Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
  • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
  • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
  • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6426—Heterocyclic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6429—Compounds containing nitrogen bound to a six-membered aromatic carbocyclic ring
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups

Definitions

• the optionally alkylated and oxyalkylated amines and polyamines used therein tend to smear in powder settings and to decompose into ammonia and volatile amines.
• DE-A 3 738 962 has succeeded in producing stable dye-auxiliary preparations, but these preparations sometimes produce spotty colorations on the leather substrates.
• condensation products are suitable for leather dyeing which are based on at least one of the amines defined above and a mixture of a dicarboxylic acid, preferably glutaric and adipic acid, and a C3-C8- ⁇ -aminocarboxylic acid or its lactam, preferably 6-caprolactam.
• condensation products of combinations of a diamine of formula (I) and a polyamine of formula (III) with combinations of glutaric or adipic acid and 6-caprolactam are condensation products of combinations of a diamine of formula (I) and a polyamine of formula (III) with combinations of glutaric or adipic acid and 6-caprolactam.
• the molar ratio of the polyamines of the formula (III) to the diamines of the formula (I) and that of the glutaric or adipic acid to 6-caprolactam can vary within wide limits and is preferably greater than 1 in both cases.
• diamines of the formula (I) are:
• Piperazine derivatives of the formula (II) are, for example, piperazine, aminoethylpiperazine, N, N'-bis [2-aminoethyl] piperazine.
• Suitable dicarboxylic acids are, for example: Oxalic acid, malonic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, terephthalic acid and isophthalic acid.
• Suitable “functional derivatives” are their anhydrides or alkyl esters and half-esters.
• ⁇ -aminocarboxylic acids and their lactams 6-aminocaproic acid, 8-aminocaprylic acid, 6-caprolactam and 8-capryllactam.
• polyamide amines to be used according to the invention are known per se (cf. e.g. DE-A 3 808 741).
• These resins can be prepared from the above-mentioned components in a likewise known manner. for example by heating the corresponding amine and carboxylic acid components under normal pressure at temperatures in the range from 110 to 250 ° C., preferably from 140 to 210 ° C. The mixture is first heated under reflux and then the temperature is reduced while the water of reaction is simultaneously reduced rise to 210 ° C over several hours. The viscous reaction mass formed can be adjusted to a viscosity which is favorable for handling by dilution with water.
• leather materials such as chrome leather, leather retanned with vegetable, synthetic or combined tanning agents, suede leather, split suede, nubuck or wool and fur skins are suitable for the process according to the invention for dyeing leather.
• the leathers can have different thicknesses, starting from thin leathers, for example glove leather, over medium strength leathers, such as upper shoe leather and clothing leather, to strong leathers, such as upholstery leather, suitcase leather and leather for sporting goods.
• the anionic dyes used in the dyeing process according to the invention can be acid, sulfone-containing metal complex, direct, pickling, reactive and solubilized sulfur dyes.
• they are the usual dyes used for dyeing leather and contain sulfo groups, as described, for example, in G. Otto, Das Desirben der Leder (1962) pp. 51-90 and pp. 107-143 or in JF Feeman, "The Chemistry of Synthetic Dyes ", edited by Venkataraman (1978) pp. 42-73.
• the sulfo Group-containing leather dyes are mainly used in the form of their alkali or ammonium salts.
• the water-soluble polyamide amine resins which are effective as auxiliaries can be applied to leather in amounts of 0.5-50%, primarily 5-20% by weight of the amount of dye before, simultaneously with or after the dyes.
• the preferred method is the simultaneous use of dye and auxiliary, preparations with dye and auxiliary being used with advantage.
• the auxiliary is incorporated into the dye in an amount which is favorable for the dyeing process.
• the resulting dye settings can be applied in any form, for example as powder preparations, liquid formulations or granules.
• auxiliaries can also contain other customary setting and auxiliary materials, in particular inorganic salts such as sodium chloride, sulfate, carbonate, buffer mixtures, alkalis such as lithium or potassium hydroxide, non-electrolyte-type adjusting agents such as dextrin, sugar, urea, starch, anionic surfactants such as lignin sulfonates, alkylnaphthalenesulfonic acids, alkylbenzenesulfonic acids, non-ionic surfactants such as ethylene oxide adducts with alkylphenols, dedusting agents such as phthalic acid esters.
• Other auxiliaries can be drying preventers, preservatives, hydrotropic substances or solvents.
• the dye settings are preferably in solid form as homogeneous mixtures of sulfo-containing dyes, the auxiliaries according to the invention and electrolyte-like setting material.
• the homogeneous mixtures can be contained in particular by dissolving or suspending these components in water and subsequent spray drying.
• Another variant consists in adding the auxiliary to the dye during or after its synthesis, but before it is isolated, and spray-drying the dye together with auxiliary and adjusting material.
• the leather is dyed in an aqueous bath with the usual liquor ratios of 50 to 1,000% by weight of water, based on the folded or dry weight of the substrate.
• the amount of dye offered can range from 0.01 to 15% by weight, depending on the leather material and the desired depth of color.
• the pH of the dyeing liquor is primarily kept at 4.0 to 8.0 and the dyeing temperature is mainly at 25 to 70 ° C.
• the claimed polyamide amines are distinguished, for example, by better dye bath stability, ie by a lower tendency to form precipitates. out.
• 292 g of adipic acid are introduced into a template consisting of 123.6 g of diethylenetriamine, 51 g of ethylenediamine and 113 g of 6-caprolactam.
• the mixture is heated under reflux at 140-150 ° C. for 45 minutes, then the reflux condenser is exchanged for a distillation bridge and the mixture is further heated for about three hours, with the water of reaction being separated, until the internal temperature has risen to 197 ° C.
• the melt is then allowed to cool to 165 ° C., 508 ml of water are carefully added and the solution is stirred at 90 ° C. for 1 hour.
• a mixture of 123.6 g of diethylenetriamine, 51 g of ethylenediamine and 153 g of 6-caprolactam is treated with 292 g of adipic acid under the same conditions as described in Example 1.
• the solids content is 49.9% by weight, the base equivalent weight is 792 and the viscosity (25 ° C) is 399 mPa.s.
• a similar product is formed when the 123.6 g diethylenetriamine of this example is replaced by a mixture of 82.4 g diethylenetriamine and 58.4 g triethylenetetramine.
• the black dye present as the sodium salt which is obtained by diazotizing 4,4'-diamino-stilbene-2,2'-disulfonic acid and p-nitroaniline and coupling to 8-amino-1-naphthol-3,6 -disulfonic acid, resorcinol, and 1,3-diaminobenzene, are struck in 350 ml of water.
• 30 g of polyamide amine condensate according to Example 1 and 6.5 g of sodium sulfate are added and the mixture is stirred vigorously for three hours.
• the mixture is worked up by spray drying via a two-component nozzle at an inlet temperature of 180 ° C. and an outlet temperature of 80 ° C. If an oil-emulsifier mixture is finally dedusted with 2 g, about 100 g of a readily water-soluble, storage-stable dye are obtained. Aid preparation.
• 0.2 mol of 4-amino-4'-nitro-diphenylamine-2'-sulfonic acid are diazotized in the usual way and coupled to 0.195 mol of 1-aminonaphthalene-6-sulfonic acid in the acetate-buffered aqueous medium.
• the monoazo dye obtained in this way is in turn diazotized and coupled in sodium hydroxide solution to 0.185 mol resorcinol.
• Repeated diazotization of 0.2 mol of 4-amino-4 -′-nitrodiphenyl-2 -′-sulfonic acid and coupling to the reaction product with resorcinol leads to the red-brown suspension of the trisazo dye.
• the suspension is mixed with 138 g of polyamide amine from Example 1, 80 g of sodium sulfate and 7.5 g of oil-emulsifier mixture, stirred vigorously for one hour and sprayed off at an inlet temperature of 180 ° C. and an outlet temperature of 80 ° C. A stable, dark red-brown coloring dye preparation is obtained.
• the following examples show the composition of other preparations made from dyes, auxiliaries, filler materials and dedusting agents. It is prepared by stirring in five times the amount of water for one to two hours and then spray drying at an inlet temperature of 180 ° C and an outlet temperature of 80 ° C.
• Example 5 41 g of red-brown dye, obtained by diazotizing 4-amino-4'-nitro-diphenylamine-2'-sulfonic acid, coupling to a 1: 1 mixture of 1-naphthylamine-6-and -7-sulfonic acid, diazotizing the reaction products, Coupling on phenol, salting out with sodium chloride, suctioning off the precipitate and drying, 48 g sodium sulfate, 18 g auxiliary agent diluted with water according to Example 1, 2 g of an oil-emulsifier mixture
• Example 6 61 g of dye CI Acid Black 1, 20 470 26 g sodium sulfate, 22 g auxiliary agent diluted with water according to Example 1, 2 g of an oil-emulsifier mixture
• 100 parts of chrome-tanned calfskin with a fold thickness of 0.7 mm and retanned with synthetic tanning agents are first broached for 60 minutes in 1,000 parts of water and 2 parts of technical ammonia at 50 ° C.
• the liquor is allowed to run off, washed with 1,000 parts of 50 ° C warm water and dyed at 50 ° C in 500 parts of fresh water with 1 part of dye C.I. Acid Brown 83, 20 250.
• the bath is acidified to pH 3.5 with 1.2 parts of 85% formic acid.
• the leather is aftertreated in a new bath of 500 parts 50 ° C warm with 0.45 part water-diluted auxiliaries according to Example 1 and 10 minutes later with 0.5 parts of the same dye.
• Example 17 100 parts of the same leather as in Example 17 are paperback and washed as described there. Then in a fresh bath of 500 parts of 50 ° C hot water 1.5 parts of undissolved dye auxiliary preparation of Example 16 were added. After a dyeing time of 60 minutes, the leather is acidified with 2 parts of 85% formic acid and finished. A level reddish medium brown coloration is obtained which is comparable in color depth to the coloration of Example 17.
• Example 18 the dye-auxiliary preparation is replaced by an amount of C.I. Acid Brown 83, 20 250 of the same color strength and let 0.45 parts of water-diluted auxiliary according to Example 1 run on, the effects are corresponding.
• the type of leather, colorant and shade of color are compared in a table.
• the dyeings are characterized by good levelness and fastness to perspiration. Bath exhaustion and depth of color are consistently better than with the same range of dyes without aids.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)

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• 1989
  • 1989-10-18 DE DE3934713A patent/DE3934713A1/de not_active Withdrawn
• 1990
  • 1990-10-02 US US07/591,926 patent/US5074884A/en not_active Expired - Fee Related
  • 1990-10-05 EP EP90119136A patent/EP0423561A1/fr not_active Withdrawn
  • 1990-10-12 JP JP2272482A patent/JPH03137282A/ja active Pending
  • 1990-10-16 CA CA002027730A patent/CA2027730A1/fr not_active Abandoned

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