EP0347373A1 - Solutions aqueuses de tannins synthétiques - Google Patents

Solutions aqueuses de tannins synthétiques Download PDF

Info

Publication number
EP0347373A1
EP0347373A1 EP89810402A EP89810402A EP0347373A1 EP 0347373 A1 EP0347373 A1 EP 0347373A1 EP 89810402 A EP89810402 A EP 89810402A EP 89810402 A EP89810402 A EP 89810402A EP 0347373 A1 EP0347373 A1 EP 0347373A1
Authority
EP
European Patent Office
Prior art keywords
component
lithium salt
formaldehyde
condensation product
anionic
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.)
Granted
Application number
EP89810402A
Other languages
German (de)
English (en)
Other versions
EP0347373B1 (fr
Inventor
Alain Dr. Lauton
Alois Dr. Püntener
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0347373A1 publication Critical patent/EP0347373A1/fr
Application granted granted Critical
Publication of EP0347373B1 publication Critical patent/EP0347373B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/04Mineral tanning
    • C14C3/06Mineral tanning using chromium compounds
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/08Chemical tanning by organic agents
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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
    • D06P1/56Condensation products or precondensation products prepared with aldehydes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02After-treatment
    • D06P5/04After-treatment with organic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02After-treatment
    • D06P5/10After-treatment with compounds containing metal

Definitions

  • the present invention relates to aqueous solutions of synthetic tanning agents, their use for tanning pelts or retanning leather and lithium salts of such tanning agents.
  • the tanning agents are generally present as ammonium salts. These salts cause unpleasant smells and pollute the resulting wastewater.
  • tannins in the form of their lithium salts do not have these disadvantages.
  • component (A) The synthetic aromatic tanning agents of component (A) are known per se, for example from Ullmann's Encyclopedia of Industrial Chemistry Vol. 16, (4) 138-140 (1979).
  • the lithium salts which can be used according to the invention are new and represent a further subject of the present invention.
  • the lithium salts of synthetic, anionic, aromatic tannins also called anionic aromatic syntans
  • anionic aromatic syntans also called anionic aromatic syntans
  • condensation products of types (I) - (III), (V) and (VII) - (X) are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, (4), 140 (1979) and can be described in the The processes described there can be produced.
  • reaction product of type (VI) and its preparation are known from EP-A-0245205. These reaction products can be condensed to products of type (V) by methods known per se (cf. e.g. GB-C-683084).
  • the ready-to-use tanning salts suitable for component (B) are described in the relevant specialist literature. These are usually chromium, aluminum, iron or zirconium salts. Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chromium and aluminum salts mentioned are also suitable as components (B) to be used.
  • the optional component (C) is used in the composition according to the invention, preference is given to the tetrasodium salt of ethylenediaminetetraacetic acid or the neutral or acidic sodium pyrophosphate (Na4P2O7 or Na2H2P2O7).
  • the optional component (C) acts as a complexing agent and is preferably used in the composition in the case of an iron-free tanning agent, provided the iron content of the oleum used in the production of component (A) is relatively high.
  • the weights of component (B) in the weight ratio of component (A) to component (B) are advantageously based on the metal atom of the corresponding tanning salts.
  • chrome tanning salts as component (C)
  • a maximum of 0.375 parts of chromium per part of component (A) can be used. Higher amounts of chromium would no longer be soluble in the composition and would lead to inhomogeneous compositions.
  • preferred compositions contain components (A) and (B) in a weight ratio (A) :( B) of (1) :( 0.03 to 0.5), based on the metal atom of component (B), at most 0.375 parts of chrome are present.
  • compositions which have the highest possible levels of tanning salts are desirable, since the tanning salts as component (B) are cheaper in comparison to the reaction products of phenol and oleum as component (A), the tanning effect of the composition on both component (A) and is also due to component (B).
  • compositions which contain components (A) and (B) in a weight ratio (A) :( B) of (1) :( 0.3 to 0.375) are particularly preferred.
  • the compositions contain the components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0 to 0.04).
  • the 1% aqueous solutions of compositions according to the invention preferably have a pH of 0 to 3.5.
  • compositions according to the invention have a water content of 40 to 80, preferably 45 to 62 percent by weight.
  • the procedure is generally such that an aqueous solution of component (A) and, if appropriate, component (C) are mixed with component (B), which may be present as an aqueous solution.
  • component (A) should first be diluted with water for safety reasons, about 50 to 70 percent by weight solutions of component (A) being obtained. As a rule, the optional component (C) is slowly added to the aqueous solution of component (A).
  • component (B) optionally added to the mixture of components (A) and optionally (C).
  • Component (C) can be added as a solid with vigorous stirring. This applies in particular when using, for example, aluminum tanning salts as component (B).
  • chrome tanning salts it has proven to be particularly advantageous to use component (B) as an aqueous solution, this aqueous solution, before mixing with components (A) and optionally (C), generally at 60 to 90 ° C. is heated. After all the components have been mixed, the composition is generally diluted with water to the preferred water content of 40 to 80 percent by weight.
  • the aqueous solutions of synthetic tanning agents preferably contain 5 to 60% by weight of component (A), 0 to 60% by weight of component (B), 0 to 60% by weight of component (C) and ad 100 wt.% water
  • compositions according to the invention obtained in this way are liquid and are particularly suitable for tanning raw materials or for retanning leather of all kinds.
  • the conventional method is used to treat pale or pretanned leather with an aqueous solution which contains the aqueous composition according to the invention, and then the material which has been tanned in the usual way, e.g. by neutralizing, washing out, greasing and drying. If desired, staining can be done.
  • 100 to 200, preferably 140 to 180 parts by weight of water and 5 to 40 parts by weight of the aqueous composition according to the invention are used per 100 parts by weight of leather or leather.
  • 100 parts by weight, preferably descaled, of tanned material are tanned with 140 to 160 parts by weight of water and 10 to 20 parts of the composition according to the invention, or 100 parts by weight in the usual manner, chrome-tanned leather neutralized with, for example, formates or bicarbonates, with 140 to 160 parts by weight of water and 5 to 15 parts retanned the composition according to the invention.
  • the tanned material is rinsed and, if necessary, subsequently greased with a commercially available fatliquor based on, for example, sulfonated fish oil, sperm oil or claw oil. After drying, a light, brilliant leather is obtained, which has good lightfastness, a firm, compact, smooth grain and a soft handle.
  • the composition according to the invention has the essential advantage of being particularly stable in storage. Even after several months of storage, no clouding or flocculation can be found in the composition.
  • lithium salts according to the invention can also be used with polyamide fibers to improve the wet fastness of dyeings or as stain protection agents (stain blockers).
  • lithium salts can also be used as dispersants, especially for dyes and chemicals.
  • the new lithium salts are produced by neutralizing the anionic syntane with lithium hydroxide or lithium hydroxide monohydrate.
  • condensation product obtained 82 parts are diluted with 36 parts of water and neutralized with 16.2 parts of lithium hydroxide monohydrate and mixed with 13.1 parts of 37% formaldehyde solution and condensed at 100 to 105 ° C. for about 6 hours until a sample is obtained diluted a little water remains clear when acidified with dilute sulfuric acid.
  • the reaction mass is then diluted with 50 parts of water, the resulting tanning agent is adjusted to pH 3.5 with 13 parts of 40% sulfuric acid and acidified with 14 parts of 85% formic acid.
  • This tanning agent is particularly suitable for the production of white leather.
  • 100 parts of decalcified veal pellet are treated with 150 parts of water and 51 parts of the composition prepared according to Example 1 for 24 hours at 20 ° C. in a rolling barrel. After washing, greasing, stretching, drying, conditioning, cleats and stretching, you get a white tanned leather that has a full grain and a soft feel.
  • 100 parts of folded chrome grain calf leather are treated with 150 parts of water and 10 parts of the composition prepared according to Example 3 for 2 hours at 50 ° C. in a rolling barrel.
  • the leather is neutralized with sodium formate and sodium bicarbonate according to customary methods, washed, with 1 part of the leather dye C.I. Acid Brown 189 colored and aftertreated with a commercially available fatliquor based on sulfonated fish oil.
  • a retanned, brown-colored, brilliant leather is obtained, which also has a full grain and a soft handle.
  • polyamide carpet 100 parts are made up of an aqueous solution at 60 ° C 5 parts of the lithium salt prepared according to Example 4, 1 part of magnesium sulfate and 5 parts of ammonium acetate, which was adjusted to pH 2.5 with formic acid, Treated for 15 minutes. The treated carpet is then rinsed with cold water and dried. The treated carpet shows no affinity at room temperature for CI FD&C Red 40.
  • 100 g of a polyamide 6,6 jersey are placed in a dyeing machine at 40 ° C. in a liquor (liquor ratio 1:40) which contains 2 g of a commercially available anionic leveling agent and 1.2 g of a dye and is adjusted to pH 5 with acetic acid is.
  • the dye bath is heated to 98 ° C. in the course of 30 minutes while the liquor is in constant circulation, and dyeing is carried out at this temperature for 30 minutes.
  • the dye bath is then cooled and the substrate rinsed.
  • the substrate is then introduced at 70 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP89810402A 1988-06-06 1989-05-30 Solutions aqueuses de tannins synthétiques Expired - Lifetime EP0347373B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2137/88 1988-06-06
CH213788 1988-06-06

Publications (2)

Publication Number Publication Date
EP0347373A1 true EP0347373A1 (fr) 1989-12-20
EP0347373B1 EP0347373B1 (fr) 1993-10-13

Family

ID=4226735

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89810402A Expired - Lifetime EP0347373B1 (fr) 1988-06-06 1989-05-30 Solutions aqueuses de tannins synthétiques

Country Status (9)

Country Link
EP (1) EP0347373B1 (fr)
JP (1) JPH0232200A (fr)
KR (1) KR910001070A (fr)
AR (1) AR245224A1 (fr)
BR (1) BR8902615A (fr)
DE (1) DE58905881D1 (fr)
ES (1) ES2045544T3 (fr)
MX (1) MX166820B (fr)
PT (1) PT90724B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0615360B2 (ja) * 1984-04-03 1994-03-02 富士通株式会社 放 射 冷 却 器
KR100617978B1 (ko) * 2006-03-08 2006-08-28 한국신발피혁연구소 숫소 원피를 이용한 암소 유사 육면가죽의 제조방법
KR101137761B1 (ko) * 2009-09-10 2012-04-24 한국신발피혁연구소 변색 또는 오염된 베지터블 양피 크러스트의 표면개선방법
JP7228139B2 (ja) * 2019-04-26 2023-02-24 山梨県 白色革の製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296304A (fr) * 1970-01-29 1972-11-15
FR2137557A1 (fr) * 1971-05-07 1972-12-29 Snia Viscosa Nale Ind Ap
FR2330795A1 (fr) * 1975-11-05 1977-06-03 Cassella Farbwerke Mainkur Ag Procede pour ameliorer les solidites au mouille de teintures sur polyamides
US4110367A (en) * 1976-02-02 1978-08-29 Diamond Shamrock Corporation Sulfonated alkylphenoxy acetones
GB2006276A (en) * 1977-09-24 1979-05-02 Bayer Ag Dyestuff formulations
DE2856883A1 (de) * 1978-12-30 1980-07-17 Hoechst Ag Verfahren zum abtrueben von lederfaerbungen
EP0024014A1 (fr) * 1979-08-11 1981-02-18 Bayer Ag Procédé de retannage de cuirs tannés au minéral avec des acides sulfoniques aromatiques
EP0245205A2 (fr) * 1986-05-05 1987-11-11 Ciba-Geigy Ag Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296304A (fr) * 1970-01-29 1972-11-15
FR2137557A1 (fr) * 1971-05-07 1972-12-29 Snia Viscosa Nale Ind Ap
FR2330795A1 (fr) * 1975-11-05 1977-06-03 Cassella Farbwerke Mainkur Ag Procede pour ameliorer les solidites au mouille de teintures sur polyamides
US4110367A (en) * 1976-02-02 1978-08-29 Diamond Shamrock Corporation Sulfonated alkylphenoxy acetones
GB2006276A (en) * 1977-09-24 1979-05-02 Bayer Ag Dyestuff formulations
DE2856883A1 (de) * 1978-12-30 1980-07-17 Hoechst Ag Verfahren zum abtrueben von lederfaerbungen
EP0024014A1 (fr) * 1979-08-11 1981-02-18 Bayer Ag Procédé de retannage de cuirs tannés au minéral avec des acides sulfoniques aromatiques
EP0245205A2 (fr) * 1986-05-05 1987-11-11 Ciba-Geigy Ag Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage

Also Published As

Publication number Publication date
PT90724A (pt) 1989-12-29
AR245224A1 (es) 1993-12-30
DE58905881D1 (de) 1993-11-18
BR8902615A (pt) 1990-01-23
EP0347373B1 (fr) 1993-10-13
JPH0232200A (ja) 1990-02-01
MX166820B (es) 1993-02-08
PT90724B (pt) 1994-11-30
KR910001070A (ko) 1991-01-30
ES2045544T3 (es) 1994-01-16

Similar Documents

Publication Publication Date Title
EP0849365B1 (fr) Agent pour la préparation du cuir
EP0245205B1 (fr) Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage
EP0717114A2 (fr) Composition aqueuse pour le prétannage de peaux ou le retannage de cuir
EP0428481B1 (fr) Moyens pour le traitement de cuir ou de fourrures
US5264000A (en) Aqueous solutions of synthetic tanning agents
EP0347373B1 (fr) Solutions aqueuses de tannins synthétiques
EP0533011B1 (fr) Procédé pour la production du cuir tanné au chrome
AT409384B (de) Wässerige zusammensetzung zum vorgerben von hautblössen oder nachgerben von leder
DE1961369A1 (de) Dioxydiphenylsulfon-Formaldehyd-Kondensationsprodukte
DE10140551A1 (de) Verfahren zur Herstellung sulfonhaltiger Gerbstoffe
EP0024014B1 (fr) Procédé de retannage de cuirs tannés au minéral avec des acides sulfoniques aromatiques
DE1593978B2 (de) Verfahren zur Herstellung sulfonsäuregruppenhaltiger Sulfone
EP0008032B1 (fr) Produits de condensation à base d'acides terphénylsulfoniques, d'acides naphtalène sulfoniques, de bis-(4-hydroxyphényl)-sulfone et de formaldéhyde et leur utilisation pour le tannage
EP1416058A1 (fr) Produits de condensation pour le retannage de cuir tanné au fer
EP0470465B1 (fr) Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques
EP0963446B1 (fr) Composition de traitement de cuir tanne, et sa preparation
EP0362134B1 (fr) Agent de traitement du cuir
DE3931978A1 (de) Lederbehandlungsmittel
DE19746445A1 (de) Mittel zur Herstellung von Leder
AT147180B (de) Verfahren zur Darstellung lichtecht gerbender Stoffe.
DE1494839C3 (de) Verfahren zum Schnellgerben von Ledern
DE687350C (de) Verfahren zur Herstellung von Kondensationserzeugnissen
DE19653549A1 (de) Mittel zur Herstellung von Leder
DE10336453A1 (de) Oberflächliche Anwendung kationischer oder amphoterer Polymere auf Leder-Halbfabrikaten
DE19713112A1 (de) Zusammensetzung zum Pickeln von Hautblößen, ihre Herstellung und Verwendung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890601

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE ES FR GB IT LI

17Q First examination report despatched

Effective date: 19920918

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58905881

Country of ref document: DE

Date of ref document: 19931118

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931126

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2045544

Country of ref document: ES

Kind code of ref document: T3

ITTA It: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950407

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950427

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19950516

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19950810

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960411

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19960531

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19960531

Ref country code: CH

Effective date: 19960531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970131

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980203

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050530