DE1156191B - Process for the production of water-insoluble colored salts of the phthalocyanine series - Google Patents

Description

Process for the production of water-insoluble colored salts of the phthalocyanine series The invention relates to a process for the production of water-insoluble colored salts the phthalocyanine series, which are particularly suitable for the production of inks for ballpoint pens and stamps are suitable.

The new color salts correspond to the general formula I. In this formula, Pc means the residue of a phthalocyanine. This is either metal-free or, more advantageously, contains metal, in particular contains heavy metals and, above all, copper. In addition to the sulfonyl substituents, the benzo radicals of the phthalocyanine dye contain at most individual halogens, in particular individual chlorine atoms. A is a saturated hydrocarbon radical connected to a, ß or a, y carbon atoms with the two nitrogen atoms. A advantageously denotes an alkylene radical, in particular an α, β-alkylene, especially the 1,2-ethylene radical. However, A can also mean an α, γ-alkylene, primarily the 1,3-propylene radical.

At least one R of Ri, R2 and R3 means a lipophilic radical, another R of R1, R2 and R3 means hydrogen, and the third R of Ri, R2 and R3 represent hydrogen, an aliphatic cycloaliphatic araliphatic or an aromatic radical. Advantageously, only one R, in particular R, or R2, a lipophilic radical, especially an aliphatic saturated group, preferably an alkyl group with at least 10 carbon atoms, especially the decyl, dodecyl and tetradecyl group. This R may also mean an araliphatic Group, such as B. a benzyl group, the saturated aliphatic substituents, such as B. tert-butyl, tert-amyl, octyl, isooctyl, decyl and dodecyl groups can. The other two Rs are preferably hydrogen; however, it can be one of these both R, in particular R2 or R1, also an organic radical, primarily one Alkyl group, e.g. B. the methyl, ethyl, a propyl, butyl, amyl, hexyl, Octyl, 3,5,5-trimethylhexyl, decyl or dodecyl group, or a cycloalkyl group mean. All N-substituents together advantageously have at least 9 carbon atoms.

m and n each represent a positive integer; their sum is 2 to 3. The color salts of the phthalocyanine series of the general formula I are prepared by adding 1 mol of a phthalocyaninesulfonic acid sulfonic acid amide of the general formula where Pc, n and rrl are what has been said in the definition and Z is a monovalent cation, preferably hydrogen, an alkali metal or ammonium ion, with n moles of a compound of the general formula III in which A, Ri, R2 and R3 mean what was stated under formula I, to form a water-insoluble amine salt of a phthalocyaninesulphonic acid containing sulphonic acid amide groups.

The phthalocyanine compound of the formula II is advantageous here the imino-di-N-heterocycle of the formula III, the latter advantageously in the form of his acidic salt, preferably of a hydrohalide, in particular of the hydrochloride or bromides in aqueous solution or suspension, optionally with the addition of inert, water-miscible organic solvents such. B. acetone, implemented.

Instead of a single compound of the formulas II and III, it is also possible to use technical-grade mixtures whose components correspond to the formulas II and III. Particularly valuable color salts of the phthalocyanine series are obtained from mixtures in which n and m in formula II each have an average value of 0.7 to 1.5.

The starting products of the general formula III are obtained according to various, methods known per se.

This gives the 1- or 1,3-substituted 1,3-di-N-heterocycles of the general formula IV where R1 and R2 mean what has been said in the definition, for example by reacting the corresponding N- or N, N'-substituted alkylenediamines with cyanogen halide, in particular cyanogen chloride, expediently in an inert solvent with cooling.

The 1-substituted 1,3-di-N-heterocycles with N-substituted 2-imino groups of the general formula Va or the tautomeric formula Vb where R1 is what has been said under formula I and R3 is what is described in the definition, with the exception of hydrogen, is obtained, for example, by reacting the thioether of the general formula VI which can be prepared by a known method where R1 is what was said under formula I and the hydrocarbon radical is above all a lower alkyl, in particular methyl group, with a primary amine of the general formula VII R3 - NH2 (VII) where R3 - apart from hydrogen - is one of the substituents described in the definition, with elimination of hydrocarbon mercaptan, expediently in inert solvents, especially in lower alkanols, such as. B. methanol at boiling point.

The finished colored salts of the formula in dispersion form I can easily be filtered off and cleaned by washing with water. they provide blue-black powders that are insoluble in water and in lower alkanols, such as z. B. methanol or ethanol, and lower ketones, such as. B. acetone, sparingly soluble are. In contrast, they dissolve easily in some higher alcohols, such as. B. benzyl alcohol, or in some ether alcohols, such as B. in diethylene glycol monoalkyl ethers, for example in diethylene glycol monoethyl ethers.

Ballpoint pen inks and stamp inks made according to the present invention Containing dyes and solvents are characterized by very good fastness writing generated with them against water, lower alkanols, acetone, ether, hydrochloric acid, Caustic soda, aqueous ammonia, sodium hypochlorite, potassium permanganate and sodium bisulfite the end. They are also very lightfast. If necessary, such inks can also be used contain other real dyes that are used to produce the desired color shade, for example carbon black.

British patents 460147 and 492 177, French patent 838 418 and Swiss patent 341591 describe water-insoluble phthalocyanine dyes which contain lipophilic groups and which are also reaction products of phthalocyanine compounds with amines. The phthalocyanine dyes obtainable according to the process differ from these in particular in that they are derived from special heteroyclic amines. In addition, the closest comparable dyes of the above-mentioned British and French patents do not give homogeneous ballpoint pen pastes due to insufficient solubility, which makes them useless for this purpose, while the ballpoint pen ink produced with the dye of Swiss patent 341 591 has poor fuel and acetone fastness .

The following examples illustrate the invention. In it mean the parts are parts by weight. The temperatures are given in degrees Celsius. Parts by weight relate to parts of volume in the ratio of grams to cubic centimeters. Example 1 14.9 Parts of a mainly made of copper phthalocyanine monosulfonic acid monosulfonic acid amide existing mixture (prepared by heating 100 parts of copper phthalocyanine for 2 hours in 800 parts of chlorosulfonic acid to 115 ° and treatment of the sulfonic acid chloride formed with ammonia) are dissolved with 3 parts of sodium carbonate in 600 parts of water at 40 ° and by adding 170 parts of a solution of 28.8 parts of 1-dodecyl-2-iminoimidazolidine hydrochloride (manufactured by reacting N-dodecyl-1,2-diaminoethane with Cyanogen chloride in chlorobenzene) precipitated again in 500 parts of water. The thus obtained, The flaky blue dye is filtered off with the solution of 0.5 part of 1-dodecyl-2-iminoimidazolidine hydrochloride washed in 500 parts of water and dried at 80 °. There will be 20 parts of one isolated blue powder, which is little in ethanol and acetone, in benzyl alcohol however, solves very well.

You get dyes of a somewhat greener hue, but of very similar ones Properties if one uses the copper phthalocyaninesulfonic acid sulfonic acid amide in this example replaced by cobalt or nickel phthalocyanine monosulfonic acid monosulfonic acid amide.

If you the 1-dodecyl-2-iminoimidazolidine hydrochloride by the 1-decyl, or 1-tetradecyl-2-iminoimidazolidine hydrochloride (made from N-decyl or Tetradecylethylenediamine and cyanogen chloride) replaced, so you get blue dyes of very similar properties. Example 2 To a solution of 14.9 parts of a main Mixture consisting of copper phthalocyanine monosulfonic acid monosulfonic acid amide and 3 parts of sodium carbonate in 800 parts of water becomes the solution of 10 parts 1-Octyl-2-imino-3-propylimidazolidine hydrobromide in 200 parts of water was added dropwise, until the blue dye flocculates completely. This is filtered off, with 500 parts Washed with water and dried at 80 °. It becomes 20 parts of a blue powder isolated, which is poor in ethanol and acetone, in benzyl alcohol and diethylene glycol monoethyl ether dissolves well with blue paint.

You get dyes with very similar properties if you click on Instead of 10 parts of 1-octyl-2-imino-3-propylimidazolidine hydrobromide, 11.7 parts 1- dodecyl-2-imino-3-isobutylimidazolidine hydrobromide, 12.5 parts 1-dodecyl-2-imino-3-cyclohexylimidazolidine hydrobromide or 12.7 parts of 1-dodecyl-2 - imino - 3 - benzylimidazolidine hydrobromide are used.

The imidazolidine derivatives used in this example are made by Action of cyanogen bromide on the resulting N-alkyl-N'-alkyl or aralkyl or -cyclohexyl-1,2-diaminoethane produced.

Example 3 To a solution of 20 parts of a mixture of copper phthalocyanine mono- and disulfonic acid monosulfonic acid amide and -monosulfonic acid disulfonic acid amide (manufactured by heating 100 parts of copper phthalocyanine in 900 parts of chlorosulfonic acid for 3 hours to 120 ° and reaction of the resulting copper phthalocyanine sulfonic acid sulfonic acid chloride with ammonia) and 3 parts of sodium carbonate in 600 parts of water is the solution of 9 parts of 1-dodecyl-2-iminoimidazolidine hydrochloride and 4.5 parts of 1,3-bis-dodecyl-2-iminoimidazolidine hydrochloride slowly added dropwise in 200 parts of water until complete precipitation of the dye originated. The dye is filtered off with the solution of 0.5 part of 1-dodecyl-2-iminoimidazolidine hydrochloride washed in 1000 parts of water and dried at 80 °. There will be 30 parts of one isolated blue powder, which has very similar properties to those in the first section of Example 1 has the dye described.

The mixture of about 2/3 parts by weight of 1-dodecyl-2-iminoimidazolidine and about 1/3 part by weight of 1,3-bis-dodecyl-2-iminoimidazolidine is formed in the Implementation of the technical mixture of N-dodecyl-1,2-diaminoethane and N, N'-bis-dodecyl-1,2-diaminoethane with cyanogen chloride. Example 4 The solution of 14.9 parts of a mainly cobalt phthalocyanine-monosulfonic acid-monosulfonic acid amide existing mixture (prepared by heating 100 parts of cobalt phthalocyanine for 13/4 hours in 800 parts of chlorosulfonic acid to 125 ° and reaction of the cobalt phthalocyanine-sulfonic acid-sulfonic acid chloride formed with ammonia) and 3 parts of sodium carbonate in 800 parts of water with the solution of 9.7 parts of 1-decyl-2-iminohexahydropyrimidine hydrobromide in 100 parts of water added until the dye flocculates completely. This is then filtered off washed with 500 parts of water and dried at 80 °. One isolates 20 parts of a blue-black powder, which is difficult in ethanol and acetone, in dimethylformamide or benzyl alcohol, on the other hand, dissolves well and with a blue color.

You get dyes of -like properties if you replace of the 9.7 parts of 1-decyl-2-iminohexahydropyrimidine hydrobromide, 11.0 parts of 1-dodecyl-2-iminohexahydropyrimidine, 11.7 parts of 1-tetradecyl-2-iminohexahydropyrimidine, 9.5 parts of 1-octyl-2-imino-3-methylhexahydropyrimidine or 11.5 parts of 1-dodecyl-2-imino-3-methylhexahydropyrimidine hydrobromide are used. The vexahydropyrimidine derivatives used in this example are activated by action produced from cyanogen bromide to the corresponding 1,3-diaminopropane.

If you have the cobalt phthalocyanine sulfonic acid sulfonic acid amide replaces the nickel or copper phthalocyanine sulfonic acid sulfonic acid amide, so obtained one dyes of very similar properties.

Example 5 14.9 parts of a mainly copper phthalocyanine - monosulfonic acid - monosulfonic acid amide existing mixture with 3 parts Sodium carbonate dissolved in 800 parts of water and by adding a solution of 10 Parts of 2-dodecylaminoimidazoline hydrochloride precipitated in 100 parts of water. The dye is filtered off, washed with water and dried at 60 °. There will be 20 parts of a blue powder, which dissolves well in benzyl alcohol.

A similar dye is obtained using 10 parts 2-decylaminoimidazoline hydrochloride.

The 2-dodecyl or 2-decylaminoimidazoline hydrochloride are through Implementation of 2-methylmercaptoimidazoline with dodecylamine or decylamine.

Claims (6)

PATENT CLAIMS: 1. Process for the preparation of water-insoluble colored salts of the phthalocyanine series, characterized in that 1 mol of a water-soluble phthalocyanine compound of the general formula I is used where Pc is the radical of a phthalocyanine, Z is a monovalent cation and h and m are positive, integer indices, the sum of n + m being at least 2 and at most 3, with n moles of a compound of the general formula II where A denotes a saturated hydrocarbon radical connected to a, ß or a, y carbon atoms with the two nitrogen atoms and of Ri, R2 and R3 at least one R denotes a lipophilic group, another denotes hydrogen and the third denotes that of hydrogen or an aliphatic, cycloaliphatic or araliphatic radical, or n mol of one of its salts is reacted with strong mineral acids to form a water-insoluble amine salt of a phthalocyaninesulfonic acid containing sulfamide groups. 2. The method according to claim 1, characterized by the use of such Compounds of the general formula II, in which the nitrogen substituents in total contain at least 9 carbon atoms. 3. The method according to claims 1 and 2, characterized by the use of such compounds of the general formula II, in which R is a saturated aliphatic radical with 10 to 14 carbon atoms and R2 and R3 are hydrogen. 4. The method according to claims 1 to 3, characterized by using such compounds of the general formula in which A means a 1,2-ethylene or 1,3-propylene radical. 5. The method according to dpn claims 1 to 4, characterized in that Pc contains copper. 6. Process according to claims 1 to 5, characterized by the use of a mixture of compounds of the general formula I, in which n and m each have an average value of 0.7 to 1.5. Documents considered French Patent No. 838,418; British Patent Nos. 460 147, 492177. In the publication of the application, two tables were laid out with photomicrographs, a coloring table and explanations of these tables.