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
  • 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
  • D06P1/60—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 polyethers
  • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
  • D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
• • 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
• • 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
• • 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
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose

Definitions

• the present invention relates to a new process for dyeing leather using pigments, the dyeing being carried out in the presence of an oxyalkylated amine, the amine having at least 20 carbon atoms.
• the object of the present invention was therefore to provide a process for dyeing leather with pigments as colorants, in which a uniformly colored surface and, in the case of thin leathers, also a full coloration of the leather is achieved.
• Oxalkylated amines which can be used in the process according to the invention and which have at least 20 carbon atoms are to be understood as secondary or tertiary amines which have hydrocarbon radicals which are saturated or unsaturated, at least one of these radicals being interrupted by one or more oxygen atoms.
• the hydrocarbon radicals are straight-chain, branched or cyclic and optionally interrupted by one or more imino groups and / or substituted by hydroxy.
• amines can be obtained, for example, if C1-C30-alkylamines, C3-C30-alkenylamines or C2-C30-hydroxyalkylamines with alkylene oxides of the formula I. in which R1 and R2 are the same or different and, depending on one another, each represent hydrogen, methyl or ethyl.
• polyamines of the formula II in the L for C2-C6-alkylene eg ethylene, 1,2-propylene or 1,2- or 1,4-butylene
• the upper limit of the number of carbon atoms in the oxyalkylated amines to be used according to the invention depends on the number of moles of the same or different alkylene oxides of the formula I which react in the oxyalkylation Amines usually around 30,000.
• the process according to the invention is preferably carried out with those alkoxylated amines whose average molecular weight is 2000 to 20,000, in particular 4,000 to 15,000 and very particularly 7,000 to 13,000.
• oxalkylated amines which derive from the reaction of C12-C25-alkylamines or C12-C25-alkenylamines with ethylene oxide and / or propylene oxide is also preferred.
• oxyalkylated amines obtained by reacting polyamines of the formula II or aromatic or cycloaliphatic diamines with 3 to 50 moles of propylene oxide per equivalent of reactive amino hydrogen and subsequent reaction with 2 to 70 moles of ethylene oxide per equivalent of reactive amino hydrogen and the proportion of terminal polyethylene oxide blocks is 35 to 80% by weight, preferably 35 to 45% by weight and in particular approximately 40% by weight.
• block copolymers generally have an average molecular weight of 4,000 to 15,000, preferably 11,000 to 15,000.
• Suitable amines which can be reacted with alkylene oxides of the formula I are e.g. Methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, pentylamine, isopentylamine, neopentylamine, tert-pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, 2-hexadecylamine, 2-heptyldecylamine, octadecylamine, eicosylamine, 2-octyldodecylamine, docosylamine, hexacosylamine, triacontylamine, octadec
• the amines to be used according to the invention are generally products known per se. In many cases, these products are commercially available. Amines of the type mentioned are e.g. in K. Lindner, Tenside-Textilhesstoff-Waschrohstoffe, Volume 1, p. 963 ff., 1964.
• inorganic and organic pigments are suitable as pigments which can be used in the process according to the invention, the use of organic pigments being preferred.
• Inorganic pigments which serve as colorants in the process according to the invention are, for example, iron oxides, titanium dioxides or carbon blacks.
• Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoacetic acid derivatives or from ⁇ -naphthol derivatives), lacquered monoazo dyes, such as lacquered ⁇ -oxy naphthoic acid dyes, disazo pigments, condensed disazo pigments, isoindoline derivatives, derivatives of naphthalene or perylene tetracarboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalocyanine enamel pigments, phthalocyanine pigment varnishes, pigment varnishes or phthalocyanine pigment varnishes,
• Pigment Yellow 42 examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007), or Pigment Black 7 (CI 77 266) , as well as the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 16 (CI 20 040), Pigment Yellow 17 (CI 21 705, Pigment Yellow 42 (CI 77 492), pigment Yellow 74 (CI 11 741), Pigment Yellow 83 (CI 21 108), Pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 13 (CI 21 110), Pigment Orange 34 (CI 21 115), Pigment Orange 36 (CI 11 780), Pigment Orange 43 (CI 71 105), Pigment Orange 67, pigment Red
• Pigment Red 146 (CI 12 485), Pigment Red 169 (CI 45 160: 2), Pigment Red 170, Pigment Violet 19 (CI 46 500), Pigment Violet 23 (CI 51 319), Pigment Violet 27 ( CI 42 555: 3), Pigment Blue 1 (CI 42 595: 2), Pigment Blue 15: 1 (CI 74 160), Pigment Blue 15: 3 (CI 74 160), Pigment Blue 61 (CI 42 765: 1) , Pigment Green 7 (CI 74 260), Pigment Green 8 (CI 10 008) or Pigment Green 36 (CI 74 265).
• the oxyalkylated amines are used, for example, in an amount of 0.1 to 5%, preferably 0.3 to 3% and in particular 0.3 to 2%, in each case based on the wet weight of the leather to be dyed. An increase in the amount of amine is possible. However, it has no further advantages.
• the pigments are used, for example, in an amount of 0.02 to 4% based on the wet weight of the leather to be dyed.
• organic pigments preference is given to using 0.1 to 2% and in particular 0.2 to 1% pigment, based on the wet weight of the leather to be dyed.
• inorganic pigments it is preferred to use 0.2 to 4% and in particular 0.4 to 2%, in each case based on the wet weight of the leather to be dyed.
• mineral leather e.g. based on the metals chrome, aluminum, titanium or zirconium
• leather to be dyed Such types of leather are e.g. used for the production of leather clothing, as upholstery leather or as upper shoe leather.
• Oxalkylated alcohols which can be used in the process according to the invention are understood to mean those alcohols which have a hydrocarbon radical which is saturated or unsaturated and is interrupted by one or more oxygen atoms.
• the hydrocarbon radical is straight-chain, branched or cyclic and optionally substituted by further hydroxyl groups.
• These alcohols can e.g. are obtained when reacting C1-C30 alkanols, C3-C30 alkenols or C2-C30 alkane polyols with alkylene oxides of the formula I.
• alkoxylated alcohols are preferred which are derived from the reaction of C10-C20 alkanols, C10-C20 alkenols or C2-C6 alkane polyols with ethylene oxide and / or propylene oxide.
• the upper limit of the number of carbon atoms in the oxyalkylated alcohols to be used according to the invention depends on the number of moles of the same or different alkylene oxides of the formula I which react in the oxyalkylation Alcohols usually around 10,000.
• the process according to the invention is preferably carried out with those alkoxylated alcohols whose molecular weight is 300 to 2000 and in particular 500 to 1500.
• Suitable alcohols which can be reacted with alkylene oxides of the formula I are, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, neopentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 2-propylheptanol , Dodecanol, 2-butyl octanol, tetradecanol, 2-pentyl nonanol, hexadecanol, octadecanol, Eico sanol, tetracosanol, hexacosanol, octacosanol, tricosanol, octadec-9 (cis) -enol, o
• the oxyalkylated alcohols to be used according to the invention are generally products known per se. In many cases, these products are commercially available. Alcohols of the type mentioned are e.g. in K. Lindner, Tenside-Textilwhismitte-Waschrohstoffe, Volume 1, pp. 837 ff., 1964 or in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Volume 22, pp. 488 ff.
• the alkoxylated alcohols are used, for example, in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight and in particular 0.2 to 2% by weight, based in each case on the leather to be dyed.
• the pigments used as colorants in the new process can advantageously be in the form of pigment preparations known per se, e.g. can be used as aqueous dispersions.
• Those aqueous pigment preparations which contain nonionic surfactants as dispersing agents are preferred.
• nonionic surfactants which may be mentioned are the above-mentioned components to be used according to the invention or also addition products of alkylene oxides with fatty acids, phenols, alkylphenols, acid amides or mercaptans.
• aqueous pigment preparations which contain an oxyalkylated amine which has at least 20 carbon atoms as a dispersing aid. They are e.g. described in DE-A-2 156 603.
• pigments which have a particle size of less than 1 ⁇ m, e.g. have from 0.01 to 0.2 ⁇ m, deliver particularly favorable results.
• a preferred procedure is to treat the leather with an aqueous pigment preparation which contains an oxyalkylated amine which has at least 20 carbon atoms as a dispersing aid.
• a particularly preferred procedure consists in treating the leather with an aqueous pigment preparation containing an oxyalkylated amine and additional oxyalkylated amine.
• a procedure is very particularly preferred in which the leather is treated with an aqueous pigment preparation containing an oxyalkylated amine and additional oxyalkylated amine and an oxyalkylated alcohol which has at least 16 carbon atoms.
• the process according to the invention is expediently carried out in such a way that a leather which has been pretreated in a customary manner is placed in an aqueous liquor in a drum and the pigment is carried out at a temperature of 20 to 60 ° C., preferably 40 to 50 ° C., preferably in the form of an aqueous one Preparation containing an oxyalkylated amine as a dispersing agent, optionally adding additional oxyalkylated amine and optionally oxyalkylated alcohol.
• the leather is then dyed at the above-mentioned temperature and at a pH of 4 to 7, preferably 4.5 to 6, with milling. The dyeing process is generally complete after 0.5 to 2 hours. After conventional fixation with formic acid, the leather is then removed from the dyeing liquor, washed with water and worked up by methods known per se.
• the process according to the invention can also be carried out in the presence of other auxiliaries or additives customary in leather dyeing, e.g. commercially available salts of condensation products of phenolic or naphthalenesulfonic acids with formaldehyde and urea, fat liquors based on emulsified paraffins or water-soluble polymers based on acrylates, which have a molecular weight of approx. 2000 to 5000, are operated.
• auxiliaries or additives customary in leather dyeing e.g. commercially available salts of condensation products of phenolic or naphthalenesulfonic acids with formaldehyde and urea, fat liquors based on emulsified paraffins or water-soluble polymers based on acrylates, which have a molecular weight of approx. 2000 to 5000, are operated.
• auxiliaries or additives can be added to the aqueous liquor either before the dyeing process or together with the pigment and the oxyalkylated amine.
• water-soluble acid dyes are azo dyes known per se which contain sulfonic acid groups and are either metal-free or can be present as a metal complex, metal phthalocyanines containing sulfonic acid groups or anthraquinones containing sulfonic acid groups.
• the water-soluble acid dyes are expediently added in powder form or in the form of a liquid preparation to the dyeing liquor. They are advantageously added with that of the pigment.
• 0.1 to 6 preferably 0.5 to 5% and in particular 0.5 to 3%, in each case based on the wet weight of the leather to be dyed, of water-soluble acid dye is used.
• the leather can be treated both with individual pigments and with mixtures of pigments. It is preferred to dye the leather with a mixture of yellow, red and blue pigments, which results in brown shades.
• the new process leads to leather dyeing that is characterized by excellent levelness, depth of color, brilliance as well as high light fastness, wet fastness and migration fastness values. In addition, they show good coloring.
• the percentages are percentages by weight and relate to seam-damp chrome leather.
• the pigments used in the examples were each used in the form of an aqueous preparation, the oxyalkylated amine ethylenediamine which was first reacted with propylene oxide and then with ethylene oxide (ethylene oxide content: 40%; M 10500). Based on the weight of the pigment, the amine content was 20%.
• the acid dyes were used in the form of an aqueous solution.
• the oxyalkylated amine is oleylamine which has been oxethylated with about 10 moles of ethylene oxide.
• the alkoxylated alcohol is tallow fatty alcohol that has been oxethylated with approx. 80 mol ethylene oxide.
• Upholstery leather was treated at a temperature of 50 ° C in 200% of an aqueous liquor containing 1% ammonia for 10 minutes. Then pigment, optionally acid dye, alkoxylated amine and alkoxylated alcohol were added to the dye liquor. The leather was then tumbled for 30 minutes, mixed with 10% of a commercially available fat liquor and tumbled for a further 60 minutes. After the addition of 2.5% formic acid (in 2 portions, at 15 minute intervals), the work was drummed for a further 30 minutes. The dye liquor was then drained off.
• the leather was then drummed at a temperature of 50 ° C in 200% of a dye liquor containing pigment, acid dye, oxalkylated amine and oxalkylated alcohol for 30 minutes. After the addition of 1% formic acid, it was drummed for a further 30 minutes.
• the leather was then removed from the liquor and drummed at a temperature of 40 ° C. in 200% of an aqueous liquor which contained 0.3% formic acid for 5 minutes. Then 0.3% of a commercially available cationic post-fixing agent was added and drummed for a further 30 minutes.
• the leather was then worked up using conventional methods, i.e. stretched wet, dried, moistened and grilled.
• Upper leather was retanned using customary methods with a polymer tanning agent based on acrylic acid / acrylonitrile, an amphoteric tanning agent based on a condensation product of phenolsulfonic acid and formaldehyde and a resin tanning agent based on a condensation product of melamine and formaldehyde and then washed out.
• a polymer tanning agent based on acrylic acid / acrylonitrile an amphoteric tanning agent based on a condensation product of phenolsulfonic acid and formaldehyde
• a resin tanning agent based on a condensation product of melamine and formaldehyde
• the retanned leather was drummed at a temperature of 55 ° C. in 150% of an aqueous liquor which contained pigment, acid dye, oxalkylated amine and optionally oxalkylated alcohol for 40 minutes. Then 6% of a commercially available fat licker was added and the fabric was drummed for 40 minutes. Finally, 1% formic acid was added in 2 portions, followed by drumming for 20 minutes after adding the 1st portion and for 30 minutes after adding the 2nd portion. The leather was then removed from the liquor and worked up by customary methods, i.e. dried, moistened and stubbed under reduced pressure.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)

Applications Claiming Priority (2)

Publications (3)

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ID=6355333

Family Applications (1)

Country Status (7)

Cited By (2)

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Family Cites Families (5)

• 1988
  • 1988-05-28 DE DE3818183A patent/DE3818183A1/de not_active Withdrawn
• 1989
  • 1989-05-20 EP EP89109121A patent/EP0344555B1/fr not_active Expired - Lifetime
  • 1989-05-20 ES ES89109121T patent/ES2042875T3/es not_active Expired - Lifetime
  • 1989-05-20 DE DE89109121T patent/DE58905506D1/de not_active Expired - Lifetime
  • 1989-05-25 CA CA000600718A patent/CA1335926C/fr not_active Expired - Fee Related
  • 1989-05-25 JP JP1130295A patent/JP2783290B2/ja not_active Expired - Lifetime
  • 1989-05-26 US US07/357,712 patent/US4983185A/en not_active Expired - Lifetime
  • 1989-05-27 KR KR1019890007203A patent/KR960015894B1/ko not_active Expired - Fee Related

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