted to ~1, and the granules were collected by filtration, washing, and drying. All products were dispersible in lithographic varnish. Table 5 below lists the pigment carriers and amines used.

[Table] Branched chain primary amine Example 70 As an aqueous slurry prepared according to Example 35
20 parts of CI Pigment Yellow 13, 0.2 parts of hydroxyethyl cellulose (Natrozol 250HR) and 5 parts of dicyclohexyl phthalate at pH 8.
C. to 85.degree. C., then 15 parts of 2-ethylhexylamine were added. The mixture was kept at 85°C for 1 hour, then the pH was adjusted to 1.5 with 10N hydrochloric acid and the granules were collected by filtration, washing and drying at 55°C.
The product could be dispersed in lithographic varnish. Example 71 10 parts of Solvent Yellow 48 were dispersed in 200 parts of water, and 0.1 part of potassium resinate and 0.1 part of hydroxyethylcellulose (Natrozol 250HR) were added. This mixture was adjusted to pH 7, and 5 parts of N.N-diethylaniline were added. The mixture was heated to 80°C and held for 30 minutes, then adjusted to pH 1 with 10N hydrochloric acid. The granules were recovered by filtering, washing and drying at 30°C. Example 72 CI Pigment Red 57: Resin composition (part ratio 16: due to the formation of pigment metal salts in the presence of Stabelite resin from Hercules Powder Co.)
4) An aqueous slurry of 20 parts, 0.5 parts of hydroxyethyl cellulose (Natrozol 250HR) and 3.3 parts of abiethylamine added as water-soluble acetate was heated to 95° C. at PH10. Next, add 10 parts of N・N-diethylaniline, adjust the pH to 7, and heat at 95℃ for 2 hours.
Stirring was continued for an hour. Then add glacial acetic acid to bring the pH to 3.2
(Adjusting the pH to 1 with concentrated hydrochloric acid should be avoided as it will give a product with poor performance at this pH, probably due to decomposition of the metal salt). The granules were isolated, washed and dried at 90°C. The product could be dispersed in lithographic ink varnish. Example 73 100 parts of CI Pigment Green 7 as a 35 wt. Ammonium salt solution was added and stirring continued for an additional 60 minutes. Next, hydroxyethyl cellulose (Natrozol 250HR) 0.4
and 20 parts of sorbitan tristearate were added and the temperature was raised to 85°C. While continuing to stir, add water
A solution of 30 parts of N·N-diethylaniline dispersed in 100 parts and 0.5 part of potassium resinate was added. Improved mixing - Continue stirring with the emulsifier for 1 minute until the pH reaches 6.
After stirring for an additional 5 minutes, the pH was adjusted to 1 with 5N hydrochloric acid. The granules were passed through a 200B.S. mesh sieve and washed until no acids or salts were detected.
Dry at 45°C. The resulting granules, all less than 0.5 mm in diameter, were easily dispersible in the plasticized polyvinyl chloride compound. When 1% by weight of Aerosil R972 (manufactured by Degutsusa) was added to the above granules, a product was obtained which had particularly improved free flow properties after storage. Example 74 Ennesin A100 (Leon Frankel) was substituted for the Stavelite resin solution.
Frankel product] 30 parts was used as the potassium salt solution, and the procedure of Example 73 was otherwise repeated.
A product with similar properties was obtained.

Claims (1)

[Claims] 1. An aqueous dispersion of a pigment or dye, aniline,
N-ethylaniline, N-butylaniline, N-
Cyclohexylaniline, N・N-diethylaniline, N-hydroxyethyl-N-cyclohexylaniline, N・N-dimethyl-3-methylaniline, N・N-dipropylaniline, N-ethyl-2-methylaniline, N. N-dibutylaniline, 2,5-dimethylaniline, methylanthranilate, N,N-dimethylbenzylamine, di-isobutylamine, n-octylamine, C6 -C12 primary amines and 2-ethylhexylamine An amine compound selected from the group consisting of is brought into contact with the amine compound at a pH of 7 or above while maintaining a temperature above the melting point of the amine compound with stirring, and the pH is adjusted to 7.
1. A process for producing a pigment or dye composition in the form of powder-free, easily dispersible granules, characterized in that the amine compound is made water-soluble by reducing the amine compound to water-soluble and the resulting granules are recovered. 2 The amount of amine per part of pigment or dye
A method according to claim 1, wherein the amount is 0.1 to 2 parts by weight. 3 The amount of amine per part of pigment or dye
A method according to claim 1, wherein the amount is 0.3 to 0.6 parts by weight. 4. Claims made in the presence of an organic carrier having a melting point of 40° C. or higher, soluble in said amine or at least softened by said amine, and insoluble in water or capable of being rendered insoluble in the entire pH range used in the process. The method described in any one of scope 1 to 3. 5 The carrier is a carboxylic acid ester, a carboxylic acid amide, a phosphoric acid ester, a resin, a vinyl polymer, a styrene polymer, a polyolefin, a fatty alcohol,
5. The method of claim 4, wherein fatty amines, fatty oxazolines, water-insoluble carboxylic acids or rosin derivatives do not yield water-soluble salts. 6. The method according to claim 4 or 5, wherein the amount of carrier is 0.05 to 2 parts by weight per part of pigment or dye. 7. The method according to claim 4 or 5, wherein the amount of carrier is 0.1 to 0.7 parts by weight per part of pigment or dye. 8. The method according to any one of claims 1 to 7, which is carried out in the presence of a protective colloid. 9. Before contacting the pigment or dye with the amine,
9. The method of claim 8, wherein the protective colloid is mixed with an aqueous slurry of pigment or dye or an aqueous dispersion of amine. 10. The method according to claim 8 or 9, wherein the protective colloid is a cellulose derivative. 11. The method according to any one of claims 8 to 10, wherein the amount of protective colloid is 15% by weight or less based on the pigment or dye. 12. The method according to any one of claims 8 to 10, wherein the amount of protective colloid is 5% by weight or less based on the pigment or dye. 13. A process according to any one of claims 4 to 7, carried out at a temperature at which the support is dissolved in the amine. 14. The method of claim 1, wherein the mixture is stirred at least until the pigment or dye has migrated from the aqueous phase to the organic phase. 15. The method according to claim 1, wherein stirring is carried out to produce granules having a diameter of 0.1 to 5 mm. 16. The method according to claim 1, wherein stirring is carried out to produce granules having a diameter of 0.5 to 2 mm. 17 Aqueous dispersion of pigment or dye and aniline, N-ethylaniline, N-butylaniline,
N-cyclohexylaniline, N·N-diethylaniline, N-hydroxyethyl-N-cyclohexylaniline, N·N-dimethyl-3-methylaniline, N·N-dipropylaniline, N-ethyl-2-methylaniline, N.N-dibutylaniline, 2.5-dimethylaniline, methylanthranilate, N.N-dimethylbenzylamine, di-isobutylamine, n-octylamine, C6 -C12 primary amines and 2-
An amine compound selected from the group consisting of ethylhexylamine is brought into contact with the amine compound at a pH of 7 or above while maintaining a temperature above the melting point of the amine compound with stirring, and the PH is lowered to 7 or below to make the amine compound water-soluble; A pigment or dye composition in the form of powder-free, easily dispersible granules, which is produced by recovering the granules that form.