CA1073880A - PROCESS FOR THE PREPARATION OF EASILY DISPERSIBLE PHTHALOCYANINE PIGMENTS OF THE .beta.-MODIFICATION - Google Patents
PROCESS FOR THE PREPARATION OF EASILY DISPERSIBLE PHTHALOCYANINE PIGMENTS OF THE .beta.-MODIFICATIONInfo
- Publication number
- CA1073880A CA1073880A CA233,796A CA233796A CA1073880A CA 1073880 A CA1073880 A CA 1073880A CA 233796 A CA233796 A CA 233796A CA 1073880 A CA1073880 A CA 1073880A
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- Prior art keywords
- alkyl
- carbon atoms
- parts
- cupc
- sulfamoyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coloring (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Abstract of the disclosure:
Copper phthalocyanines (CuPc) of the .beta.-modification are obtained in a easily dispersible form of high stability to flocculation and of high tinctorial strength when highly pure CuPc of the .beta.-modification is subjected to a mechanical fine distribution together with a compound of the formula Pc - Am wherein Pc is a phthalocyanine radical, A is a carboxy or sulfo group or a functional derivative of said groups or an aminomethylene group and ? is 1 to 6.
Copper phthalocyanines (CuPc) of the .beta.-modification are obtained in a easily dispersible form of high stability to flocculation and of high tinctorial strength when highly pure CuPc of the .beta.-modification is subjected to a mechanical fine distribution together with a compound of the formula Pc - Am wherein Pc is a phthalocyanine radical, A is a carboxy or sulfo group or a functional derivative of said groups or an aminomethylene group and ? is 1 to 6.
Description
1~73~80 The present invention relates to a process for the pre-paration of easily dispersible phthalocyanine pigments of the ~-modification.
It is known that copper phthalocyanine (CuPc) of the ~-modification which has been prepared by condensation according to the phthalic acid anhydride process and, if desired, has been extracted with dilute acid, can be brought into the pig-ment form with the use of various methods of fine distribution.
Preferred methods of fine distribution are the grinding with salt in the presence of additives preventing a phase trans-formation or the grinding in organic solvents. The products obtained according to these processes have sufficient tincto-rial strength, however, their shade and the purity of the ! shade, and various technical properties must be improved. To this effect, the crude pigment containing impurities must be purified. The German Offenlegungsschriften Nos. 2,262,911 and
It is known that copper phthalocyanine (CuPc) of the ~-modification which has been prepared by condensation according to the phthalic acid anhydride process and, if desired, has been extracted with dilute acid, can be brought into the pig-ment form with the use of various methods of fine distribution.
Preferred methods of fine distribution are the grinding with salt in the presence of additives preventing a phase trans-formation or the grinding in organic solvents. The products obtained according to these processes have sufficient tincto-rial strength, however, their shade and the purity of the ! shade, and various technical properties must be improved. To this effect, the crude pigment containing impurities must be purified. The German Offenlegungsschriften Nos. 2,262,911 and
2,262,895 describe processes according to which the crude ; pigment is converted into the CuPc-sulfate with sulfuric acid which dissolves the undesired impurities, the CuPc-sulfate is separated, the pure sulfate is hydrolized and the pure CuPc is isolated.
The pure CuPc of the ~-modification obtained upon that purification is rearranged according to known methods, for ex-ample by a thermal treatment or by the action of aromatic sol-vents, into the ~-modification. When the highly pure CuPc of the ~-modification obtained upon these purification and rearr-- angement processes is finely distributed according to one of the known mechanical processes, for example solvent grinding, pig-ments are obtained unexpectedly that do not have any colori-- . .
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stical interest because of their dull shade and their extreme lack of tinctorial strength.
The present invention is based on the discovery of a process for the preparation of easily dispersible phthalocyanine pigments of the ~-modification having high tinctorial strength and high stability towards flocculation. According to the invention, there is provided a process for the preparation of a copper phthalocyanine pigment of the ~-modification which comprises subjecting a highly pure copper phthalo-cyanine of the ~-modification to a mechanical fine distribution together with from 2% to 15% by weight, calculated on the copper phthalocyanine of the ~-modification used, of a compound of the general formula Pc - A (I) in which Pc stands for a phthalocyanine radical, A stands for identical or different groups selected from -COOM or -SO3M (where M is hydrogen, an alkali metal, an ammonium ion, or one molar equivalent of an al-kaline-earth metal, carbamoyl, sulfamoyl, N-alkylcarbamoyl of 1 to 12 carbon atoms, N-alkylsulfamoyl of 1 to 18 carbon atoms, N,N-dialkyl-sulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzylsulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexyl-sulfamoyl, N-alkyl-N-cyclohexylsulfamoyl with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenylsulfamoyl with 1 to 4 carbon atoms in the alkyl, carboalkoxy with 1 to 4 carbon atoms in the alkoxy, sulfonic acid phenyl ester, sulfonic acid alkyl ester of 1 to 4 carbon atoms, and an aminomethyl group of the formula -CH - N /
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~738~0 in which Rl is hydrogen, alkyl of 1 to 18 carbon atoms, 2-aminoethyl, benzyl, phenylethyl, phenyl, alkylphenyl ~ith 1 to 4 carbon atoms in the alkyl, alkanoyl with 1 to 4 carbon atoms in the aIkyl moiety, or benzoyl, R2 is hy-drogen or alkyl of 1 to 4 carbon atoms, or ~ and R2 together are phthaloyl;
m is 1 or 2 if A is -S03M, m is an integer of 1 to 4, if A is one of said sulfamoyl or sulfonic acid ester groups, m is an integer of 1 to 3, if A is a -COOM or, one of said carbamoyl or;carbalkoxy groups, or m is an integer of 1 to 6 (an integer of 2 to 4 is preferred), if A is said aminomethyl group.
The invention also provides a new copper phthalocyanine pigment of the ~-modification obtained by the above defined process and characterized by high tinctorial strength and by ready dispersibility and high stability to flocculation in lacquer systems.
Preferred additives of the formula I are compounds in which A are identical or different groups of the formula -COOH or -S03H and their alkali metal, calcium, barium or ammonium salts, sulfamoyl, sulfonic acid phenyl ester, N-alkylsulfamoyl of 1 to 18 carbon atoms, N~N-dialkylsulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzylsulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexylsulfamoyl, N-alkyl-N-cyclohexylsulfamoyl with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenyl-sulfamoyl with 1 to 4 carbon atoms in the alkyl, carbamoyl, or an aminoethyl group of the for3ula -CH - NHR , -CH - N / or -CH2 - N
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in which Rl is alkyl of 1 to 18 carbon atoms, phenyl or alkylphenyl with 1 to 4 carbon atoms in the alkyl, R3 and R4 are identical or different alky~ each having 1 to 4 carbon atoms; m is 1 or 2, if A stands for -COOH or -SO3H or their salts, or carbamoyl, m is 2 or 3, if A is one of said sulfamoyl or sulfonic acid ester groups, and m is 2 to 4, if A is one of said aminomethyl groups.
Suitable phthalocyanines of the general formula I
are metal containing or metal free compounds, preferably copper phthalocyanines which may carry further substituents in addition to the substituents A, such as, for example copper phthalocyanine car-boxylic acids, especially CuPc-monocarboxylic acid, -dicarboxylic acid and mixtures thereof; alkali metal, alkaline earth metal or aluminum salts of CuPc-carboxylic acids, salts of CuPc-carboxylic acids with ammonia or aliphatic amines; copper phthalocyanine sul-fonic acids and CuPc-sulfonic acid mixtures, especially copper phthalocyanine-monosulfonic acid; alkali metal and alkaline earth metal salts of copper phthalocyanine sulfonic acid, especially of copperphthalocyanine monosulfonic acid; salts of CuPc-sulfonic acids with ammonia or aliphatic amines; copper phthalocyanine carbon amides, preferably those in which m is 1 to 2 which may be alkylated by alkyl groups of 1 to 18 carbon atoms; copper phthalocyanine carboxylic acid esters; copper phthalocyanine sulfonamides, preferably those in which m is 2 to 3 which may be obtained by reacting CuPc-sulfochlorides with primary or secondary aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic amines, such as, for example am-: ~ - 5 -' ' . .
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monia, methyl amine, hexylamine~ ~-ethylhexyl amine, dodecyl amine, stearyl amine, diethyl amine, di-n-butyl amine, cyclohexyl amine, ethylene diamine, aniline, N-methyl aniline, benzyl amine, phenyl-ethyl amine; copper phthalocyanine sulfonic acid esters, for example alkyl esters or aryl esters; alkyl aminomethyl or dialkylaminomethyl copper phthalocyanines, preferably those in which m is 2 to 4, which may be obtained by reacting chloromethylated copper phthalocyanines with primary or secondary aliphatic amines, such as, for example methyl amine, butyl amine, hexyl amine, octyl amine, dodecyl amine, stearyl amine, di-n-butyl amine or ethylene diamine;
arylaminomethyl or alkylarylaminomethyl copper phthalocyanines, preferably those in which m is 2 to 4 or phthalimidomethyl copper phthalocyanines, preferably those in which m is 2 to 4 and which may be obtained by reacting copper phthalocyanines with N-methylolphthalimide.
Except for other definitions, "alkyl" and "alkanoyl" are to be understood as groups which contain from 1 to 4 carbon atoms in the alkane radical, "aryl" is preferably "phenyl" and "cycloalkyl" are groups having ~¦ 4 to 8, preferably 6 carbon atoms.
`i By "highly pure copper phthalocyanine of the ~-modification", there are to be understood products which were purified according to the methods described in German Offenlegungsschriften Nos. 2,262,911 and 2,262,895 and rearranged into the ~-modification according to known methods.
German Offenlegungsschrift No. 2,262,911 relates to a process for the preparation of highly pure copper phthalocyanine pigments of the ~-modification, which process comprises converting unsubstituted or substi-; tuted, preferably halogenated, especially chlorinated (above all those having a chlorine content of up to 6%) copper phthalocyanines having different degrees of purity by means of suitable acids which dissolve the impurities contained in the pigment, preferably sulfuric acid, into ,! .
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~73880 copper phthalocyanine salts capable of being isolated, separating them from the acid, setting free from the copper phthalocyanine salts, under the action of water, the copper phthalocyanines of the ~-modification in pure form and subjecting the isolated copper phthalocyanines ;n an aqueous suspension to a mechanical fine distribution. The starting material is preferably dissolved in sulfuric acid or oleum and the solution diluted to a concentration of acid of down to 80% by adding water or dilute sulfuric acid or the crude material is introduced into sulfuric acid of 80 to 86%
strength.
German Offenlegungsschrift No. 2,262,895 relates to a process for the purification of unsubstituted or substituted preferable halogenated, especially chlorinated ~above all those having a chlorine content of up to 6% by weight) copper phthalocyanines which comprises introducing the copper phthalocyanine into sulfuric acid of 84 to 88% strength or dissolving it at first in concentrated sulfuric acid or oleum and then adjusting it with water or dilute sulfuric acid to the concentration mentioned, subjecting the copper phthalocyanine sulfate so formed at 60 - 100C, preferably 70 -90C, in an inert gas atmosphere, preferably under nitrogen, to a process of crystal growth, isolating the copper phthalocyanine sulfate and recover-ing the copper phthalocyanine by the action of water. The sulfuric acid is used preferably in 4 to 15 times the amount, calculated on the weight of ; the starting material, and the crystal growth process is preferably carried out at a concentration of sulfuric acid of 85.5 to 86.5%.
The amount of compounds of the general formula I is in general within the range of from 2 to 15%, calculated on the CuPc of the ~-modification used.
The amount required for obtaining optimum pigments depends on the chemical constitution of the additive. ~hen CuPc-sulfonic acids are used, the most favourable amount is within the range of ~ to 6%, in the case of the .
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CuPc-carboxylic acids of 5 to 8%, and in the case of the other compounds of the general formula I of 4 to 10%.
The preparation of an effective mixture of pure CuPc of the ~-modification with an added compound of the general formula I is advantageous-ly carried out by means of the process of fine distribution required for the conditioning to the pigment, in which case the compounds of the general formula I can be added at the beginning or during the process of the fine distribution.
In principle, it is also possible to finely distribute the pure CuPc of the ~-modification and compounds of the general formula I separately and to mix the ground suspensions afterwards. The mixture of finely distributed pure CuPc of the ~-phase and finely distributed additives of the general formula I in the form of dry pigment powders, however, yields pigments of less good properties.
When CuPc-carboxylic acids are used which are very important as additives of the general formula I, an especially economical process for the preparation of the mixture is the synthesis of CuPc containing the desired amount of CuPc carboxylic acids by cosynthesis starting from phthalic acid anhydride and a small amount of trimellitic acid or other suitable benzene-polycarboxylic acids according to the phthalic acid anhydride process.
By following purification with sulfuric acid and rearrangement of the phase, the products so synthesized yield the starting products required -for the mechanical fine distribution. When other CuPc-derivatives of the general formula I are used, that kind of cosynthesis is not expedient.
When CuPc-sulfonic acids are used as additive, a separate synthesis is not necessary, as in the course of the purification of the CuPc by reprecipitation from sulfuric acid the CuPc can partially be sulfonated.
The added CuPc-sulfonic acids and CuPc-carboxylic acids can be converted , . .
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, into the salts mentioned during or after the fine distribution by reacting them with bases or with amines.
Suitable mechanical fine distribution processes are the generally known ones, for example salt grinding in mills or kneaders, preferably the grinding in a liquid grinding medium in a roller mill, a vibration mill, a bead mill or a stirrer ball mill with the aid of the grinding bodies and under the conditions generally used in practice.
Suitable grinding media are above all organic liquids and mixtures of water with organic liquids. Water can be used only to a limited extent because of the partial rearrangement of the phases into the a-phase. Suit-able organic liquids are aliphatic and aromatic compounds. When aromatic liquids are used, for example xylene, a prior rearrangement of phases of the purified CuPc of the ~-phase can be dispensed with because the use of .~:
such grinding media allows the rearrangement of phases into the ~-phase, the mixture with an additive and the fine distribution to be carried out in a single-step operation.
Preferred mixtures of water with organic liquids are homogenous mixtures of water with primary, secondary or tertiary aliphatic aIcohols having from 1 to 6 carbon atoms. Should coarser grains be required for determined application fields, an after-treatment of the ground pigment in organic or aqueous-organic media at elevated temperature may be advan-tageous. The pigments are isolated according to known methods, preferably by evaporation or spray-drying.
~; The pigment~ prepared according to ~he process of the invention are suitable for dyeing lacquers, paper, plastics and synthetic resins, synthetic fibers in the mass, for printing paper, textiles, films and sheets and other materials and for metal effect lacquerings as well as paints.
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. . , : . . -1~73880 The addition of the above-mentioned phthalocyanine derivatives of the general formula I to phthalocyanines has been described in U.S. Patents Nos. 2,526,345 and 3,028,392 and in German Patent No. 1,239,270. The pigment mixtures described there;n show an improved stabilty towards flocculation, however, they have a low tinctorial strength and a bad dispersibility. In comparison thereto, the addition of these phthalo-cyanine derivatives to highly pure phthalocyanines yields pigments having a clear shade and a distinctly improved dispersibility and tinctorial strength.
The following Examples illustrate the invention, the parts and percentages being by weight.
E X A M P L E l:
For the preparation of copper phthalocyanine which contains about 8%
- calculated on the pure pigment - of copper phthalocyanine carboxylic acid, 1400 parts of nitrobenzene, 740 parts of phthalic acid anhydride, 21 parts of trimellitic acid, 1170 parts of urea, 85 parts of ammonium chloride, 240 parts of anhydrous copper sulfate and 1 part of ammonium molybdate were mixed and heated to 200C within 8 hours while stirring. The mixture was after-stirred at 200C for 4 hours and after turning off the heating, 200 parts of nitrobenzene were added. The suspension was cooled to room temperature, filtered and washed with nitrobenzene; the filter cake was then washed with methanol and then with water. The moist filter cake was introduced into a mixture of 2,000 parts of water and 1,000 parts of ~ concentrated hydrochloric acid, stirred at 90C for 5 hours, filtered and ; washed with water until neutral. The filter cake was dried at 100C. 716 Parts of a 93% crude copper-phthalocyanine were obtained that contained about 8% - calculated on the pure dye - of copper phthalocyanine carboxylic acid.
1~731~80 For the preparation of the pure dye, 21.5 parts of the crude dye obtained were introduced in 215 parts of 86% sulfuric acid and the mixture was stirred for 4 hours at 7Q - 80C in a nitrogen atmosphere. The mixture was cooled to room temperature and the sulfuric acid concentration was adjusted to 75% with 31.5 parts of water. The mixture of the sulfates of copper phthalocyanine and copper phthalocyanine carboxylic acid was filtered off, washed with 75% sulfuric acid and then hydrolized in 250 parts of water. The dye was filtered off and washed until neutral. For the rearrangement into the ~-modification, the moist filter cake was stirred in 200 parts of water, 20 parts of chlorobenzene were added and the mixture was stirred at 100C for 5 hours. The chlorobenzene was distilled off with steam, the aqueous dye suspension was filtered and the filter cake was dried at 100C.
20 Parts of pure copper phthalocyanine of the ~-modification were obtained which contained about 8% of copper phthalocyanine carboxylic acid being mainly in the form of the copper phthalocyanine monocarboxylic acid.
To bring it into the pigment form, the pure dye was ground with 120 parts of acetone and 1,200 parts of glass beads of a 2 mm diameter in a porcelain mill for about 20 hours on a vibration table. Then, the pigment was isolated and dried at 60C under reduced pressure. The pigment so prepared serves for the dyeing of enamels according to known methods in brilliant, greenish blue shades of high degree of purity and high color intensity. As compared with known commercial dyestuffs, the pigment of the invention is distinguished by a very good flocculation stability and an excellent dispérsibility in lacquering systems.
When the fine distribution is effected with a mixture of 8.4 parts of isobutanol and 111.4 parts of water or a mixture of 60 parts of iso-propanol and 60 parts of water as grinding medium instead of 120 parts of - :: . : : .
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1~73880 acetone, the pigments obtained already after a shorter grinding period have the same quality.
E X A M P L E 2:
22.2 Parts of unsubstituted crude copper phthalocyanine ~in the form of a 90% commercial product) were introduced into 200 parts of a 86%
sulfuric acid and stirred at 70C to 80DC for 4 hours in a nitrogen atmosphere. The copper phthalocyanine sulfate obtained in the form of coarse crystals was filtered off, washed with 80% sulfuric acid and -hydrolized in 250 parts of water. Then, the dye was filtered off and washed until neutral. The moist filter cake was introduced into 200 parts of water to perform the rearrangement of the ~-modification into the ~-modification, 20 parts of chlorobenzene were added and the mixture was stirred at 100C for 5 hours. Then the chlorobenzene was eliminated by steam distillation, the aqueous dyestuff suspension was filtered and the filter cake was dried at 100C. 20 Parts of 100% pure copper phthalo-cyanine of the ~-modification were obtained.
For the fine distribution, the pure dyestuff obtained and 1.2 parts of copperphthalocyanine-4-carboxylic acid were ground with 120 parts of acetone and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill for about 20 hours on the "Vibratom" vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was isolated and dried at 60C under reduced pressure.
The pigment so obtained yields in the dyeing of enamels according to known methods especially brilliant greenish blue shades of a high tinctorial strength and a good stability towards flocculation. As compared wi~h known commercial dyestuffs, the pigment of the invention is distin-guished by a high degree of purity of the shade and an excellent dispersi-bility in lacquering systems.
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The pigment yields in polyvinyl chloride according to known methods dyeings of high color intensity and a high degree of purity and good dispersibility.
When instead of 120 parts of acetone 120 parts of methanol or 120 parts of isopropanol or 120 parts of glycolmonomethyl ether or 120 parts of acetic acid-n-butyl ester were used as grinding medium, pigments of equal quality were obtained. When the fine distribution is obtained not by vibration grinding but by a continuous grinding in a bead mill, pigments of equal quality were also obtained.
The fine distribution could also be performed with good success by grinding on a roller mill.
E X A M P L E 3:
When the 1.2 parts of copper phthalocyanine monocarboxylic acid indicated in Example 2 were replaced by 1.2 parts of copper phthalocyanine-4,4'-dicarboxylic acid and the grinding and working up was performed as described in Example 2, a pigment was obtàined which corresponded to the pigment obtained in Example 2 with respect to its coloristal properties.
E X A M P L E 4:
When the 1.2 parts of copper phthalocyanine monocarboxylic acid indicated in Example 2 were replaced by a mixture of 1 part of copper phthalocyanine-4 carboxylic acid and 0.2 part of copper phthalocyanine-4-carboxylic acid amide and the grinding and working up was carried out as indicated in Example 2, a pigment was obtained which corresponded to that indicated in Example 2 with respect to its coloristical properties.
E X A M P L E 5:
20 Parts of pure copper phthalocyanine of the ~-modification (obtained according to the method described in Example 2) and 2 parts of the sodium salt of copper phthalocyanine-4-carboxylic acid were ground : . , .: , - , . ~ - :
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1(~7388~) together with 120 parts of acetone and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill during about 20 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment ~as isolated and dried at 60C under reduced pressure.
The pigment so obtained corresponded to that obtained according to Example 2 with respect to its coloristical behaviour.
~hen instead of 2 parts of the sodium salt of copper phthalocyanine monocarboxylic acid 2 parts of the barium salt of copper phthalocyanine monocarboxylic acid were used as additive, a pigment was obtained which had the same properties.
E X A M P L E 6:
32.6 Parts of unsubstituted crude CuPc (in the form of a 93%
commercial product) were introduced into 300 parts of a 86% sulfuric acid and stirred at 70 to 80C for 4 hours in a nitrogen atmosphere. The so obtained CuPc-sulfate in the form of coarse crystals was filtered off after cooling to room temperature, washed with 80% sulfuric acid and then hydrolized by introducing the filter cake into 300 parts of water. The ; copper phthalocyanine was filtered off and washed with water until neutral.
In order to attain the rearrangement of phases from the a-modification into the ~-modification, the moist filter cake was introduced into 300 parts of water, 30 parts of chlorobenzene were added and the mixture was boiled ` under reflux for 4 hours. Then, the chlorobenzene was removed by steam ; distillation.
The pigment suspension was filtered and the filter cake was dried at 100 C. 30 Parts of pure CuPc of the ~-modification were obtained.
For the fine distribution, the 30 parts of the pure CuPc so obtained were ground after the addition of 1.2 parts of CuPc-monosulfonic acid ~' .
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1~7388~
(prepared by sulfonation of CuPc in oleum and having a sulfur content of 5.1%) together with 150 parts of isopropanol and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill during 20 hours on a "Vibratom" vibration table. Then, the pigment suspension was separated from the grinding media. The pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained which had a specific surface of about 70 m /g yielded upon dyeing enamels according to known methods brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distinguished as compared with known commercial brands by a good stability towards flocculation and an excellent dispersibility in lacquering systems.
When used in book printing according to known methods, the pigment so obtained yielded prints that were distinguished by a high tinctorial strength and an especially high purity of shade.
When the grinding medium used in the fine distribution is 150 parts of methanol or 150 parts of glycolmonomethyl ether or 120 parts of acetone, instead of the 150 parts of isopropanol, pigments of the same quality were obtained.
When the additive used for the fine distribution is 1.5 parts of 1.8 parts of CuPc-monosulfonic acid instead of the 1.2 parts of CuPc-monosulfonic acid, pigments of the same quality were obtained.
However, when instead of 1.2 parts of ~uPc-monosulfonic acid 3 parts of this compound were used, pigments were obtained which were dis-tinguished in the dyeing of lacquers by a very high transparency and an excellent tinctorial strength, but which had a minor dispers-ibility.
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lC~73880 E X A M P L E 7:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and 1.2 parts of CuPc-monosulfonic acid were ground together with 1,200 parts of glass beads of 3 mm diameter and a mixture of 139 parts of water and 11 parts of isobutanol in a porcelain mill during 24 hours on a "Vibratom" vibration table. Then, thc pigment suspension was separated from the grinding bodies. The pigment was isolated by filtration and dried ~-at 60C under reduced pressure.
Upon dyeing enamels according to known methods, the pigment so prepared yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distinguished by an excellent dispersibility in lacquers.
When instead of the mixture of 139 parts of water and 11 parts of isobutanol a mixture of 75 parts of water and 75 parts of isopropanol or a mixture of 112 parts of water and 38 parts of isopropanol was used, pigments were obtained which had the same quality.
Pigments of the same quality were also obtained when the fine distribution was not performed discontinuously on a "Vibratom" vibration table, but continuously on a continuous vibration mill or a continuous roller mill.
E X A M P L E 8:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and 3 parts of the sodium salt of CuPc-monosulfonic acid were ground together with 150 parts of isopropanol and 1,200 parts of quartzite beads of 2 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. ThenJ the pigment suspension was separated from the grinding bodies and the pigment was isolated by distilling off the solvent.
.:
' - ~
1~7388~) When dyeing enamels accordin~ to known methods, the pigment so obtained yielded brilliant greenish blue shades of high tinctorial strength. The pigment was distinguished by a very good dispersibility in lacquers.
Pigments of the same quality were obtained when instead of 3 parts of the sodium salt 3 parts of the barium salt or 3 parts of the ammonium salt of CuPc-monosulfonic acid were used as additive.
E X A M P L E 9:
32.6 Parts of unsubstituted crude CuPc ~in the form of a 93%
commercial product) were introduced into 300 parts of 86% sulfuric acid and then stirred for 4 hours at 70 - 80C in a nitrogen atmosphere. The coarse crystals of CuPc-sulfate so obtained were filtered off after cooling to room temperature, washed with 80% sulfuric acid and then hydrolized by introducing the filter cake into 300 parts of water. The CuPc was filtered off, washed with water until neutral and dried at 100C. 30 Parts of coarse crystals of pure CuPc of the ~-modification were obtained.
For the rearrangement of the phases and the fine distribution at the same time the pure CuPc of the ~-modification was ground after the addition of 1.5 parts of CuPc-monosulfonic acid together with 150 parts of xylene and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was - isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained, which is in the form of the ~-crystal modification yielded upon dyeing enamels colorings of high tinctorial strength. The pigment was distinguished by a very good dispersibility in lacquers.
.` :
,` -.
.. . . ..
- '' : . :' ' '. -' '', . :
- - . . . . ., . :
.. . . . : , ..
,:. , : . . . : . .
1~7388~1 E X A M P L E 10:
95 Parts of unsubstituted crude CuPc ~in form of a 95% commercial product) and 7.5 parts of CuPc-monosulfonic acid were dissolved together in 1,000 parts of 96% sulfuric acid. At 70 to 80C, 116 parts of water were added dropwise and the suspension was stir~ed at 70 - 80C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the CuPc-sulfate was filtered off, washed with 80% sulfuric acid and the filter cake was hydrolized in 1,000 parts of water. To the suspension, 100 parts of chlorobenzene were added and the suspension was boiled under reflux for 4 hours. The chlorobenzene was eliminated by steam distillation.
The pigment was isolated by filtration, washed with water until neutral and dried at 100C.
30 Parts of the pure pigment so obtained which was in the form of the ~-modification and contained about 6% of CuPc-monosulfonic acid, were ground with 150 parts of isopropanol and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. Then, the pigment was isolated by filtration and dried at 60C
under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength.
The pigment was distinguished by a very good dispersibility in lacquers.
E X A M P L E 11:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 were subjected after the addition of a mixture of 0.9 part of CuPc-monosulfonic acid and 0.3 part of CuPc-disulfonic acid to the process of fine distribution as described in Example 6. The pigment obtained corresponded to that obtained according to Example 6 with respect to its quality.
~ . - .
16~7388~) E X A M P L E 12:
30 Parts of t~e pure CuPc of the ~-modification according to Example 6 and 1.5 parts of N,N'-bis~dodecyl)-CuPc-disulfonamide (prepared by reacting dodecyl amine with the dichloride of CuPc-disulfonic acid) were ground together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of acetone in a porcelain mill during 20 hours on a "Vibratom"
vibration table. The pigment suspension was then separated from the grinding bodies and the pigment was isolated by evaporation.
When dyeing enamels according to known methods the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment dyestuff was distinguished by an excellent dispersibility.
When instead of 1.5 parts of the above sulfonamide - additive a mixture of 1.2 parts of N,N'-bis-(isobutyl~-CuPc-disulfonamide and 0.3 part of N,N',N"-tris-(isobutyl)-CuPc-trisulfonamide was used as additive, a pigment was obtained which had the same quality.
E X A M P L E 13:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and 1.5 parts of N,N'-bis-(phenyl)-CuPc-disulfonamide were ground together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of isopropanol in a porcelain mill during 24 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was isolated by filtration and dried at 60C
under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength.
The pigment was distinguished by a very good dispersibility in lacquering systems.
, ~ . , , ~ , `
. ' , . , : - ~ : ' ' " ~ ' 1~73880 Pigments of the same quality were obtained, when instead of N,N'-bis-(phenyl)-CuPc-disulfonamide one of the following compounds was used as additive:
CuPc-disulfonamide N,N'-bis-(di-n-butyl)-CuPc-disulfonamide N,N'-bis-(a-ethylhexyl)-CuPc-disulfonamide N,N'-bis-(octadecyl)-CuPc-disulfonamide N,N'-bis-(~-aminoethyl)-CuPc-disulfonamide CuPc-disulfonic acld diphenyl ester E X A M P L E 14:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and a mixture of 1.3 parts of N,N'-bis-(di-n-butyl)-CuPc-; Disulfonamide and 0.3 part of N,N',N"-tris-(di-n-butyl)-CuPc-trisulfonamide (prepared by reacting a corresponding mixture of CuPc-disulfochloride and CuPc-trisulfochloride with di-n-butyl amine) were ground together with 1,200 parts of glass beads of 2 mm diameter, 139 parts of water and 11 parts of isobutanol in a porcelain mill during 24 hours on a "Vibratom"
vibration table. The pigment suspension was separated from the grinding bodies and the pigment was isolated by filtration and dried at 60C under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant shades of a high degree of purity and tinctorial strength.
When dyeing polyvinyl chloride according to known methodsJ the pigment was easily dispersible and yielded dyeings that were distinguished by a high tinctorial strength and an extraordinary degree of purity of the shade.
When the fine distribution was performed not discontinuously on a vibration table but continuously in a bead mill of the type "~olinex" of Messrs. Netzsch with glass beads of 1 mm diameter, a pigment was obtained ;
:
.
which had the same quality.
E X A M P L E 15:
32.6 Parts of unsubstituted crude CuPc (in the form of a 93%
commercial product) were introduced into 300 parts of 86% sulfuric acid and stirred during 4 hours at 70 - 80C in a nitrogen atmosphere. The coarse crystals of the CuPc-sulfate so formed were filtered off after cooling to room temperature, washed with 80% sulfuric acid and then hydrolized by introducing the filter cake into 300 parts of water. The CuPc was filtered off and washed with water until neutral.
To obtain the rearrangement of the phases from the~-modification into the ~-modification, the moist filter cake was introduced into 300 parts of water, 30 parts of chlorobenzene were added and the mixture was stirred under reflux during 4 hours. The chlorobenzene was removed by steam distillation.
The pigment suspension was filtered and the filter cake was dried at 100C.
30 Parts of pure CuPc of the ~-modification were obtained.
For the fine filter distribution, the 30 parts of the pure CuPc so obtained were ground after the addition of 3 parts of tris-(isobutylamino-methyl)-CuPc ~prepared by reacting tris-(chloromethyl)-CuPc with isobutyl amine) together with 150 parts of isopropanol and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was isolated by filtration and dried a~
60C under reduced pressure.
When dyeing enamels according to known methods, the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strengthJ and an excellent fastness to light and to ~' atmospheric influences. The pigment was distinguished by a good stability towards flocculation and excellent dispersibility in lacquering systems.
` :.
',: ' . .~ , .: . : . .
,.. . ~
. , .. : . . .
~738~3~
When the grinding medium in the fine distribution was 150 parts of methanol, 150 parts of glycolmonomethyl ether or 120 parts of acetone instead of the 150 parts of isopropanol, the pigment obtained had the same quality.
The same result was obtained when the fine distribution was not effected discontinuously on a "Vibratom" vibration table, but continuously on a continuously operating vibration mill or roller mill E X A M P L E 16:
30 Parts of the pure CuPc of the ~-modification prepared according to Example 15 and a mixture of 0.5 part of bis-(isobutylaminomethyl)CuPc and 2 parts of tris-(isobutylaminomethyl)-CuPc and 0.5 part of tetrakis-~iso-butylaminomethyl)-CuPc were introduced into 150 parts of isopropanol and stirred until a homogeneous suspension had formed. The suspension was ground continuously on a continuously operating bead mill of the type "Molinex" with the use of glass beads of 1 mm diameter. The pigment was isolated by distilling of the solvent. The pigment so obtained corresponded to that obtained according to Example 15 with respect to its quality.
E X A M P L E 17:
~!
30 Parts of the pure CuPc of the ~-modification obtained according to Example 15 and 3 parts of tris-(n-octylaminomethyl)-CuPc were ground i 20 together with 150 parts of acetone and 1,200 parts of quartzite beads of
The pure CuPc of the ~-modification obtained upon that purification is rearranged according to known methods, for ex-ample by a thermal treatment or by the action of aromatic sol-vents, into the ~-modification. When the highly pure CuPc of the ~-modification obtained upon these purification and rearr-- angement processes is finely distributed according to one of the known mechanical processes, for example solvent grinding, pig-ments are obtained unexpectedly that do not have any colori-- . .
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.
-1~738~
stical interest because of their dull shade and their extreme lack of tinctorial strength.
The present invention is based on the discovery of a process for the preparation of easily dispersible phthalocyanine pigments of the ~-modification having high tinctorial strength and high stability towards flocculation. According to the invention, there is provided a process for the preparation of a copper phthalocyanine pigment of the ~-modification which comprises subjecting a highly pure copper phthalo-cyanine of the ~-modification to a mechanical fine distribution together with from 2% to 15% by weight, calculated on the copper phthalocyanine of the ~-modification used, of a compound of the general formula Pc - A (I) in which Pc stands for a phthalocyanine radical, A stands for identical or different groups selected from -COOM or -SO3M (where M is hydrogen, an alkali metal, an ammonium ion, or one molar equivalent of an al-kaline-earth metal, carbamoyl, sulfamoyl, N-alkylcarbamoyl of 1 to 12 carbon atoms, N-alkylsulfamoyl of 1 to 18 carbon atoms, N,N-dialkyl-sulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzylsulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexyl-sulfamoyl, N-alkyl-N-cyclohexylsulfamoyl with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenylsulfamoyl with 1 to 4 carbon atoms in the alkyl, carboalkoxy with 1 to 4 carbon atoms in the alkoxy, sulfonic acid phenyl ester, sulfonic acid alkyl ester of 1 to 4 carbon atoms, and an aminomethyl group of the formula -CH - N /
,~
. ~ - 3 -: . . . . . . : . . : -- -: . : . - -. - . : - .
, . . : :
.-: . . ~ . :
,' " ' '' ' ' ' ~
~738~0 in which Rl is hydrogen, alkyl of 1 to 18 carbon atoms, 2-aminoethyl, benzyl, phenylethyl, phenyl, alkylphenyl ~ith 1 to 4 carbon atoms in the alkyl, alkanoyl with 1 to 4 carbon atoms in the aIkyl moiety, or benzoyl, R2 is hy-drogen or alkyl of 1 to 4 carbon atoms, or ~ and R2 together are phthaloyl;
m is 1 or 2 if A is -S03M, m is an integer of 1 to 4, if A is one of said sulfamoyl or sulfonic acid ester groups, m is an integer of 1 to 3, if A is a -COOM or, one of said carbamoyl or;carbalkoxy groups, or m is an integer of 1 to 6 (an integer of 2 to 4 is preferred), if A is said aminomethyl group.
The invention also provides a new copper phthalocyanine pigment of the ~-modification obtained by the above defined process and characterized by high tinctorial strength and by ready dispersibility and high stability to flocculation in lacquer systems.
Preferred additives of the formula I are compounds in which A are identical or different groups of the formula -COOH or -S03H and their alkali metal, calcium, barium or ammonium salts, sulfamoyl, sulfonic acid phenyl ester, N-alkylsulfamoyl of 1 to 18 carbon atoms, N~N-dialkylsulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzylsulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexylsulfamoyl, N-alkyl-N-cyclohexylsulfamoyl with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenyl-sulfamoyl with 1 to 4 carbon atoms in the alkyl, carbamoyl, or an aminoethyl group of the for3ula -CH - NHR , -CH - N / or -CH2 - N
o . ~
., ' - ` ' ' ', ~73~8V
in which Rl is alkyl of 1 to 18 carbon atoms, phenyl or alkylphenyl with 1 to 4 carbon atoms in the alkyl, R3 and R4 are identical or different alky~ each having 1 to 4 carbon atoms; m is 1 or 2, if A stands for -COOH or -SO3H or their salts, or carbamoyl, m is 2 or 3, if A is one of said sulfamoyl or sulfonic acid ester groups, and m is 2 to 4, if A is one of said aminomethyl groups.
Suitable phthalocyanines of the general formula I
are metal containing or metal free compounds, preferably copper phthalocyanines which may carry further substituents in addition to the substituents A, such as, for example copper phthalocyanine car-boxylic acids, especially CuPc-monocarboxylic acid, -dicarboxylic acid and mixtures thereof; alkali metal, alkaline earth metal or aluminum salts of CuPc-carboxylic acids, salts of CuPc-carboxylic acids with ammonia or aliphatic amines; copper phthalocyanine sul-fonic acids and CuPc-sulfonic acid mixtures, especially copper phthalocyanine-monosulfonic acid; alkali metal and alkaline earth metal salts of copper phthalocyanine sulfonic acid, especially of copperphthalocyanine monosulfonic acid; salts of CuPc-sulfonic acids with ammonia or aliphatic amines; copper phthalocyanine carbon amides, preferably those in which m is 1 to 2 which may be alkylated by alkyl groups of 1 to 18 carbon atoms; copper phthalocyanine carboxylic acid esters; copper phthalocyanine sulfonamides, preferably those in which m is 2 to 3 which may be obtained by reacting CuPc-sulfochlorides with primary or secondary aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic amines, such as, for example am-: ~ - 5 -' ' . .
, ~ ~ ' ' . ' - . - ' .
- . . -.. . . .
.
. .
monia, methyl amine, hexylamine~ ~-ethylhexyl amine, dodecyl amine, stearyl amine, diethyl amine, di-n-butyl amine, cyclohexyl amine, ethylene diamine, aniline, N-methyl aniline, benzyl amine, phenyl-ethyl amine; copper phthalocyanine sulfonic acid esters, for example alkyl esters or aryl esters; alkyl aminomethyl or dialkylaminomethyl copper phthalocyanines, preferably those in which m is 2 to 4, which may be obtained by reacting chloromethylated copper phthalocyanines with primary or secondary aliphatic amines, such as, for example methyl amine, butyl amine, hexyl amine, octyl amine, dodecyl amine, stearyl amine, di-n-butyl amine or ethylene diamine;
arylaminomethyl or alkylarylaminomethyl copper phthalocyanines, preferably those in which m is 2 to 4 or phthalimidomethyl copper phthalocyanines, preferably those in which m is 2 to 4 and which may be obtained by reacting copper phthalocyanines with N-methylolphthalimide.
Except for other definitions, "alkyl" and "alkanoyl" are to be understood as groups which contain from 1 to 4 carbon atoms in the alkane radical, "aryl" is preferably "phenyl" and "cycloalkyl" are groups having ~¦ 4 to 8, preferably 6 carbon atoms.
`i By "highly pure copper phthalocyanine of the ~-modification", there are to be understood products which were purified according to the methods described in German Offenlegungsschriften Nos. 2,262,911 and 2,262,895 and rearranged into the ~-modification according to known methods.
German Offenlegungsschrift No. 2,262,911 relates to a process for the preparation of highly pure copper phthalocyanine pigments of the ~-modification, which process comprises converting unsubstituted or substi-; tuted, preferably halogenated, especially chlorinated (above all those having a chlorine content of up to 6%) copper phthalocyanines having different degrees of purity by means of suitable acids which dissolve the impurities contained in the pigment, preferably sulfuric acid, into ,! .
'. ' , . '~, . .,' , ~ . ' ' '' ' ' . ~
.
.
~73880 copper phthalocyanine salts capable of being isolated, separating them from the acid, setting free from the copper phthalocyanine salts, under the action of water, the copper phthalocyanines of the ~-modification in pure form and subjecting the isolated copper phthalocyanines ;n an aqueous suspension to a mechanical fine distribution. The starting material is preferably dissolved in sulfuric acid or oleum and the solution diluted to a concentration of acid of down to 80% by adding water or dilute sulfuric acid or the crude material is introduced into sulfuric acid of 80 to 86%
strength.
German Offenlegungsschrift No. 2,262,895 relates to a process for the purification of unsubstituted or substituted preferable halogenated, especially chlorinated ~above all those having a chlorine content of up to 6% by weight) copper phthalocyanines which comprises introducing the copper phthalocyanine into sulfuric acid of 84 to 88% strength or dissolving it at first in concentrated sulfuric acid or oleum and then adjusting it with water or dilute sulfuric acid to the concentration mentioned, subjecting the copper phthalocyanine sulfate so formed at 60 - 100C, preferably 70 -90C, in an inert gas atmosphere, preferably under nitrogen, to a process of crystal growth, isolating the copper phthalocyanine sulfate and recover-ing the copper phthalocyanine by the action of water. The sulfuric acid is used preferably in 4 to 15 times the amount, calculated on the weight of ; the starting material, and the crystal growth process is preferably carried out at a concentration of sulfuric acid of 85.5 to 86.5%.
The amount of compounds of the general formula I is in general within the range of from 2 to 15%, calculated on the CuPc of the ~-modification used.
The amount required for obtaining optimum pigments depends on the chemical constitution of the additive. ~hen CuPc-sulfonic acids are used, the most favourable amount is within the range of ~ to 6%, in the case of the .
::,, :, - , , . : . . ~
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-: . . - . . . :.
.. . : . .
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,. . . ~ . : ., 1C~7388U
CuPc-carboxylic acids of 5 to 8%, and in the case of the other compounds of the general formula I of 4 to 10%.
The preparation of an effective mixture of pure CuPc of the ~-modification with an added compound of the general formula I is advantageous-ly carried out by means of the process of fine distribution required for the conditioning to the pigment, in which case the compounds of the general formula I can be added at the beginning or during the process of the fine distribution.
In principle, it is also possible to finely distribute the pure CuPc of the ~-modification and compounds of the general formula I separately and to mix the ground suspensions afterwards. The mixture of finely distributed pure CuPc of the ~-phase and finely distributed additives of the general formula I in the form of dry pigment powders, however, yields pigments of less good properties.
When CuPc-carboxylic acids are used which are very important as additives of the general formula I, an especially economical process for the preparation of the mixture is the synthesis of CuPc containing the desired amount of CuPc carboxylic acids by cosynthesis starting from phthalic acid anhydride and a small amount of trimellitic acid or other suitable benzene-polycarboxylic acids according to the phthalic acid anhydride process.
By following purification with sulfuric acid and rearrangement of the phase, the products so synthesized yield the starting products required -for the mechanical fine distribution. When other CuPc-derivatives of the general formula I are used, that kind of cosynthesis is not expedient.
When CuPc-sulfonic acids are used as additive, a separate synthesis is not necessary, as in the course of the purification of the CuPc by reprecipitation from sulfuric acid the CuPc can partially be sulfonated.
The added CuPc-sulfonic acids and CuPc-carboxylic acids can be converted , . .
- : .
. ~ .
..... ~
, into the salts mentioned during or after the fine distribution by reacting them with bases or with amines.
Suitable mechanical fine distribution processes are the generally known ones, for example salt grinding in mills or kneaders, preferably the grinding in a liquid grinding medium in a roller mill, a vibration mill, a bead mill or a stirrer ball mill with the aid of the grinding bodies and under the conditions generally used in practice.
Suitable grinding media are above all organic liquids and mixtures of water with organic liquids. Water can be used only to a limited extent because of the partial rearrangement of the phases into the a-phase. Suit-able organic liquids are aliphatic and aromatic compounds. When aromatic liquids are used, for example xylene, a prior rearrangement of phases of the purified CuPc of the ~-phase can be dispensed with because the use of .~:
such grinding media allows the rearrangement of phases into the ~-phase, the mixture with an additive and the fine distribution to be carried out in a single-step operation.
Preferred mixtures of water with organic liquids are homogenous mixtures of water with primary, secondary or tertiary aliphatic aIcohols having from 1 to 6 carbon atoms. Should coarser grains be required for determined application fields, an after-treatment of the ground pigment in organic or aqueous-organic media at elevated temperature may be advan-tageous. The pigments are isolated according to known methods, preferably by evaporation or spray-drying.
~; The pigment~ prepared according to ~he process of the invention are suitable for dyeing lacquers, paper, plastics and synthetic resins, synthetic fibers in the mass, for printing paper, textiles, films and sheets and other materials and for metal effect lacquerings as well as paints.
' ::
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., . , . - , .- ~ ' ,' ,, - ~ ~:'-', ,. . . , ~ ..
. . , : . . -1~73880 The addition of the above-mentioned phthalocyanine derivatives of the general formula I to phthalocyanines has been described in U.S. Patents Nos. 2,526,345 and 3,028,392 and in German Patent No. 1,239,270. The pigment mixtures described there;n show an improved stabilty towards flocculation, however, they have a low tinctorial strength and a bad dispersibility. In comparison thereto, the addition of these phthalo-cyanine derivatives to highly pure phthalocyanines yields pigments having a clear shade and a distinctly improved dispersibility and tinctorial strength.
The following Examples illustrate the invention, the parts and percentages being by weight.
E X A M P L E l:
For the preparation of copper phthalocyanine which contains about 8%
- calculated on the pure pigment - of copper phthalocyanine carboxylic acid, 1400 parts of nitrobenzene, 740 parts of phthalic acid anhydride, 21 parts of trimellitic acid, 1170 parts of urea, 85 parts of ammonium chloride, 240 parts of anhydrous copper sulfate and 1 part of ammonium molybdate were mixed and heated to 200C within 8 hours while stirring. The mixture was after-stirred at 200C for 4 hours and after turning off the heating, 200 parts of nitrobenzene were added. The suspension was cooled to room temperature, filtered and washed with nitrobenzene; the filter cake was then washed with methanol and then with water. The moist filter cake was introduced into a mixture of 2,000 parts of water and 1,000 parts of ~ concentrated hydrochloric acid, stirred at 90C for 5 hours, filtered and ; washed with water until neutral. The filter cake was dried at 100C. 716 Parts of a 93% crude copper-phthalocyanine were obtained that contained about 8% - calculated on the pure dye - of copper phthalocyanine carboxylic acid.
1~731~80 For the preparation of the pure dye, 21.5 parts of the crude dye obtained were introduced in 215 parts of 86% sulfuric acid and the mixture was stirred for 4 hours at 7Q - 80C in a nitrogen atmosphere. The mixture was cooled to room temperature and the sulfuric acid concentration was adjusted to 75% with 31.5 parts of water. The mixture of the sulfates of copper phthalocyanine and copper phthalocyanine carboxylic acid was filtered off, washed with 75% sulfuric acid and then hydrolized in 250 parts of water. The dye was filtered off and washed until neutral. For the rearrangement into the ~-modification, the moist filter cake was stirred in 200 parts of water, 20 parts of chlorobenzene were added and the mixture was stirred at 100C for 5 hours. The chlorobenzene was distilled off with steam, the aqueous dye suspension was filtered and the filter cake was dried at 100C.
20 Parts of pure copper phthalocyanine of the ~-modification were obtained which contained about 8% of copper phthalocyanine carboxylic acid being mainly in the form of the copper phthalocyanine monocarboxylic acid.
To bring it into the pigment form, the pure dye was ground with 120 parts of acetone and 1,200 parts of glass beads of a 2 mm diameter in a porcelain mill for about 20 hours on a vibration table. Then, the pigment was isolated and dried at 60C under reduced pressure. The pigment so prepared serves for the dyeing of enamels according to known methods in brilliant, greenish blue shades of high degree of purity and high color intensity. As compared with known commercial dyestuffs, the pigment of the invention is distinguished by a very good flocculation stability and an excellent dispérsibility in lacquering systems.
When the fine distribution is effected with a mixture of 8.4 parts of isobutanol and 111.4 parts of water or a mixture of 60 parts of iso-propanol and 60 parts of water as grinding medium instead of 120 parts of - :: . : : .
. . , : ~ :
.: : . .: : -~ `
1~73880 acetone, the pigments obtained already after a shorter grinding period have the same quality.
E X A M P L E 2:
22.2 Parts of unsubstituted crude copper phthalocyanine ~in the form of a 90% commercial product) were introduced into 200 parts of a 86%
sulfuric acid and stirred at 70C to 80DC for 4 hours in a nitrogen atmosphere. The copper phthalocyanine sulfate obtained in the form of coarse crystals was filtered off, washed with 80% sulfuric acid and -hydrolized in 250 parts of water. Then, the dye was filtered off and washed until neutral. The moist filter cake was introduced into 200 parts of water to perform the rearrangement of the ~-modification into the ~-modification, 20 parts of chlorobenzene were added and the mixture was stirred at 100C for 5 hours. Then the chlorobenzene was eliminated by steam distillation, the aqueous dyestuff suspension was filtered and the filter cake was dried at 100C. 20 Parts of 100% pure copper phthalo-cyanine of the ~-modification were obtained.
For the fine distribution, the pure dyestuff obtained and 1.2 parts of copperphthalocyanine-4-carboxylic acid were ground with 120 parts of acetone and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill for about 20 hours on the "Vibratom" vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was isolated and dried at 60C under reduced pressure.
The pigment so obtained yields in the dyeing of enamels according to known methods especially brilliant greenish blue shades of a high tinctorial strength and a good stability towards flocculation. As compared wi~h known commercial dyestuffs, the pigment of the invention is distin-guished by a high degree of purity of the shade and an excellent dispersi-bility in lacquering systems.
~, : - ' . ' . , :' .
~ -. ' ' . ~ ''.' - ' ~' ; ' ~ , . , ,, ' 1C~7388~
The pigment yields in polyvinyl chloride according to known methods dyeings of high color intensity and a high degree of purity and good dispersibility.
When instead of 120 parts of acetone 120 parts of methanol or 120 parts of isopropanol or 120 parts of glycolmonomethyl ether or 120 parts of acetic acid-n-butyl ester were used as grinding medium, pigments of equal quality were obtained. When the fine distribution is obtained not by vibration grinding but by a continuous grinding in a bead mill, pigments of equal quality were also obtained.
The fine distribution could also be performed with good success by grinding on a roller mill.
E X A M P L E 3:
When the 1.2 parts of copper phthalocyanine monocarboxylic acid indicated in Example 2 were replaced by 1.2 parts of copper phthalocyanine-4,4'-dicarboxylic acid and the grinding and working up was performed as described in Example 2, a pigment was obtàined which corresponded to the pigment obtained in Example 2 with respect to its coloristal properties.
E X A M P L E 4:
When the 1.2 parts of copper phthalocyanine monocarboxylic acid indicated in Example 2 were replaced by a mixture of 1 part of copper phthalocyanine-4 carboxylic acid and 0.2 part of copper phthalocyanine-4-carboxylic acid amide and the grinding and working up was carried out as indicated in Example 2, a pigment was obtained which corresponded to that indicated in Example 2 with respect to its coloristical properties.
E X A M P L E 5:
20 Parts of pure copper phthalocyanine of the ~-modification (obtained according to the method described in Example 2) and 2 parts of the sodium salt of copper phthalocyanine-4-carboxylic acid were ground : . , .: , - , . ~ - :
: -.
.
: . , - . : :
.
1(~7388~) together with 120 parts of acetone and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill during about 20 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment ~as isolated and dried at 60C under reduced pressure.
The pigment so obtained corresponded to that obtained according to Example 2 with respect to its coloristical behaviour.
~hen instead of 2 parts of the sodium salt of copper phthalocyanine monocarboxylic acid 2 parts of the barium salt of copper phthalocyanine monocarboxylic acid were used as additive, a pigment was obtained which had the same properties.
E X A M P L E 6:
32.6 Parts of unsubstituted crude CuPc (in the form of a 93%
commercial product) were introduced into 300 parts of a 86% sulfuric acid and stirred at 70 to 80C for 4 hours in a nitrogen atmosphere. The so obtained CuPc-sulfate in the form of coarse crystals was filtered off after cooling to room temperature, washed with 80% sulfuric acid and then hydrolized by introducing the filter cake into 300 parts of water. The ; copper phthalocyanine was filtered off and washed with water until neutral.
In order to attain the rearrangement of phases from the a-modification into the ~-modification, the moist filter cake was introduced into 300 parts of water, 30 parts of chlorobenzene were added and the mixture was boiled ` under reflux for 4 hours. Then, the chlorobenzene was removed by steam ; distillation.
The pigment suspension was filtered and the filter cake was dried at 100 C. 30 Parts of pure CuPc of the ~-modification were obtained.
For the fine distribution, the 30 parts of the pure CuPc so obtained were ground after the addition of 1.2 parts of CuPc-monosulfonic acid ~' .
' .
:, .' : - . - , :
.
1~7388~
(prepared by sulfonation of CuPc in oleum and having a sulfur content of 5.1%) together with 150 parts of isopropanol and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill during 20 hours on a "Vibratom" vibration table. Then, the pigment suspension was separated from the grinding media. The pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained which had a specific surface of about 70 m /g yielded upon dyeing enamels according to known methods brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distinguished as compared with known commercial brands by a good stability towards flocculation and an excellent dispersibility in lacquering systems.
When used in book printing according to known methods, the pigment so obtained yielded prints that were distinguished by a high tinctorial strength and an especially high purity of shade.
When the grinding medium used in the fine distribution is 150 parts of methanol or 150 parts of glycolmonomethyl ether or 120 parts of acetone, instead of the 150 parts of isopropanol, pigments of the same quality were obtained.
When the additive used for the fine distribution is 1.5 parts of 1.8 parts of CuPc-monosulfonic acid instead of the 1.2 parts of CuPc-monosulfonic acid, pigments of the same quality were obtained.
However, when instead of 1.2 parts of ~uPc-monosulfonic acid 3 parts of this compound were used, pigments were obtained which were dis-tinguished in the dyeing of lacquers by a very high transparency and an excellent tinctorial strength, but which had a minor dispers-ibility.
, : , ~ :
- - , . : .
;, . . . . ~ . , ~ . - .
- - : . . - . . - . ~ . : :
: - . -: :: . . ~ , - . :- : . . . . ... .
, - , - ~ . . ., :, : . . . : , , - . : . - . . . .: . , - , . : ': . ~ : : ::
: , . - : ~ . . -: . .
. : : : .
lC~73880 E X A M P L E 7:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and 1.2 parts of CuPc-monosulfonic acid were ground together with 1,200 parts of glass beads of 3 mm diameter and a mixture of 139 parts of water and 11 parts of isobutanol in a porcelain mill during 24 hours on a "Vibratom" vibration table. Then, thc pigment suspension was separated from the grinding bodies. The pigment was isolated by filtration and dried ~-at 60C under reduced pressure.
Upon dyeing enamels according to known methods, the pigment so prepared yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distinguished by an excellent dispersibility in lacquers.
When instead of the mixture of 139 parts of water and 11 parts of isobutanol a mixture of 75 parts of water and 75 parts of isopropanol or a mixture of 112 parts of water and 38 parts of isopropanol was used, pigments were obtained which had the same quality.
Pigments of the same quality were also obtained when the fine distribution was not performed discontinuously on a "Vibratom" vibration table, but continuously on a continuous vibration mill or a continuous roller mill.
E X A M P L E 8:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and 3 parts of the sodium salt of CuPc-monosulfonic acid were ground together with 150 parts of isopropanol and 1,200 parts of quartzite beads of 2 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. ThenJ the pigment suspension was separated from the grinding bodies and the pigment was isolated by distilling off the solvent.
.:
' - ~
1~7388~) When dyeing enamels accordin~ to known methods, the pigment so obtained yielded brilliant greenish blue shades of high tinctorial strength. The pigment was distinguished by a very good dispersibility in lacquers.
Pigments of the same quality were obtained when instead of 3 parts of the sodium salt 3 parts of the barium salt or 3 parts of the ammonium salt of CuPc-monosulfonic acid were used as additive.
E X A M P L E 9:
32.6 Parts of unsubstituted crude CuPc ~in the form of a 93%
commercial product) were introduced into 300 parts of 86% sulfuric acid and then stirred for 4 hours at 70 - 80C in a nitrogen atmosphere. The coarse crystals of CuPc-sulfate so obtained were filtered off after cooling to room temperature, washed with 80% sulfuric acid and then hydrolized by introducing the filter cake into 300 parts of water. The CuPc was filtered off, washed with water until neutral and dried at 100C. 30 Parts of coarse crystals of pure CuPc of the ~-modification were obtained.
For the rearrangement of the phases and the fine distribution at the same time the pure CuPc of the ~-modification was ground after the addition of 1.5 parts of CuPc-monosulfonic acid together with 150 parts of xylene and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was - isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained, which is in the form of the ~-crystal modification yielded upon dyeing enamels colorings of high tinctorial strength. The pigment was distinguished by a very good dispersibility in lacquers.
.` :
,` -.
.. . . ..
- '' : . :' ' '. -' '', . :
- - . . . . ., . :
.. . . . : , ..
,:. , : . . . : . .
1~7388~1 E X A M P L E 10:
95 Parts of unsubstituted crude CuPc ~in form of a 95% commercial product) and 7.5 parts of CuPc-monosulfonic acid were dissolved together in 1,000 parts of 96% sulfuric acid. At 70 to 80C, 116 parts of water were added dropwise and the suspension was stir~ed at 70 - 80C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the CuPc-sulfate was filtered off, washed with 80% sulfuric acid and the filter cake was hydrolized in 1,000 parts of water. To the suspension, 100 parts of chlorobenzene were added and the suspension was boiled under reflux for 4 hours. The chlorobenzene was eliminated by steam distillation.
The pigment was isolated by filtration, washed with water until neutral and dried at 100C.
30 Parts of the pure pigment so obtained which was in the form of the ~-modification and contained about 6% of CuPc-monosulfonic acid, were ground with 150 parts of isopropanol and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. Then, the pigment was isolated by filtration and dried at 60C
under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength.
The pigment was distinguished by a very good dispersibility in lacquers.
E X A M P L E 11:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 were subjected after the addition of a mixture of 0.9 part of CuPc-monosulfonic acid and 0.3 part of CuPc-disulfonic acid to the process of fine distribution as described in Example 6. The pigment obtained corresponded to that obtained according to Example 6 with respect to its quality.
~ . - .
16~7388~) E X A M P L E 12:
30 Parts of t~e pure CuPc of the ~-modification according to Example 6 and 1.5 parts of N,N'-bis~dodecyl)-CuPc-disulfonamide (prepared by reacting dodecyl amine with the dichloride of CuPc-disulfonic acid) were ground together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of acetone in a porcelain mill during 20 hours on a "Vibratom"
vibration table. The pigment suspension was then separated from the grinding bodies and the pigment was isolated by evaporation.
When dyeing enamels according to known methods the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment dyestuff was distinguished by an excellent dispersibility.
When instead of 1.5 parts of the above sulfonamide - additive a mixture of 1.2 parts of N,N'-bis-(isobutyl~-CuPc-disulfonamide and 0.3 part of N,N',N"-tris-(isobutyl)-CuPc-trisulfonamide was used as additive, a pigment was obtained which had the same quality.
E X A M P L E 13:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and 1.5 parts of N,N'-bis-(phenyl)-CuPc-disulfonamide were ground together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of isopropanol in a porcelain mill during 24 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was isolated by filtration and dried at 60C
under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength.
The pigment was distinguished by a very good dispersibility in lacquering systems.
, ~ . , , ~ , `
. ' , . , : - ~ : ' ' " ~ ' 1~73880 Pigments of the same quality were obtained, when instead of N,N'-bis-(phenyl)-CuPc-disulfonamide one of the following compounds was used as additive:
CuPc-disulfonamide N,N'-bis-(di-n-butyl)-CuPc-disulfonamide N,N'-bis-(a-ethylhexyl)-CuPc-disulfonamide N,N'-bis-(octadecyl)-CuPc-disulfonamide N,N'-bis-(~-aminoethyl)-CuPc-disulfonamide CuPc-disulfonic acld diphenyl ester E X A M P L E 14:
30 Parts of the pure CuPc of the ~-modification obtained according to Example 6 and a mixture of 1.3 parts of N,N'-bis-(di-n-butyl)-CuPc-; Disulfonamide and 0.3 part of N,N',N"-tris-(di-n-butyl)-CuPc-trisulfonamide (prepared by reacting a corresponding mixture of CuPc-disulfochloride and CuPc-trisulfochloride with di-n-butyl amine) were ground together with 1,200 parts of glass beads of 2 mm diameter, 139 parts of water and 11 parts of isobutanol in a porcelain mill during 24 hours on a "Vibratom"
vibration table. The pigment suspension was separated from the grinding bodies and the pigment was isolated by filtration and dried at 60C under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant shades of a high degree of purity and tinctorial strength.
When dyeing polyvinyl chloride according to known methodsJ the pigment was easily dispersible and yielded dyeings that were distinguished by a high tinctorial strength and an extraordinary degree of purity of the shade.
When the fine distribution was performed not discontinuously on a vibration table but continuously in a bead mill of the type "~olinex" of Messrs. Netzsch with glass beads of 1 mm diameter, a pigment was obtained ;
:
.
which had the same quality.
E X A M P L E 15:
32.6 Parts of unsubstituted crude CuPc (in the form of a 93%
commercial product) were introduced into 300 parts of 86% sulfuric acid and stirred during 4 hours at 70 - 80C in a nitrogen atmosphere. The coarse crystals of the CuPc-sulfate so formed were filtered off after cooling to room temperature, washed with 80% sulfuric acid and then hydrolized by introducing the filter cake into 300 parts of water. The CuPc was filtered off and washed with water until neutral.
To obtain the rearrangement of the phases from the~-modification into the ~-modification, the moist filter cake was introduced into 300 parts of water, 30 parts of chlorobenzene were added and the mixture was stirred under reflux during 4 hours. The chlorobenzene was removed by steam distillation.
The pigment suspension was filtered and the filter cake was dried at 100C.
30 Parts of pure CuPc of the ~-modification were obtained.
For the fine filter distribution, the 30 parts of the pure CuPc so obtained were ground after the addition of 3 parts of tris-(isobutylamino-methyl)-CuPc ~prepared by reacting tris-(chloromethyl)-CuPc with isobutyl amine) together with 150 parts of isopropanol and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the grinding bodies. The pigment was isolated by filtration and dried a~
60C under reduced pressure.
When dyeing enamels according to known methods, the pigment so obtained yielded brilliant greenish blue shades of a high degree of purity and tinctorial strengthJ and an excellent fastness to light and to ~' atmospheric influences. The pigment was distinguished by a good stability towards flocculation and excellent dispersibility in lacquering systems.
` :.
',: ' . .~ , .: . : . .
,.. . ~
. , .. : . . .
~738~3~
When the grinding medium in the fine distribution was 150 parts of methanol, 150 parts of glycolmonomethyl ether or 120 parts of acetone instead of the 150 parts of isopropanol, the pigment obtained had the same quality.
The same result was obtained when the fine distribution was not effected discontinuously on a "Vibratom" vibration table, but continuously on a continuously operating vibration mill or roller mill E X A M P L E 16:
30 Parts of the pure CuPc of the ~-modification prepared according to Example 15 and a mixture of 0.5 part of bis-(isobutylaminomethyl)CuPc and 2 parts of tris-(isobutylaminomethyl)-CuPc and 0.5 part of tetrakis-~iso-butylaminomethyl)-CuPc were introduced into 150 parts of isopropanol and stirred until a homogeneous suspension had formed. The suspension was ground continuously on a continuously operating bead mill of the type "Molinex" with the use of glass beads of 1 mm diameter. The pigment was isolated by distilling of the solvent. The pigment so obtained corresponded to that obtained according to Example 15 with respect to its quality.
E X A M P L E 17:
~!
30 Parts of the pure CuPc of the ~-modification obtained according to Example 15 and 3 parts of tris-(n-octylaminomethyl)-CuPc were ground i 20 together with 150 parts of acetone and 1,200 parts of quartzite beads of
3 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration table. The pigment suspension was separated from the grinding bodies, the pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so prepared yielded according to known methods enamels of brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distinguished by a very good dispersibility in lacquers.
:' , .
: .
; . .. . :. , , . ~ , :
.
. . ~ '-: . . , ' -,: . : . . ~ :
Pigments of the same quality were obtained, when instead of tris-(n-octylaminomethyl)-CuPc one of the following compounds was used as additive:
tris-(n-propylaminomethyl)-CuPc tris-(n-butylaminomethyl)-CuPc tris-(n-hexylaminomethyl)-CuPc bis-(~-aminoethylaminomethyl)-CuPc tris-(n-dodecylaminomethyl)-CuPc tris-(N-phenylaminomethyl)-CuPc tris-(N-methyl-N-phenyl-aminomethyl)-CuPc When instead of 3 parts of tris-(n-octylaminomethyl)-CuPc only 1.5 parts of this compound were used as additive, a pigment was obtained which also yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength.
E X A M P L E 18:
30 Parts of the pure CuPc of the ~-modification prepared according to Example 15 and 2 parts of tris-(phthalimidomethyl)-CuPc (prepared by reacting CuPc with N-methylolphthalimide in sulfuric acid) were ground together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of isopropanol in a porcelain mill during 24 hours on a "Vibratom" vibration ~I table. The pigment suspension was separated from the grinding bodies, the pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained dyed enamels brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distin-guished by an excellent dispersibility in lacquers.
E X A M P L E 19:
30 Parts of the pure CuPc of the ~-modification prepared according to Example 15 and 1.5 parts of tris-(n-octylaminomethyl)-CuPc were ground .,.- . : .. . .- - :,, -. . . . : . ., .. . .: . : . . . . .
:.: :, ~., , , .. ,. ,:- : : : .
'' .'-':' . ' . ' . .: '' - ' . ''.. . : . ' . ' .: . : , ' ', ,, :.' ' , . ' . ' ' ' . ' ' , 1~73880 together with 139 parts of water, 11 parts of isobutanol and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill during 24 hours on a "Vibra-tom" vibration table. The pigment suspension was separated from the grinding bodies, the pigment was isolated by filtration and dried at 60C under reduced pressure.
; The pigment so obtained dyed enamels brilliant shades of a high degree of purity and tinctorial strength. When dyeing polyvinyl chloride according to known methods, the pigment was easily dispersible and yielded dyeings of high tinctorial strength which were distinguished by a high degree of purity.
When instead of the mixture of 139 parts of water and 11 parts of isopropanol a mixture of 75 parts of water and 75 parts of isopropanol or a mixture of 112 parts of water and 38 parts of isopropanol was used as grinding medium, pigments were obtained that had the same qumllty.
`: :
~ , ':
- : - . : . . . ..
'.-. ' .'~
- - . ,: , . ~ - :
. , ... . . . ,,~ .. ,. - :
- -: : : ..
: : :
. .
.
. : . .
The pigment so prepared yielded according to known methods enamels of brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distinguished by a very good dispersibility in lacquers.
:' , .
: .
; . .. . :. , , . ~ , :
.
. . ~ '-: . . , ' -,: . : . . ~ :
Pigments of the same quality were obtained, when instead of tris-(n-octylaminomethyl)-CuPc one of the following compounds was used as additive:
tris-(n-propylaminomethyl)-CuPc tris-(n-butylaminomethyl)-CuPc tris-(n-hexylaminomethyl)-CuPc bis-(~-aminoethylaminomethyl)-CuPc tris-(n-dodecylaminomethyl)-CuPc tris-(N-phenylaminomethyl)-CuPc tris-(N-methyl-N-phenyl-aminomethyl)-CuPc When instead of 3 parts of tris-(n-octylaminomethyl)-CuPc only 1.5 parts of this compound were used as additive, a pigment was obtained which also yielded brilliant greenish blue shades of a high degree of purity and tinctorial strength.
E X A M P L E 18:
30 Parts of the pure CuPc of the ~-modification prepared according to Example 15 and 2 parts of tris-(phthalimidomethyl)-CuPc (prepared by reacting CuPc with N-methylolphthalimide in sulfuric acid) were ground together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of isopropanol in a porcelain mill during 24 hours on a "Vibratom" vibration ~I table. The pigment suspension was separated from the grinding bodies, the pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained dyed enamels brilliant greenish blue shades of a high degree of purity and tinctorial strength. The pigment was distin-guished by an excellent dispersibility in lacquers.
E X A M P L E 19:
30 Parts of the pure CuPc of the ~-modification prepared according to Example 15 and 1.5 parts of tris-(n-octylaminomethyl)-CuPc were ground .,.- . : .. . .- - :,, -. . . . : . ., .. . .: . : . . . . .
:.: :, ~., , , .. ,. ,:- : : : .
'' .'-':' . ' . ' . .: '' - ' . ''.. . : . ' . ' .: . : , ' ', ,, :.' ' , . ' . ' ' ' . ' ' , 1~73880 together with 139 parts of water, 11 parts of isobutanol and 1,200 parts of glass beads of 2 mm diameter in a porcelain mill during 24 hours on a "Vibra-tom" vibration table. The pigment suspension was separated from the grinding bodies, the pigment was isolated by filtration and dried at 60C under reduced pressure.
; The pigment so obtained dyed enamels brilliant shades of a high degree of purity and tinctorial strength. When dyeing polyvinyl chloride according to known methods, the pigment was easily dispersible and yielded dyeings of high tinctorial strength which were distinguished by a high degree of purity.
When instead of the mixture of 139 parts of water and 11 parts of isopropanol a mixture of 75 parts of water and 75 parts of isopropanol or a mixture of 112 parts of water and 38 parts of isopropanol was used as grinding medium, pigments were obtained that had the same qumllty.
`: :
~ , ':
- : - . : . . . ..
'.-. ' .'~
- - . ,: , . ~ - :
. , ... . . . ,,~ .. ,. - :
- -: : : ..
: : :
. .
.
. : . .
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a copper phthalocyanine pig-ment of the .beta.-modification which comprises subjecting highly pure copper phthalocyanine of the .beta.-modification to a mechanical fine distribution to-gether with from 2 to 15% by weight, calculated on the copper phthalocyanine of the .beta.-modification used, of a compound of the formula Pc - Am wherein Pc is a phthalocyanine radical and A stands for identical or differ-ent groups selected from -COOM, -S03M (wherein M is hydrogen, an alkali metal, an ammonium ion, or one molar equivalent of alkaline earth metal, carbamoyl, sulfamoyl, N-alkyl carbamoyl of 1 to 12 carbon atoms, N-alkyl sulfamoyl of 1 to 18 carbon atoms, N,N-dialkyl sulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzyl sulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexylsulfamoyl, N-alkyl-N-cyclohexylsul-famoyl with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenylsulfamoyl with 1 to 4 carbon atoms in the alkyl, carboalkoxy with 1 to 4 carbon atoms in the alkoxy, sulfonic acid phenyl ester, sulfonic acid alkyl ester of 1 to 4 carbon atoms, and an aminomethyl group of the formula in which R1 is hydrogen, alkyl of 1 to 18 carbon atoms, 2-aminoethyl, benzyl, phenylethyl, phenyl, alkylphenyl with 1 to 4 carbon atoms in the alkyl, alkanoyl with 1 to 4 carbon atoms in the alkyl moiety, or benzoyl, R2 is hydrogen or alkyl of 1 to 4 carbon atoms, or R1 and R2 together are phthaloyl:
m is 1 or 2, if A is -S03M, m is an integer of 1 to 4, if A is one of said sulfamoyl or sulfonic acid ester groups, m is an integer of 1 to 3, if A is -COOM or one of said carbamoyl or carb-alkoxy groups, or m is an integer of 1 to 6, if A is said aminomethylene group.
m is 1 or 2, if A is -S03M, m is an integer of 1 to 4, if A is one of said sulfamoyl or sulfonic acid ester groups, m is an integer of 1 to 3, if A is -COOM or one of said carbamoyl or carb-alkoxy groups, or m is an integer of 1 to 6, if A is said aminomethylene group.
2. A process as claimed in claim 1, wherein A is COOH or S03H or the alkali metal, calcium, barium or ammonium salt of said acid groups, sulfamoyl, sulfonic acid phenyl ester, N-alkylsulfamoyl of 1 to 18 carbon atoms, N,N-dialkylsulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzylsulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexyl-sulfamoyl, N-alkyl-N-cyclohexylsulfamoyl with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenylsulfamoyl with 1 to 4 carbon atoms in the alkyl, carbamoyl or an aminomethyl group of the formula or wherein R1 is alkyl of 1 to 18 carbon atoms, phenyl or alkylphenyl with 1 to 4 carbon atoms in the alkyl, R3 and R4 are identical or different alkyl each having 1 to 4 carbon atoms;
m is 1 or 2, if A is -COOH or -S03H or their salts, or carbamoyl, m is 2 or 3, if A is one of said sulfamoyl or sulfonic acid ester groups, and m is 2 to 4, if A is one of said aminomethyl groups.
m is 1 or 2, if A is -COOH or -S03H or their salts, or carbamoyl, m is 2 or 3, if A is one of said sulfamoyl or sulfonic acid ester groups, and m is 2 to 4, if A is one of said aminomethyl groups.
3. A process as claimed in claim 1, wherein the mechanical fine dis-tribution is effected by grinding in an aqueous-organic or organic grinding medium on a vibration table or in a bead mill, ball mill or roller mill.
4. A process as claimed in claim 1, 2 or 3 wherein Pc is a copper phthalocyanine radical.
5. A process as claimed in claim 1, wherein the starting material is of the .alpha.-modification and the phase rearrangement occurs during the mech-anical fine distribution.
6. A process as claimed in claim 1, wherein the grinding medium is an aqueous alkanol of 1 to 6 carbon atoms.
7. Copper phthalocyanine pigment of the .beta.-modification obtained by the process claimed in claim 1, and characterized by high tinctorial strength and by ready dispersibility and high stability to flocculation in lacquer systems.
8. A lacquer containing as pigment the copper phthalocyanine of
7. Copper phthalocyanine pigment of the .beta.-modification obtained by the process claimed in claim 1, and characterized by high tinctorial strength and by ready dispersibility and high stability to flocculation in lacquer systems.
8. A lacquer containing as pigment the copper phthalocyanine of
claim 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742439983 DE2439983C3 (en) | 1974-08-21 | Process for the production of easily dispersible phthalocyanine pigments of the beta modification and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073880A true CA1073880A (en) | 1980-03-18 |
Family
ID=5923674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA233,796A Expired CA1073880A (en) | 1974-08-21 | 1975-08-20 | PROCESS FOR THE PREPARATION OF EASILY DISPERSIBLE PHTHALOCYANINE PIGMENTS OF THE .beta.-MODIFICATION |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5147024A (en) |
| AU (1) | AU8414475A (en) |
| BE (1) | BE832622A (en) |
| BR (1) | BR7505311A (en) |
| CA (1) | CA1073880A (en) |
| CH (1) | CH586740A5 (en) |
| DK (1) | DK374875A (en) |
| FR (1) | FR2282455A1 (en) |
| GB (1) | GB1502884A (en) |
| IN (1) | IN143503B (en) |
| IT (1) | IT1041858B (en) |
| NL (1) | NL7509758A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492563A (en) * | 1994-04-21 | 1996-02-20 | Hoechst Ag | Fine division in the preparation of copper phthalocyanine pigments |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2905114C2 (en) * | 1979-02-10 | 1981-03-19 | Basf Ag, 6700 Ludwigshafen | Pigment preparations |
| DE3061493D1 (en) * | 1979-06-01 | 1983-02-03 | Ciba Geigy Ag | Process for manufacturing copper phthalocyanine-blue pigment compositions |
| DE3163191D1 (en) * | 1980-06-19 | 1984-05-24 | Ciba Geigy Ag | Process for the manufacture of pigment alloys |
| JPS59102958A (en) * | 1982-12-03 | 1984-06-14 | Sumitomo Chem Co Ltd | Preparation of copper phthalocyanine pigment |
| JPS59155467A (en) * | 1983-02-25 | 1984-09-04 | Toyo Ink Mfg Co Ltd | Production of copper phthalocyanine pigment |
| JPS60188470A (en) * | 1984-03-08 | 1985-09-25 | Sumitomo Chem Co Ltd | Production method of copper phthalocyanine pigment |
| JPS60195161A (en) * | 1984-03-16 | 1985-10-03 | サン・ケミカル・コ−ポレ−シヨン | Method of conditioning phthalocyanine pigment and product |
| JPS61163978A (en) * | 1985-01-11 | 1986-07-24 | バスフ・コーポレイション | Production of phthalocyanine dispersing material |
| GB9007924D0 (en) * | 1990-04-07 | 1990-06-06 | Ciba Geigy Ag | Production of pigments |
| US5284511A (en) * | 1993-04-12 | 1994-02-08 | Miles Inc. | Conditioning process for phthalocyanine pigments |
| US5534055A (en) | 1994-08-24 | 1996-07-09 | Bayer Corporation | Process for alpha-phase metal phthalocyanine pigments |
| US5728204A (en) * | 1996-01-31 | 1998-03-17 | Bayer Corporation | Preparation of phthalocyanine-containing waterborne coating systems |
| TW588091B (en) | 1998-08-29 | 2004-05-21 | Ciba Sc Holding Ag | Pigment compositions containing substituted amido phthalocyanine derivatives |
| GB9818824D0 (en) * | 1998-08-29 | 1998-10-21 | Ciba Geigy Ag | Pigment compositions containing substituited amido phthalocyanine derivatives |
| US6440207B1 (en) | 2000-03-03 | 2002-08-27 | Bayer Corporation | Method for preparing organic pigments |
| ATE318868T1 (en) | 2001-08-23 | 2006-03-15 | Du Pont | METHOD FOR PRODUCING STABILIZED ORGANIC COLOR PARTICLES AND DEVICE THEREFOR |
| EP2057234B1 (en) | 2006-08-18 | 2014-10-08 | Sun Chemical Corporation | Pu-coated pigments |
| WO2009060573A1 (en) * | 2007-11-07 | 2009-05-14 | Nippon Kayaku Kabushiki Kaisha | Water-soluble naphthalocyanine dye and aqueous ink containing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2238243A (en) * | 1939-12-28 | 1941-04-15 | Du Pont | Liquid coating composition |
| DE1223086B (en) * | 1961-05-18 | 1966-08-18 | Basf Ag | Flocculation-resistant and solvent-resistant phthalocyanine pigment mixtures |
| FR1353759A (en) * | 1962-03-14 | 1964-02-28 | Ici Ltd | Manufacture of pigment compositions |
| JPS4933326A (en) * | 1972-08-05 | 1974-03-27 |
-
1975
- 1975-08-07 GB GB33013/75A patent/GB1502884A/en not_active Expired
- 1975-08-15 NL NL7509758A patent/NL7509758A/en unknown
- 1975-08-18 CH CH1075175A patent/CH586740A5/xx not_active IP Right Cessation
- 1975-08-19 IT IT26421/75A patent/IT1041858B/en active
- 1975-08-19 IN IN1616/CAL/1975A patent/IN143503B/en unknown
- 1975-08-20 BR BR7505311*A patent/BR7505311A/en unknown
- 1975-08-20 AU AU84144/75A patent/AU8414475A/en not_active Expired
- 1975-08-20 CA CA233,796A patent/CA1073880A/en not_active Expired
- 1975-08-20 DK DK374875A patent/DK374875A/en not_active Application Discontinuation
- 1975-08-20 FR FR7525734A patent/FR2282455A1/en active Granted
- 1975-08-20 JP JP50100237A patent/JPS5147024A/ja active Pending
- 1975-08-21 BE BE159360A patent/BE832622A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492563A (en) * | 1994-04-21 | 1996-02-20 | Hoechst Ag | Fine division in the preparation of copper phthalocyanine pigments |
Also Published As
| Publication number | Publication date |
|---|---|
| IN143503B (en) | 1977-12-10 |
| BE832622A (en) | 1976-02-23 |
| NL7509758A (en) | 1976-02-24 |
| DE2439983A1 (en) | 1976-03-04 |
| GB1502884A (en) | 1978-03-08 |
| DE2439983B2 (en) | 1976-11-18 |
| CH586740A5 (en) | 1977-04-15 |
| BR7505311A (en) | 1976-08-03 |
| DK374875A (en) | 1976-02-22 |
| FR2282455A1 (en) | 1976-03-19 |
| AU8414475A (en) | 1977-02-24 |
| IT1041858B (en) | 1980-01-10 |
| FR2282455B1 (en) | 1979-03-16 |
| JPS5147024A (en) | 1976-04-22 |
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