CH627489A5 - Process for preparing phthalocyanine pigment compositions - Google Patents

Description

However, the invention resides in that the ammonium salt can be formed in the solvent in the presence of the pigment.

The pigment composition can be separated from the solvent directly by filtration, preferably after dilution with water. Before filtering, the more volatile solvents can also be distilled off first, but preferably only after adding a little water. In any case, the pigment composition is washed free of any trace of inorganic salts and then dried.

The pigment compositions of the present invention can be used to pigment various media, such as paints, printing inks, nitrocellulose, alkyd-melamine / formaldehyde and acrylic-melamine / formaldehyde systems, but especially in the media which contain high amounts of hydrocarbons Contain solvents.

The following examples illustrate the invention. Parts by weight are in the same ratio of parts by volume as kg / 1. Parts and percentages are by weight unless otherwise stated.

example 1

175 parts of crude copper phthalocyanine are ground with 23 parts of inorganic salts, 1.6 parts of diethylaniline and 0.8 part of glycerol monooleate until the phthalocyanine is in pigment form.

103 parts of this mixture, which correspond to 90 parts of copper phthalocyanine, are added to 600 parts of isopropanol and boiled at reflux temperature for 5 1/2 hours with thorough stirring. Then 4 parts of the compound of the formula CuPc (S03H) x, in which X denotes the number 2, are added in the form of presscakes and the mixture is boiled further at the reflux temperature. After 15 minutes, 6 parts of amine of the formula III dissolved in hot isopropanol, in which R4 is a methyl group and R2 and R3 are hydrogenated valley residues (Kemamine T.9701, Humko Chemical Products), are added. After a further 15 minutes, 600 parts of water are added and the isopropanol is distilled off. The pigment composition formed is filtered off, washed salt-free and neutral and dried at 50-60 ° C. 99.1 parts of the finished pigment composition are obtained. An ink with 6% pigment content and a pigment / binder ratio of 1: 5 was prepared by grinding the pigment composition of this example with a phenolic resin varnish and toluene as a solvent in a ball mill. In comparison to a similar printing ink obtained from untreated β-copper phthalocyanine, the printing ink obtained with the product of this example shows significantly better flow properties, as well as higher color strength, purity and gloss.

Example 2

Example 1 is repeated, except that 3.4 parts of the compound of the formula CuPc (SChH) x, in which X is 2.4, and 5.6 parts of the hydrogenated tallow amine are used. A printing ink produced with the product obtained in this way shows better flow properties and increased color strength compared to a similar printing ink produced from untreated β-kuperphtha-locyanin.

Example 3

a) 20 parts of the compound of the formula CuPc (S03H) x, in which X is 2, are added to 200 parts of isopropanol in the form of a press cake and heated to reflux temperature with good stirring. 29.2 parts of the amine of the formula III, in which R4 is a methyl group and R2 and R3 are hydrogenated tallow residues, are dissolved in 200 parts of hot isopropanol and within 5

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Minutes of the boiling pigment / isopropanol suspension added. After 30 minutes of treatment at the reflux temperature, 600 parts of water are metered in within 60 minutes and the isopropanol is distilled off at the same time. The blue-green reaction product is filtered off, washed with warm water and dried at 60 ° C. 48.1 parts of the amine salt are obtained.

b) 175 parts of crude copper phthalocyanine are ground according to the procedure described in Example 1. 103 parts of this mixture, which correspond to 90 parts of copper phthalocyanine, are added to 600 parts of isopropanol and are boiled at reflux temperature for 5 1/2 hours with thorough stirring. Then 10 parts of the product of Example 3a dissolved in hot isopropanol are added and the mixture is boiled at reflux temperature for a further 30 minutes. Finally, 600 parts of water are added and the isopropanol is distilled off. The pigment composition is filtered off, washed salt-free and neutral and dried at 50-60 ° C. A yield of 99.3 parts is obtained. An ink obtained with the product of Example 3b by the method described in Example 1 shows similar properties to the ink obtained with the product of Example 1.

Example 4

Example 3b is repeated, except that 108.6 parts of the ground mixture, corresponding to 95 parts of copper phthalocyanine, are used together with 5 parts of the product from Example 3a. When the product thus obtained is incorporated into a printing ink, properties similar to those obtained with the printing inks produced with the products from Examples 1 and 3b are obtained.

Example 5

a) an amine salt of the formula I is prepared by the process described in Example 3a with 32.6 parts of the amine of the formula II, in which R2 and R3 are eicosyl radicals and R4 is a methyl group.

b) 150 parts of a phthalocyanine green pigment in pigment form with 47.1% chlorine content are added to 800 parts of acetone with vigorous stirring and heated to reflux temperature. After 10 minutes, 15 parts of the product from Example 5a slurried in acetone are added and the mixture is refluxed for a further 15 minutes. Then 800 parts of water are added, the acetone is distilled off and a mixture of 15 parts of concentrated hydrochloric acid and 15 parts of water is metered in over the course of 2 minutes. The mixture is stirred well for 30 minutes before the product is filtered off, washed with warm water and dried at 50-60 ° C. A yield of 163.2 parts is obtained. The pigment composition is incorporated into a nitrocellulose varnish by ball milling and diluted to a pigment content of 11.7% and a pigment / binder ratio of 1: 1.38 by adding a mixture of nitrocellulose and maleic condensate varnishes. The dispersion obtained shows approximately the same color properties, but significantly better flow properties than a similar dispersion which was produced with untreated phthalocyanine green.

Example 6

89 parts of ground copper phthalocyanine are in 500

Parts of n-butanol are stirred in, heated to the reflux temperature and boiled at this temperature for 5 hours. 11 parts of the product from Example 3a are added and the mixture is boiled at the reflux temperature for a further 15 minutes. 1000 parts of water are metered in at 55 ° C. and the n-butanol is distilled off. The mixture is acidified with 15 parts of 25% aqueous hydrochloric acid and stirred vigorously for 15 minutes. Then the pigment composition is filtered off, washed neutral with hot water and dried at 50-60 ° C. A yield of 98 parts is obtained. The printing ink obtained with this product according to the process described in Example 1 has a higher color strength and a somewhat more pronounced green shade, as well as significantly better flow properties than a printing ink produced with the same but untreated copper phthalocyanine.

Example 7

Example 6 is repeated, except that 87.5 parts of ground copper phthalocyanine, 12.5 parts of the product from Example 3a and methylene ethyl ketone are used as solvents. 97 parts of the finished pigment composition are obtained. The printing ink obtained with this product by the process described in Example 1 shows approximately the same properties as the printing ink obtained with the product from Example 6, that is to say higher color strength and significantly better flow properties than one produced with the same but untreated copper phthalocyanine Printing ink.

Example 8

Example 1 is repeated, except that 8.6 parts of an amine of the formula III are used, in which R2, R3 are hydrogenated valley residues (Adogen 340 ex Ashland Chemicals). The properties of the printing ink obtained with this product correspond to those of the printing ink of Example 1.

Example 9

Example 1 is repeated, except that 4.0 parts of an amine of the formula III are used, in which R2, R3 and R4 are isoctyl radicals (Adogen 381 ex Ashland Chemicals). The properties of the printing ink obtained with this product correspond to those of the printing ink of Example 1.

Example 10

Example 1 is repeated, except that 6.6 parts of an ammonium salt of the formula IV are used, in which R2 and R3 each denote a methyl group, R4 and Rs each denote a hydrogenated tallow residue and B chlorine (Kemamin Q.9702.C). The properties of the printing ink obtained with this product correspond to those of the printing ink of Example 1.

Example 11

Example 10 is repeated, except that 4.0 parts of an ammonium salt of the formula IV are used, in which R2 and R3 each represent a methyl group, R4 a dodecyl and Rs a benzyl radical (Kemamin BQ.6502.C). The properties of the printing ink obtained with this product correspond to those of the printing ink obtained with the product from Example 10.

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Claims (11)

627489 2nd 1. A method for producing a phthalocyanine composition by treating a phthalocyanine pigment with a polar aliphatic solvent that is at least partially miscible with water and separating the solvent from the treated pigment, characterized in that a small amount is added to the phthalocyanine pigment before or during the solvent treatment an ammonium salt of a sulfonated phthalocyanine of the formula N - SO Pc admits, where Pc is a phthalocyanine residue, R2, R3 and R4 are each alkyl or alkenyl, Rs is hydrogen, alkyl, alkenyl or aralkyl and X is the numbers 1-4. 2. The method according to claim 1, characterized in that the ammonium salt of the formula I by reacting a phthalocyanine dye of the formula Pc (SChM) x II wherein Pc and X have the meaning given in claim 1 and M is hydrogen or an alkali metal with a tertiary amine of the general formula R2-N-R3 I R4 III or with a quaternary ammonium salt of the formula I © Q R - N - R ß IV I J is obtained in which R2, R3 and R4 have the meaning given in claim 1, Rs alkyl, alkenyl or arakyl and Be are an anion, the total number of carbon atoms in the tertiary amine or in the cation of the quaternary ammonium salt can be 20 to 60 , and at least one of the groups R2, R3, R4 and R «has a chain length of at least 12 carbon atoms. 3. Process according to claims 1 and 2, characterized in that 1-12 percent by weight of the sulfonated phthalocyanine of the formula II is used based on the phthalocyanine pigment. 4. The method according to claim 3, characterized in that 4-8 percent by weight of the sulfonated phthalocyanine of the formula II is used based on the phthalocyanine pigment. 5. Process according to claims 1 and 2, characterized in that an alkanol with 1 to 4 carbon atoms, an alkyl monocarboxylate with 1 to 4 carbon atoms in the alkyl radical, a dialkyl ketone with 1 to 4 carbon atoms are used as solvents in each alkyl radical, an alkoxyalkanol with 1 to 4 carbon atoms in the alkoxy and alkanol component or an alkylene glycol with 2 to 6 carbon atoms in the alkylene radical. 6. The method according to claims 1 and 2, characterized in that the solvent is isopropanol. 7. The method according to claims 1 and 2, characterized in that the reaction is carried out at a temperature between 50 CC and the boiling point of the solvent at atmospheric pressure. 8. The method according to claims 1 and 2, characterized in that 5 to 10 parts by weight of solvent are used based on 1 part by weight of untreated pigment. 9. The method according to claims 1 and 2, characterized in that the phthalocyanine ammonium sulfonate of the formula I is formed in the solvent in the presence of the pigment. 10. With a phthalocyanine composition pigmented printing ink prepared according to claim 1. 11. With a phthalocyanine composition pigmented paint prepared according to claim 1. CH-PS 554 928 describes a process for the preparation of pigment compositions in which a metal phthalocyanine blue pigment is treated in a polar aliphatic solvent and a copper phthalocyanine derivative is added. By adding a different phthalocyanine derivative to a phthalocyanine pigment, pigment compositions with improved color strengths and theological properties are obtained in an analogous process. Accordingly, the invention relates to a method for producing a phthalocyanine composition according to claim 1. Ammonium salts of the formula I can be obtained by the process according to claim 2. When the dye of formula II is reacted with a tertiary amine of formula III, Rs in formula I is hydrogen. When the dye of formula II is reacted with a quaternary ammonium salt of formula IV, Rs is alkyl, alkenyl, alkapolyenyl or arakyl. Preferably 2 of the radicals R2, R3, R4 and Rs have a chain length of at least 12 carbon atoms and the total number of carbon atoms in the tertiary amine or in the cation of the quaternary ammonium salt is between 25 and 45. The anion B® is preferably a halide -, an acetate or a hydroxide ion. The phthalocyanine dye of Fomel II can be metal-free or a copper, zinc, cobalt, nickel or another transition metal phthalocyanine and can contain halogen, in particular chlorine, in the phthalocyanine molecule. Preferred are copper phthalocyanine dyes of the formula CuPc (S03H) x, in which CuPc represents a copper phthalocyanine residue and X has the meaning given. The phthalocyanine pigment can be metal-free or a copper, zinc, cobalt, nickel or other transition metal phthalocyanine and can contain up to 50 percent by weight of chlorine. A copper phthalocyanine pigment in the a- or β-form or a mixture of the two forms is preferred. The phthalocyanine dye of the formula II can be prepared by customary methods. The amount of sulfonated phthalocyanine dye of the formula II based on the phthalocyanine pigment can vary between 1 and 12 percent by weight, but is preferably between 4 and 8 percent by weight. Ammonium salts of the formula I in which X is between 1 and 2.5 are preferred. The amines on which the compounds of the formulas III and IV are based can contain specific alkyl, alkenyl or alkali 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 be polyenylamine. However, expediently, these are derivatives of mixed hydrocarbon residues from natural oils and fats such as tallow, cereal oil, fish or whale oil. Suitable tertiary amines of this type can be, for example: dimethyl tallow, hydrogenated dimethyl tallow, dimethyl soya, dimethyl octadecyl, dimethyl icosyl, dimethyl tyl docosyl, monomethyl di (dodecyl), hydrogenated monomer thyl-di- (tallow), monomethyl-di (eicosyl), monomethyl-di (docosyl), tri (dodecyl) and tri (octadecyl) amine or mixtures thereof. The quaternary ammonium salts are expediently prepared from such tertiary amines by reaction with methylene chloride or dimethyl sulfate, the quaternary methylammonium salt being formed, or with benzyl chloride, in order to obtain the corresponding quaternary benzylammonium salt. The ammonium salts of the formula I can be obtained, for example, by reacting a phthalocyanine compound which contains x sulfonic acid groups with a sufficient amount of one or more tertiary amines or quaternary ammonium salts neutralizing the sulfonic acid groups. The ammonium salts of the formula I can be prepared in aqueous solution if nitrogen compounds of the formulas III and IV are used which are soluble in an aqueous mineral acid or organic acid. However, they can also be prepared in a suitable organic solvent and isolated by precipitation, for example with water, or by distilling off the solvent. Such a preparation in organic solvents is advantageous for compounds of the formulas III and IV which are sparingly soluble in aqueous acidic medium. Suitable solvents can be, for example: acetone, ethyl methyl ketone, ethanol, methanol and, particularly preferably, isopropanol. The polar aliphatic solvent with which the pigment composition is treated must be at least partially miscible with water. Suitable solvents and also solvent / water mixtures are described in GB-PS 1,140,836. The pigment which is to be mixed with the ammonium salt of the formula I can be added to the solvent in powder form or as an aqueous press cake. The pigment can be in full pigment form or in a highly aggregated state, as is obtained in dry grinding. If the pigment is in the form of a mixture of a phthalocyanine and a salt, a sufficient amount of water to dissolve the salt present can be added to the organic solvent. For the solvent treatment, the temperature, pressure and duration of the treatment must be selected according to the nature of the pigment and the solvent. The solvent treatment can be carried out at a temperature between 10 ° C. and the boiling point of the solvent and at atmospheric pressure or, if appropriate, under excess pressure. The amount of solvent with which the pigment is treated can be between 0.5 and 20 parts by weight of solvent based on 1 part by weight of pigment. However, 1 to 15 parts by weight of solvent are preferred, particularly preferably 5 to 10 parts by weight of solvent based on 1 part by weight of pigment. The ammonium salt of the formula I can be added at any time during the treatment, but preferably such that the pigment and the ammonium salt can react together for at least 10 minutes at the reflux temperature in the solvent, for example in isopropanol or in an azeotropic mixture of water and isopropanol. The ammonium salt of formula I can be prepared separately and then reacted with the pigment. An additional advantage of 627489