DE4338201A1 - Prepn. of mixed aluminium-heavy metal dyestuff/complexes - Google Patents

Abstract

Prepn. of a mixed aluminium-heavy metal dyestuff complex contg. 10-98 mole% heavy metal and 2-90 mole% aluminium comprises: (a) reacting the free metal dyestuff with less than a stoichiometric amt. of a heavy metal cpd.; then (b) reacting the prod. with an aluminium cpd. to produce a stoichiometric excess of metal (calculated on all he metal present) to form the complex.Pref. the heavy metal is cobalt, copper, chromium or nickel. The chromium cpds. used are pref. alkali dichromates, the cobalt cpd is pref. a chloride or sulphate, the nickel and copper cpds. are pref. halides, sulphates or acetates, and the aluminium cpd. is aluminium sulphate.

Description

In the manufacture of heavy metal complex dyes, the Complete metallization, always a certain stoichio metric excess of metal used to ensure that after metallization no unmetallized dye, the quality of the end product would deteriorate, more is available. Mostly achieved the stoichiometric excess of metal sizes up to 15%. That surplus can cause big ecological problems because after the separation (Filtering off) the metal complex dye remains up to 15% heavy tall salts in the filtrate, which is then drained off before it is drained can be subjected to a mostly expensive cleaning process. The disposal of heavy metals - especially chrome, nickel, Ko waste containing copper and copper - encountering increasing difficulty The problems are in the case of these heavy metal complex dyes, we due to the great toxicity of the metals, particularly difficult. But after especially the chrome, nickel, cobalt and copper complex dyes one of the most important metal complexes in the dye industry do not do without them.

In the course of the work to avoid the occurrence of toxic wastewater the heavy metal complex dye preparation has now been found that one in the production of aluminum-heavy metal mixed complex dyes, Dyes with qualities practically like pure heavy metal complex colors preserve substances and heavy by skillful control of the metallization Metal salt excesses that contaminate the wastewater almost completely can avoid.  

The invention now relates to the process for the preparation of aluminum-heavy metal mixed complex dyes with a heavy metal content of, stoichiometric, 10 to 98%, or 80 to 98% and an aluminum content of 90 to 2%, or 20 to 2% , which is characterized in that one carries out the implementation of the metal-free dyes only with a stoichiometric excess of heavy metal compound and then, calculated with the sum of the metals, a stoichiometric excess of aluminum compound. As heavy metal compounds are known to the person skilled in the art, in the case of chromating in particular an alkali dichromate, in the case of cobalt preferably the salts, for. B. the chloride, sulfate (in particular special CoSO ₄ · 7H ₂ O), nitrate or acetate, in the case of nickel and copper also the salts, in particular halides, sulfates or the acetates, into consideration.

The deficit in the 2: 1 metal complex dyes becomes Heavy metal salt selected so that 0.1 to 0.98 mol per 2 mol of dye Heavy metal is coming. The amount of aluminum compound (in excess, before preferably aluminum sulfate) per mol of dye is preferably between 0.1 and 1.2 moles.

In the case of chromium plating with an alkali bichromate is called reducing Substance preferably used glucose.

The invention also relates to those produced according to the invention Dyes belonging to all classes of metal complex dyes can, e.g. B. water-soluble, solvent-soluble and insoluble Dyes (pigments). The solutions are particularly preferred here medium-soluble (water-insoluble) dyes. Occur as dyes especially the 2: 1 azo metal complexes.

As already indicated, the properties of the invention differ Dyes hardly of the corresponding, aluminum-free Heavy metal complex dyes, in some cases the nuance alone is depending on the aluminum content, slightly hypsochromic.

Preferred aluminum-chrome, nickel and nickel produced according to the invention Cobalt mixed complex dyes correspond to formulas I and I ′

wherein the cores A, independently of one another, one or two substituents from the series C _1-3 alkyl, C _1-3 alkoxy, cyano, nitro, C _1-3 alkoxy carbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, mono- or di (C _1-4 alkyl) aminocarbonyl, mono- or di (C _1-3 alkoxy-C _2-4 alkyl) aminocarbonyl, phenylaminocarbonyl, aminosulfonyl, mono- or di (C _1-4 alkyl) ) -aminosulfonyl, mono- or di (C _1-3 -alkoxy-C _2-4 -alkyl) -aminosulfonyl and phenylaminosulfonyl,
all R ₁ independently of one another, an atomic group necessary for the completion of a mononuclear or dinuclear system of aromatic character, which may optionally carry substituents,
the two R ₂ independently of one another have an optionally substituted phenyl radical or a C _1-12 alkyl or C _1-2 alkoxy- C _2-8 alkyl radical,
Me 0.1 to 0.98 chromium, nickel, cobalt or copper atoms, preferably chromium or cobalt atoms and 0.02 to 0.9 aluminum atoms
and X⁺ is a cation
mean.

One- or two-nucleus aromatic systems (as R ₁ ) are to be understood in addition to benzene and naphthalene nuclei also heterocyclic nuclei. The heterocyclic nuclei are to be understood primarily as the five-membered rings containing nitrogen and / or sulfur, especially pyrazolone or pyridone. Unless otherwise stated, all substituents known in dye chemistry come into consideration as substituents on all nuclei of aromatic character, e.g. B. halogen, which is mainly to be understood as chlorine or bromine, hydroxyl, C _1-4 -alkyl, C _1-4 -alkoxy, cyano, nitro, rhodan, C _1-3 -alkylcarbonyl, benzoyl, C _1-3 -Al kylcarbonyloxy, aminocarbonyl, mono- or di- (C _1-4 -alkyl) -aminocarbonyl, mono- or di- (C _1-3 -alkoxy-C _2-3 -alkyl) -aminocarbonyl, C _1-3 - Alkoxycarbonyl, aminosulfonyl, mono- or di- (C _1-4 -alkyl) -aminosulfonyl, mono- or di- (C _1-3 -alkoxy-C _2-3 -alkyl) -aminosulfonyl. The same substituents are also suitable for R ₂ if this is a phenyl radical. In this case, however, preference is given to halogen atoms, which are to be understood above all to mean chlorine and bromine, C _1-4 alkyl, C _1-4 alkoxy or acetyl.

In the formulas I and I ', the symbols R ₁ denote the atoms / atom groups required to complete a coupling component; in formula I, the atomic groups necessary to complete a benzene or 1-phenyl-3-methylpyrazolyl coupling component, in formula I ', R ₁ preferably denotes the atomic group necessary to complete a naphthalene or benzene ring. In particular, the benzene nuclei can optionally substituents, for. B. chlorine, bromine, C _1-2 alkyl, C _1-2 alkoxy, carbonamide or sulfonamide.

As the cation X⁺ come the alkali metal ions, especially sodium or Potassium ions, ammonium, mono-, di- or trialkylammonium and above all 4-amino, 4-hydroxy or 4-keto-2,2,6,6-tetramethylpiperidinium ions in Consideration.

In particular preferred dyes of the formulas I and I 'correspond to Formulas Ia, Ib and Ic

in these formulas, each independently of the other substituents
all R nitro or a group of the formula -SO ₂ NHR ₃ ,
the R _{3 is} hydrogen, C _1-3 -alkyl, C _1-2 -alkoxy-C _2-3 -alkyl or phenyl, in particular methyl, ethyl, C _1-2 -alkoxy-C _2-3 -alkyl or phenyl,
R _{4 is} hydrogen, halogen, C _1-2 alkyl or C _1-2 alkoxy, preferably hydrogen, chlorine or methyl, in particular hydrogen,
the two R ₅ each have a 2-ethylhexyl radical or a phenyl radical which can carry up to three substituents, including up to two from the group chlorine, bromine, C _1-2 alkyl, C _1-3 alkoxy or acetyl, preferably one or two C _1-2 alkoxy groups and / or a chlorine or bromine atom or a methyl group, in particular one or two methoxy groups,
Me 0.25 to 0.95 atoms chromium or cobalt and 0.75 to 0.05 atoms aluminum and
X ₁ ⁺ a sodium, potassium, ammonium or C _1-10 alkylammonium ion, but in particular a 4-amino, 4-hydroxy or 4-keto-2,2,6,6-tetramethylpiperidinium ion
mean, the two cores B (formula Ia) can each carry one or two substituents, including one each from the group halogen, hydroxyl, C _1-2 alkyl, C _1-3 alkoxy, acetyl, benzoyl or 4,6 -Bis- (2 ', 4'-dimethylphenyl) -triazinyl-2, in particular one hydroxyl and one acetyl or benzoyl group, or the cores B carry the atomic group necessary to complete a naphthalene nucleus, preferably in 5'- and 6th 'Position bound, the substituents R are preferably bound in 4- or 5-position.

The metallization of the metal-free dyes is generally found in alkaline aqueous environment, at temperatures between 40 and 100 ° C, before preferably between 70 and 95 ° C, instead. The pH is z. B. between 10 and 12. It may be advantageous to add a ge to the aqueous alkaline phase rings amount of a wetting, solubilizing compound, e.g. B. a Glycol or a glycol ether. One adds to the chrome plating after good distribution (suspension) of the dye the bichromate and about double the amount of reducing compound, stir one to three Hours and then adds the aluminum, always at temperatures up to 100 ° C  salt, dissolved in water, slowly. The implementation with the other salts takes place in the same way, but without the addition of a reducing agent. After the (salting out and) washing out the dissolved salts, the metal becomes Complex dye isolated in the usual way.

The dyes produced according to the invention are suitable, like the be known, pure heavy metal complex dyes for all known applications fertilize. The dyes free from water-solubilizing substituents are excellent for dyeing (including bulk dyeing) plastic masses, including solvent-free and solvent-containing masses Plastics or synthetic resins are understood (in paints oily or aqueous basis, in varnishes of various types, for spinning dyeing viscose or cellulose acetate, for dyeing natural and synthetic polyamides, of polyester, polyethylene, polystyrene, poly vinyl chloride, rubber and synthetic leather). You can also print inks for the graphic arts industry, for pulp dyeing, for coating processing of textiles and leather, or use for pigment printing the.

The dyeings obtained are characterized by their excellent heat, Light and weather fastness, chemical resistance, their migration, Efflorescence, varnish and solvent fastness, their color strength and the very good application properties, e.g. B. Resistant to flocculation out of.

The dyeing or printing of the materials mentioned is carried out in the usual way Wise.

In the following examples, parts mean parts by weight and Percentages by weight. 1 part by volume corresponds to the volume of one Mostly water. The temperatures are given in degrees Celsius.

example 1

• a) 51.3 parts of 1-amino-2-hydroxy-4-nitrobenzene are stirred in a solution of 250 parts of water and 92.5 parts of 30% HCl. After adding 100 parts of ice, the amine is diazotized with 83 parts by volume of 4N NaNO ₂ solution. It is then buffered to pH 4.5 with sodium acetate and a solution of 56 parts of 1-phenyl-3-methyl-pyrazolone-5 in 400 parts of water and 48 parts of NaOH solution 30% run in slowly. By simultaneously adding 39 parts of 30% HCl, the pH is kept at 4.5 in the course of the coupling. The resulting suspension is then stirred for 8 hours at room temperature and for half an hour at 80 °, the precipitate is filtered off, washed with 150 ° parts of hot water and finally dried.
• b) 36.6 parts of the monoazo dye obtained in a) are in 120 Parts of water, 20 parts by volume of diethylene glycol monomethyl ether and 33 Parts of aqueous NaOH 30% suspended, heated to 70 ° and 30 minutes stirred. The pH of the suspension is approximately 11.9.

After further heating to 95 °, a solution of 7.8 parts of cobalt sulfate (CoSO ₄ .7H ₂ O) in 50 parts of water is added over the course of 30 minutes. After stirring for two hours at 95 °, a solution of 1 part of aluminum sulfate in two parts of water is slowly added.

After stirring for another two hours at 950, the dye is filtered hot, washed with a 1% NaCl solution until the filtrate is colorless and neutral, then the soluble inorganic salts are washed out with about 300 parts of cold water. This gives the dye of the formula Ib, in which R = nitro (in the 5-position), R _{4 is} hydrogen, X ₁ sodium and Me is 98 mol percent cobalt and 2 mol percent aluminum, which colors the plastic in orange-yellow shades.

Example 2

The procedure is as in Example 1, under a) and b), but adds after heating to 95 ° in the course of 30 minutes, a solution of 7.8 parts len sodium bichromate and 16.3 parts glucose in 50 parts water to, stirring at 95 ° for 2 hours, gives 1 part of aluminum sulfate, in 2 parts Dissolved water, stir, stir for another two hours, and finally isolate the mixed complex dye, the 98 mole percent chromium and 2 mole percent Aluminum contains, as stated in Example 1.  

In the following tables, further, analogous to the information in the 1st, be drawn in the second example, cobalt or chrome aluminum Complex dyes specified.

The dyes in Table 1 correspond to Formula Ia.

Table 1

The dyes in Table 2 below correspond to the formula Ib.

Table 2

The dyes according to Examples 24 to 28 can also, by analogy to the information in Example 2, be metallized with chrome; the ent speaking examples then bear the numbers 29 to 33.

Application example

Made in 95 parts of a nitrocellulose varnish

18.8% nitrocellulose A 15 moistened with 35% isopropanol (in the form of white flakes),
6.3% butyl acrylate polymers, plasticizer resin (Acronal 4F, BASF),
3.3% diphenyl octyl phosphate, plasticizer (Santicizer 141, Monsanto),
10.0% methoxypropanol (Dowanol PM, Dow Chemical),
10.0% ethoxypropanol,
41.6% ethanol and
10.0% ethyl acetate,

5 parts of the dye according to Example 1 were used with the dissolver stirs and loosened on the roller block overnight. The solubility is very Good.

With the 25 µm drawing rod, a wet film with this lacquer composition was created Made on aluminum foil and dried at 130 ° for 5 hours. Man he holds such an orange-yellow lacquer layer with very good light and migration authenticity.

Claims (8)

1. A process for the preparation of aluminum-heavy metal mixed comp lex dyes with a heavy metal content of, stoichiometric, 10 to 98% and an aluminum content of 90 to 2%, characterized in that the reaction of the metal-free dyes with a stoichiometric deficit of heavy metal compound and, calculated with the sum of the metals, performs a stoichiometric excess of aluminum compound. 2. The method according to claim 1, characterized in that as Heavy metals chrome, cobalt, nickel or copper, especially chrome or Cobalt can be used. 3. The method according to claim 1 or 2, characterized in that to produce 2: 1 azo metal complex dyes. 4. The method according to claim 3, characterized in that one 2 moles of dye 0.1 to 0.98 moles of heavy metal compound and 0.1 to 1.2 Mol uses aluminum compound. 5. The method according to any one of the preceding claims, characterized characterized in that water-insoluble, solvent-soluble Manufactures dyes. 6. The manufactured according to one of the preceding claims Aluminum-heavy metal mixed complex dyes. 7. The use of those free of water-solubilizing groups in organic solvent-soluble dyes, according to claim 6, for Coloring plastic masses. 8. The method according to claim 1, characterized in that one Aluminum / chrome or aluminum / cobalt mixed complex dyes with one Chromium or cobalt content of, stoichiometric, 80 to 98% and one Produces aluminum content from 2 to 20%.