EP0243788B1 - Agent de traitement du cuir - Google Patents

Agent de traitement du cuir Download PDF

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Publication number
EP0243788B1
EP0243788B1 EP87105532A EP87105532A EP0243788B1 EP 0243788 B1 EP0243788 B1 EP 0243788B1 EP 87105532 A EP87105532 A EP 87105532A EP 87105532 A EP87105532 A EP 87105532A EP 0243788 B1 EP0243788 B1 EP 0243788B1
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EP
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Prior art keywords
leather
groups
weight
formula
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87105532A
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German (de)
English (en)
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EP0243788A3 (fr
EP0243788A2 (fr
Inventor
Harro Dr. Träubel
Helmut Dr. Woynar
Hans Werner Müller
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Bayer AG
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Bayer AG
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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
    • D06P1/64—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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups
    • 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
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6131—Addition products of hydroxyl groups-containing compounds with 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
    • 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
    • D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
    • D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
    • 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

Definitions

  • the leather treatment compositions according to the invention preferably contain components a) and b) in a weight ratio of 95: 5 to 5:95. They are used as a solution, emulsion or dispersion, preferably as an aqueous solution.
  • the pH of the aqueous solutions is between 3 and 9, preferably between 5 and 8.
  • the total concentration of a) and b) in the leather treatment compositions is, for example, 15-60% by weight, preferably 30-60% by weight.
  • the components a) preferably have a molecular weight of 500-10,000.
  • the components b) in particular have a molecular weight of 300-10,000.
  • Components a) are produced by adding ethylene and / or propylene oxide to suitable starters.
  • suitable starters examples include: water; Monoalcohols such as methanol, ethanol, butanol; Diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4- and 3,6-dianhydrosorbitol, 4,4'-dihydroxydiphenylpropane; Triols such as glycerin, trimethylolethane, trimethylolpropane; higher polyols such as pentaerythritol, sorbitol, mannitol, formitol, formose, sucrose; Phenol and alkylphenols such as nonylphenol.
  • Preferred compounds a) are those which are more than 1 g / l water-soluble at 20 ° C.
  • Components b) are obtained by reacting polyvalent carboxylic acids with polyhydric alcohols, amines and amino alcohols to give oligoester amide carboxylic acids.
  • the carboxylic acids can be used in the form of their anhydrides.
  • carboxylic acids are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, glutaric acid, maleic acid, fumaric acid.
  • polyhydric alcohols are: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentylglycol, 1, 4-bis- [hydroxymethyl] cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinite, mannitol, sorbitol, formite , Methylglycoside, furthermore in particular oligoethylene glycols and oligopropylene glycols.
  • polyvalent amines examples include: ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, 1-amino-3-aminomethyl-3,5,5, -trimethylcyclohexane, 1,4-diaminocyclohexane , Diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine.
  • amino alcohols are: ethanolamine, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, isopropanolamine, diisopropanolamine, N-methylisopropanolamine, N-methyldiisopropanolamine.
  • DE-AS 2 856 628 describes ethylene oxide adducts with alkylamines with 8-20 C atoms as leveling agents and penetration aids for dyes.
  • DE-AS 2 539 671 also shows that C4 ⁇ 22-alkylamines with hydroxyethyl end groups equalize colorations.
  • An alkylamine with preferably more than 12 carbon atoms in the alkyl group and with hydroxyethyl groups is described as a dyeing aid in GB-PS 705 335,
  • Nonionic addition products of ethylene oxide are described together with ethoxylated C10 ⁇ 22 fatty amines as surface-active dyeing aids for nitrogen-containing substrates such as leather in US Pat. No. 3,334,960.
  • FR-A 23 54 383 relates to a process for tanning leather, according to which ester and / or urethane and / or amide group-containing carboxylic acids are used as tanning active substances; as emulsifiers i.a. Called polyalkylene glycol ethers of alkylphenols (p. 6, penultimate paragraph); Alkylene oxide adducts with aliphatic alcohols are not mentioned. It has been found according to the invention that undesired foaming during the dyeing process can be avoided by using alkylene oxide adducts with aliphatic alcohols. Mixtures which contain alkylene oxide adducts with aliphatic alcohols according to the invention are mixtures of the prior art which contain alkylene oxide adducts with phenols are clearly superior in terms of the levelness of the colorations.
  • EP-A-209 780 represents prior art within the meaning of Art. 54 (3) EPC. It relates to mixtures for treating leather which contain carboxyl group-containing compounds and amino group-containing alkylene oxide adducts with aliphatic alcohols.
  • the mixtures according to the invention do not have these disadvantages. They result in a deep penetration of the dye into the leather and at the same time a high color strength on the surface and excellent exhaustion of the dye liquor.
  • the process for leather treatment with the new mixtures is carried out according to known methods in tanning drums or tanning mixers.
  • the temperatures are generally 10-90 ° C, preferably 30-60 ° C.
  • the aqueous treatment liquors contain a total of 0.01-20% by weight, preferably 0.2-2% by weight (based on the shaved weight) of the agents according to the invention.
  • the treatment can be carried out before or at the same time as the coloring and also together with the oiling.
  • the products according to the invention are preferably used together with the dye in solution.
  • Suitable dyes are the dyes customary for leather dyeing, which are described, for example, in the Color Index, Vol. 2, 3rd Edition.
  • the amount of the dye applied to the leather and the amount of dye in the remaining liquor is determined optically in the following examples in accordance with the test described by H. Traubel and A. Goffin in “Leather and Skin Market, Sept. 1985” (hereinafter referred to as "Test A” designated) determined.
  • Alkylene oxide adducts are prepared in a known manner by adding oxiranes to starter alcoholates and then neutralizing, filtering salts and optionally adding oxidation inhibitors.
  • trimellitic anhydride 576 parts are melted at 180 ° C. 268 parts of dipropylene glycol are added dropwise over the course of 2 hours. Then 54 parts of water are distilled off in a water jet vacuum until the acid number of the product is 288 mg KOH / g. After cooling to 100 ° C., the product is dissolved in a mixture of 618 parts of water and 260 parts of 25% ammonia.
  • compositions 3.1.-3.9 listed in Tab. 1 were produced and tested in detail.
  • Chrome-tanned leather (4.0% Cr2O3 based on 14% water) is divided and processed in various ways (percentages refer to the shaved weight).
  • the leather is washed, neutralized, retanned and dyed according to the following formula: To wash: 300% Water 40 ° C 10 min Neutralization: 200% Water 40 ° C 0.4% Calcium formate 0.3% Sodium bicarbonate 45 min pH 4.7-5.0, rinse 40 ° Retanning: 200% Water 40 ° 2% ® TANIGAN OS 2% ® RETINGAN R7 2% Mimosa 40 min pH 4.7-5.0
  • the liquor is drained off after retanning and 300% water at 50 ° C. and 0.5% of the mixtures 3.1.-3.9 according to the invention are added. After 15 minutes, 1.5% Direct Brown 80 (CI 20210) and 3% fat liquor mixture (1) added. After a running time of 40 minutes, the dye is fixed by treatment with 1% 85% formic acid (pH 4-4.5) for 20 minutes.
  • (1) mixture of 60 parts of natural and synthetic fatty acids, 30 parts of unbranched chlorinated hydrocarbons and 10 parts of synthetic foot oil.
  • the leather is finished as usual. It has a satisfactory surface color strength and good depth of penetration of the dye.
  • washing, neutralizing and retanning are carried out as in method A.
  • the dyeing is carried out as follows.
  • the leather is first tanned with 0.8% of the mixture according to the invention 3.3 without retanning. or 3.6. Treated for 15 min (300% water, 50 ° C). The coloring is then carried out with 1% C.I. Acid Black 173 (40 min). Greasing, dye fixation and completion are the same as for method A (Table 2).
  • C.I. Acid Black 173 can also C.I. Acid Red 279 and C.I. Acid Brown 429 can be used.
  • the leather is treated as in method C, but a retanning as in method A is carried out between neutralization and dyeing.
  • the leathers are washed, neutralized and dyed as in Method C, using either 1% C.I. Acid Red 279 (Table 3) or 1% C.I. Acid Brown 429 (Table 4) can be used.
  • the leathers are washed, neutralized and retanned as in Method D and dyed as in Method F.
  • the chrome extract is then made.
  • washing, retanning, neutralizing and retanning are carried out analogously to method E and staining analogously to method F.
  • the chrome extract is then again produced.
  • the determination of the color strength on the leather obtained by the CH methods and the amounts of dye in the remaining liquor are determined according to "Test A" and listed in Tables 2-4.
  • the leather is cut open at an angle of 10-20 ° C to the surface and the penetration behavior is assessed visually for comparison.

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

Claims (8)

  1. Agents de traitement du cuir, caractérisés en ce qu'ils contiennent un mélange de
    (a) 2 à 98 % en poids d'un produit d'addition, dépourvu de groupes amino et ayant un poids molaire de 500 à 50 000, d'un oxyde d'alkylène sur un composé aliphatique contenant un ou plusieurs groupes hydroxyles, et de :
    (b) 98 à 2 % en poids d'un produit de réaction, contenant des groupes carboxyles ou leurs sels, et ayant un poids molaire de 170 à 20 000, d'un compose aliphatique, cycloaliphatique ou aromatique contenant au moins deux groupes carboxyles ou leurs anhydrides, et
    d'un composé aliphatique ou cycloaliphatique contenant au moins deux groupes hydroxy et/ou des groupes amino primaires ou secondaires et éventuellement des groupes éthers et amino tertiaires.
  2. Agents selon la revendication 1, caractérisés en ce qu'ils contiennent comme constituant
    (a) un produit d'addition de l'oxyde d'éthylène et/ou de l'oxyde de propylène sur un composé de formule



            HO-CH₂-R



    dans laquelle R représente H, ou un groupe alkyle en C₁-C₅, linéaire ou ramifié, éventuellement substitué par 1 à 5 groupes OH,
    et comme constituant
    (b) un produit de réaction d'un acide de formule



            HOOC - X - COOH



    dans laquelle X représente un groupe alkylène en C₁-C₈, -CH=CH-, un groupe cyclohexylène ou un groupe phénylène éventuellement substitué par COOH ou Cl),
    ou son anhydride, et un composé de formule



            HO-Y-OH,

    Figure imgb0019

            H₂N-Y₁-NH₂,

    Figure imgb0020
     ou
    Figure imgb0021
     formules dans lesquelles
    Y   représente un groupe alkylène en C₂-C₈, linéaire ou ramifié, éventuellement substitué par 1 à 4 groupes OH, où
    Figure imgb0022
    Y₁   représente un groupe alkylène en C₂-C₆, ou un groupe cyclohexylène éventuellement substitué par un groupe méthyle,
    Y₂   représente un groupe éthylène ou un groupe 1,2- ou 1,3-propylène,
    R₂ et R₃   représentent chacun H ou CH₃,
    R₄   représente H ou -Y₂-OH,
    m   vaut 3 à 13, et a notament une valeur moyenne de 8,
    n   vaut 2, 3 ou 4.
  3. Agents selon la revendication 1, caractérisés en ce qu'ils contiennent, comme constituant (a), le produit d'addition d'un oxyde d'alkylène sur un alcool de formule



            HO-CH₂-R,



    et, comme constituant (b), un produit de réaction de l'acide maléique ou de l'acide phtalique ou de leurs anhydrides et d'un alcool de formule
    Figure imgb0023
     dans laquelle R, R₂, R₃ et m ont le sens indiqué à la revendication 2.
  4. Agents selon la revendication 1, caractérisés en ce qu'ils constituent des solutions, des émulsions ou des dispersions ayant une teneur totale en (a) et (b) de 15 à 60% en poids.
  5. Agents selon la revendication 1, caractérisés en ce qu'ils constituent des solutions aqueuses ayant une teneur totale en (a) et (b) de 15 à 60 % en poids et un pH de 3 à 9.
  6. Procédé pour traiter le cuir, caractérisé en ce qu'on fait agir sur du cuir tanné un agent selon la revendication 1, avant de traiter par un colorant ou en même temps qu'on traite ce cuir par un colorant.
  7. Procédé selon la revendication 6, caractérisé en ce qu'on traite le cuir entre 10 et 90°C avec un bain aqueux qui contient 0,01 à 20 % en poids d'un agent selon la revendication 1.
  8. Cuir obtenu par traitement à l'aide d'un agent selon la revendication 1.
EP87105532A 1986-04-26 1987-04-14 Agent de traitement du cuir Expired - Lifetime EP0243788B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3614280 1986-04-26
DE19863614280 DE3614280A1 (de) 1986-04-26 1986-04-26 Lederbehandlungsmittel

Publications (3)

Publication Number Publication Date
EP0243788A2 EP0243788A2 (fr) 1987-11-04
EP0243788A3 EP0243788A3 (fr) 1991-09-04
EP0243788B1 true EP0243788B1 (fr) 1993-09-22

Family

ID=6299664

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87105532A Expired - Lifetime EP0243788B1 (fr) 1986-04-26 1987-04-14 Agent de traitement du cuir

Country Status (4)

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US (1) US4831075A (fr)
EP (1) EP0243788B1 (fr)
JP (1) JPS62263390A (fr)
DE (2) DE3614280A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8701548A (nl) * 1987-07-01 1989-02-01 Tno Polymeer netwerk, werkwijze voor het bereiden daarvan alsmede, de toepassing daarvan voor het bekleden en/of impregneren of voor het vervaardigen van ooglenzen, alsmede gevormd voortbrengsel, geheel of ten dele bestaande uit een dergelijk polymeer netwerk.
US10378262B2 (en) 2014-10-23 2019-08-13 Leon Yulkowski Door operator and clutch
CN114478810B (zh) * 2022-01-21 2023-02-24 中国皮革制鞋研究院有限公司 一种生物基有机鞣剂及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2446581A (en) * 1946-03-02 1948-08-10 Milprint Inc Adhesive composition comprising a polyalkylene glycol and an alkyd resin
NL300987A (fr) * 1962-11-27
US3862072A (en) * 1972-11-16 1975-01-21 Desoto Inc Thermosetting aqueous coatings containing branched hydroxy functional polyester and hydroxy functional polyether or polyester adducts of an at least trifunctional alcohol
DE2626430C2 (de) * 1976-06-12 1982-06-03 Bayer Ag, 5090 Leverkusen Verfahren zum Gerben von Leder und Gerbmischung
DE2710993C3 (de) * 1977-03-14 1981-05-14 Henkel KGaA, 4000 Düsseldorf Wäßrige Dispersion von als Überzugsmittel bzw. Lackbindemittel geeigneten Harzen
DE3525605A1 (de) * 1985-07-18 1987-01-22 Bayer Ag Lederbehandlungsmittel und ihre verwendung
US4907736A (en) * 1986-06-27 1990-03-13 Airfoil Textron Inc. Method of forming articles

Also Published As

Publication number Publication date
DE3787493D1 (de) 1993-10-28
EP0243788A3 (fr) 1991-09-04
JPS62263390A (ja) 1987-11-16
DE3614280A1 (de) 1987-10-29
US4831075A (en) 1989-05-16
EP0243788A2 (fr) 1987-11-04

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