DE2034542A1 - Quinone dye compsns - in dry form - Google Patents

Abstract

Preparation contains (a) quinone deriv. of formula: (where X is halogen, 2 is O or =N,X, =N-alkyl, where Y is H, halogen, alkyl, alkoxy or NO2, R1 to R4 are H, halogen, alkyl, alkoxy, or phenyl or R1 and R2 or R3 and R4 can forma condensed benzene ring) (b) an inorganic hydratable salt (c) tensides and (d) opt. dust-removing agent.

Description

Dry preparations of quinone derivatives are the subject of the present Invention are dry preparations of N-haloquinonimines, their preparation and Use for dyeing structures made of hydrophobic materials.

It is well known (see e.g. German patent specifications 1 145 137 and 1 202 245) that N-haloquinonimines are excellent for production true colorations, especially black colorations on structures pretreated with amines made of hydrophobic materials are suitable.

However, the practicality of these quinone derivatives is because of this limited that on the one hand the resulting press cake due to their creation the easy sublimability, the tendency to deflagration and a certain toxicity does not allow these substances to dry in the conventional way and that on the other hand the aqueous preparations - especially at temperatures above 300 ° C. - do not are sufficiently durable.

It has now been found that a non-flammable, storage-stable dry setting of N-haloquinoniinines of the general formula in which X is halogen, Z RUr is an oxygen atom or one of the radicals = NX, = N-alkyl, and where YH, halogen, alkyl. Alkoxy or NO2 is, R1 to R4 are independently hydrogen, halogen, alkyl, alkoxy or phenyl and in which R1 and R2 or R3 and R4 can collectively form the remaining members of a fused benzene ring, if the aqueous press cake of this is obtained Compounds with t) inorganic hydratable salts, b) surfactants and c) optionally dedusting agents mixed, ground and / or granulated.

It can be described as extremely surprising that the thermodynamic unstable dispersions of the quinone derivatives in the presence of the hydratable salts do not flake, as it is known that "almost all electrolytes are in higher concentrations Cause flocculation "(A. Kuhn:" Kolloidchemisches Taschenbuch "Akademische Verlagsgesellschaft Leipzig 1960 page 114). Nor was it foreseeable that the Schulze-Hardy rule would apply here (see e.g.

Mangold: "Colloidkunde", Verlag Straßenbau, Chemie und Technik 1958, Page 1108) does not apply, which says that polyvalent ions are much stronger flaky act as monovalent.

In formula 1 given above, the alkyl and alkoxy radicals are preferably for such radicals with 1 to 4 carbon atoms. The expression halogen is intended in particular Chlorine can be understood.

Suitable N-haloquinone imines of the formula (I) are: N-chloro-p-benzoquinone monoimine 2-chloro-N-chloro-p-benzoquinone monoimine, 2-bromo-N-chloro-p-benzoquinone monoimine, 2-methyl-N-chloro-p-benzoquinone monoimine 3-chloro-N-chloro-p-benzoquinone monoimine 3-bromo-N-chloro-p-benzoquinone monoimine 3-methoxy-N-chloro-p-benzoquinone monoimine 3-methyl-N-chloro-p-benzoquinone monoimine 2,5-dimethyl-N-chloro-p-benzoquinone monoimine 2,5-dichloro-N-chloro-p-benzoquinone monoimine 2,6-dichloro-N-chloro-p-benzoquinone monoimine 2,6-dibromo-N-chloro-p-benzoquinone monoimine 2,3,6-trichloro-N-chloro-p-benzoquinone monoimine 2,3,5,6-tetrachloro-N-chloro-p-benzoquinone monoimine L i) chloro-p-denzoquinone diimine 2-methyl-N, N'-dichloro-p-benzoquinonediimine 2-chloro-N, N'-dichloro-p-benzoquinonediimine 2-Bromo-N, N'-dichloro-p-benzoquinone diimine 2,3-dimethyl-N, N'-dichloro-p-benzoquinone diimine 2,5-dichloro-N, N'-dichloro-p-benzoquinone diimine 2,6-dichloro-N, N'-dichloro-p-benzoquinone diimine 2,6-dibromo-N, N'-dichloro-p-benzoquinone diimine 2,3,6-trichloro-ST, N'-dichloro-p-benzoquinone diimine 2,3,5,6-tetrachloro-N, N'-dichloro-p-benzoquinone diimine N-chloro-N'-methyl-p-benzoquinone diimine, N-chloro-N'-phenyl-p-benzoquinone diimine, N, N'-dichloro-1,4-naphthoquinone diimine, N-chloro-1,4-naphthoquinone monoimine.

Of these, these are N, N'-dichloro-p-benzoquinonediimine and, above all, that See N-chloro-p-benzoquinone monoimine as particularly preferred.

This N-chloro-p-benzoquinone monoimine has to do with previously known Quinone-based black developers have some technical advantages in terms of dyeing. To be highlighted is especially the good solubility of this compound in aqueous dye baths, which results in a more even dyeing and sometimes a higher dyeing speed is achieved. Compared to the equally suitable N, N'-dichloro-p-benzoquinonediimine Despite the lower oxidation value, it comes with a lower or at most equal application rate. Finally, you can use the N-chloro-p-benzoquinone imine in combination with suitable "black bases" such as 4-aminodiphenyl and its derivatives, Greenish black colorations can be produced using the previously described black developers based on quinone was not possible O Suitable inorganic hydratable salts, which are completely or partially freed from water are, for. Bs aluminum sulfate, chromium (III) sulfate, Iron (II) sulfate, copper (II) sulfate, cobalt (II) sulfate, manganese (II) sulfate, nickel (II) sulfate, Nickel (II) chloride, nickel (II) nitrate, magnesium sulfate, sodium sulfate, zinc sulfate as well as alums of the type MeI MeIII (SO4) 2 + 12H2O where MeI stands for Na, K or NH4 and MeIII stand for Al, Cr, Mn, Fe or Co.

The use of magnesium sulfate is particularly advantageous.

In general, you use an excess of these salts, based on the water content of the press cake of the quinone derivatives. at.

As surfactants, to improve the dissolution, to lower it the viscosity of highly concentrated settings and for spontaneous distribution with added are non-ionic and ionic surfactants to be used, such as anion-active, cation-active or amphoteric surfactants. A compilation of the ionogenic ones that can be used Tenside is in the Schwartz-Perry-Berch "Surface Active Agents and Detergents (Vol. 2 Interscienoe Publishers Inc. New York, 1958).

As anion-active surfactants, which are preferably to be used, come in question: alkyl sulfonates as described a.a.0. Pp. 63 - 71, alkylarylsulfonates, as described above, pp. 78 - 100 and So 278, FettsSureamidalkansulfonate, as described are loc. cit. p. 76, alkylsulfuric acid ester salts as described are loc. cit. pp. 40 - 61.

Condensed aryl sulfonic acids can also be used, such as z .D. Di-naphthyl methane sulfonic acids, condensation products from naphtholsulfonic acid, Cresol, formaldehyde and sodium bisulfite (Fiat Final Report No. 1013), diphenyl ether sulfonic acid and formaldehyde (US Patent 2,315,951), as well as from sulfonated phenols and formaldehyde and urea (German patents 1,113,457 and 1,178,081).

Suitable amphoteric compounds are, for example, alkylamine alkyl sulfonates, as described in DAS 1.020.144.

Cation-active products are mentioned above on pages 112-118.

Suitable non-ionic surfactants are mentioned above on the pages 125 - 138. These are polyethylene oxide, polyalkoxylated alcohols, Mercaptans, phenols, amines and carboxylic acids as well as polyhydroxy compounds.

Suitable means for dedusting and increasing the granulability are e.g .: higher-boiling esters, in particular dimethyl phthalate, diethyl phthalate, Dipropyl phthalate, dibutyl phthalate, glycerine acetate, non-volatile Oils, especially silicone oils with a viscosity of 102-106 cP, paraffin oils with boiling points > 100 ° C, natural products such as linseed oil, peanut oilE Polyalkoxylated compounds, in particular polyethylene oxides, polypropylene oxides and their addition products Alcohols and phenols are aromatic hydrocarbons that are fully or partially hydrogenated can be, in particular tetrahydronaphthalene and decahydronaphthalene; gelling Substances, in particular gelatine, alginates, tragacanth, cellulose esters, cellulose ethers, Starch ethers, polyacrylic acid and its derivatives, colloidal silica.

Under structures made of hydrophobic materials, in particular fibers, Threads, fabrics, bristles, tapes and foils made of polyesters, preferably polyethylene glycol terephthalates, Esters of terephthalic acid with p, p'-dihydroxydimethyldyolohexane, polyvinyl chloride, Polyacrylonitrile and its copolymers, cellulose esters, such as cellulose triacetate and -2 1/2 acetate, polyolefins such as polyethylene and polypropylene, synthetic polyamides as well as polycarbonates and modifications.

The dry preparations according to the invention, their degree of distribution at least corresponds to that before the shaping, can be used directly for the dyeing process.

The creation of colorations on the structures made of hydrophobic materials can be carried out according to the method as described in the German patents cited above are described.

The production according to the invention of the powdery dry settings will be explained in more detail using the following examples.

Example 1: 100 g of a press cake of N-chloro-p-quinonimine with a A content of 50% is added with 10 g of the sodium salt of 2,2'-dinaphthylmethanedisulfonic acid a homogeneous paste, which is mixed with 70 g of finely ground in a horizontal mixer Magnesium sulfate monohydrate and 1 g of dimethyl phthalate (as a dedusting agent) added and mixed until the water has completely set.

A yellowish, non-flammable powder is obtained, which at 810 C melts with decomposition. The preparation is storage-stable for at least 6 months at 450 a.

Example 2: 100 g of a 46 own press cake of p-quinonedichlorodiimine are with 20 g of an Na salt of the condensation product of 2 moles of diphenyl ether sulfonic acid mixed with 1 mol of formaldehyde and the coarse dispersion obtained 2 times by a Agitator mill prevailed. The fine dispersion thus obtained is in a screw mixer with the addition of 73 g of finely ground magnesium sulfate monohydrate and 1 g of silicone oil (as a defoamer) mixed until the setting of the water is complete.

A white, non-flammable powder is obtained, which at 1120 C is charred and has a shelf life of at least 6 months at 450 ° C.

Example 3: 100 g of 2,5-dichloro-N, N'-dichloro-p-benzoquinone dilmin press cake with a content of 45% with 12 g of the Na salt of a condensation product suspended on cresol-2-naphthol-6-sulfonic acid and formaldehyde and with 65 g of sodium sulfate Anhydrous added, with the addition of 1 g of decahydronaphthalene in a mixing granulator mixed and formed into granules.

The finished granulate consists of white, free-flowing PormX particles, which are non-flammable and have a storage stability of over 6 months at 450 C.

Example 4: 100 g of a 56 point press cake of N, N'-dichloro-1,4-naphthoquinonediimine are suspended in 25 g of dibutylnaphthalene sulfonate as Na salt, with 85 g of potassium aluminum sulfate anhydrous and 1 g of glycerol triacetate mixed and closed with a plate granulator Processed moldings.

The finished granules have properties similar to those in the example 3 described granules.

Claims (10)

Claims: 1.) Dry preparations of quinone derivatives consisting of or containing a) quinone derivatives of the formula in which X denotes halogen, Z denotes an oxygen atom or one of the radicals = NX, = N-alkyl, and where Y is H, halogen, alkyl, alkoxy or NO2, R1 to R4 are independently hydrogen, halogen, alkyl, alkoxy or phenyl and in which R1 and R2 or R3 and R4 together can form the remaining members of a fused benzene ring, b ) inorganic hydratable salts, c) surfactants and d) optionally dedusting agents. 2.) dry preparations according to claim 1, characterized in that these quinone derivatives of the formula in which X is chlorine, Z 'for an oxygen atom or one of the radicals -N-X', and where Y 'denotes H, chlorine, C1-C4-alkyl, C1-C4-alkoxy or NO2 and R11 to R4' independently of one another denote hydrogen, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy or phenyl . 3.) dry preparations according to claim 1, characterized in that that these contain N-chloro-p-benzoquinone as quinone derivatives in the in. 4.) dry preparations according to claim 1, characterized in that that these contain N, N'-dichloropbenzoquinone diimine as quinone derivatives. 5.) dry preparations according to claim 1, characterized in that that these contain magnesium sulfate as the inorganic hydratable salt. 6.) dry preparations according to claim 1, characterized in that that these as surfactants are anionic emulsifying or Contain dispersants. 7.) Process for the preparation of dry preparations of quinone imine halides, characterized in that aqueous press cakes of compounds of the general formula in which X denotes halogen, Z denotes an oxygen atom or one of the radicals = NX,: N-alkyl, where Y is H, halogen, alkyl, alkoxy or NO2, R1 to R4 independently of one another are hydrogen, halogen, alkyl, alkoxy or phenyl and in which R1 and R2 or3 and R4 together can form the remaining members of a fused benzene ring, with a ) inorganic hydratable salts, b) surfactants and c) optionally dedusting agents mixed, ground and / or granulated. 8.) Dry preparations of quinone derivatives, prepared according to claim 7th 9.) Use of dry preparations according to claim 1 for dyeing of structures made of hydrophobic materials. 10.) Use of dry preparations according to claim 1 for dyeing of fibers and fabrics made from polyester.