EP0347373B1 - Solutions aqueuses de tannins synthétiques - Google Patents

Solutions aqueuses de tannins synthétiques Download PDF

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Publication number
EP0347373B1
EP0347373B1 EP89810402A EP89810402A EP0347373B1 EP 0347373 B1 EP0347373 B1 EP 0347373B1 EP 89810402 A EP89810402 A EP 89810402A EP 89810402 A EP89810402 A EP 89810402A EP 0347373 B1 EP0347373 B1 EP 0347373B1
Authority
EP
European Patent Office
Prior art keywords
component
formaldehyde
condensates
parts
sulfonated
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
EP89810402A
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German (de)
English (en)
Other versions
EP0347373A1 (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
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Publication date
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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

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • 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
    • D06P1/56—Condensation products or precondensation products prepared with aldehydes
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/10—After-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.
  • 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 also 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 methods are 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.
  • the resulting condensation product is mixed with 90 to 100 parts of phenol, and as soon as the phenol is thoroughly mixed, the reaction mass is again slowly put under vacuum and heated at 165 ° C until 1 g of the condensation product is only 2.7 to 2.5 cm3 of 1N sodium hydroxide solution neutralized against Congo red. Yield 900-940 parts.
  • 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 tricot 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)

Claims (9)

  1. Solution aqueuse de tannins synthétiques, caractérisée en ce qu'elle contient :
    (A) un sel de lithium d'un tannin synthétique aromatique anionique, choisi dans le groupe constitué par :
    (I) les produits de condensation à base de formaldéhyde et de phénol ou de crésol sulfoné,
    (II) les produits de condensation à base d'acide naphtalènesulfonique et de formaldéhyde,
    (III) les produits de condensation au formaldéhyde de 4,4'-dihydroxydiphénylsulfones avec des acides (hydroxy)arylsulfoniques,
    (IV) les produits de condensation au formaldéhyde de composés hydroxy-aromatiques sulfonés avec des halogénures d'aralkyle,
    (V) les produits de condensation au formaldéhyde et à l'urée de phénols et d'acides phénolsulfoniques,
    (VI) les produits de réaction d'un phénol et d'un agent de sulfonation, le rapport molaire phénol/SO₃ valant de 1/1,1 à 1/2,2,
    (VII) les produits de condensation à base d'éthers diaryliques sulfonés et de formaldéhyde,
    (VIII)les produits de condensation à base de diphénylènes ou de terphénylènes sulfonés et de formaldéhyde,
    (IX) les produits de condensation à base de 4,4'-dihydroxydiphénylsulfone et de 4,4'-dihydroxydiphénylsulfone sulfonée avec du formaldéhyde, et
    (X) les produits de condensation au formaldéhyde d'acide diaryléthersulfonique et de 4,4'-dihydroxydiphénylsulfone,
    et éventuellement
    (B) un sel hydrosoluble de chrome, d'aluminium, de fer ou de zirconium, ou un mélange de tels sels, et
    (C) un sel de métal alcalin de l'acide éthylènediaminetétraacétique ou un pyrophosphate.
  2. Solution aqueuse conforme à la revendication 1, qui contient, en tant que composant (B), du chlorure ou du sulfate de chrome(III) basique, un alun de chrome, du chlorure ou du sulfate d'aluminium éventuellement basique, un alun, du chlorure ou du sulfate de fer(III), de l'oxychlorure de zirconium ou du sulfate de zirconium éventuellement basique, ou des mélanges des sels de chrome ou d'aluminium mentionnés.
  3. Solution aqueuse conforme à la revendication 2, qui contient, en tant que composant (B), [CrCl₂(OH₂)₄]Cl.2H₂O, [Cr(OH₂)₆]Cl₃, Cr(OH)SO₄, Cr₂(OH)₄SO₄, KCr(SO₄)₂.12H₂O, AlCl₃.6H₂O, Al₂(SO₄)₃.16H₂O, Al₂(OH)₄SO₄, Al(OH)₂Cl, Al(OH)Cl₂, KAl(SO₄)₂.12H₂O, Fe₂(SO₄)₃.9H₂O, Zr(OH)₂SO₄, ZrOCl₂.8H₂O ou Zr(SO₄)₂.4H₂O.
  4. Solution aqueuse conforme à la revendication 1, qui contient, en tant que composant (C), du sel tétrasodique de l'acide éthylènediaminetétraacétique ou du pyrophosphate neutre ou acide de sodium.
  5. Solution aqueuse conforme à la revendication 1, qui contient de 5 à 60 % en poids de composant (A), de 0 à 60 % en poids de composant (B), de 0 à 60 % en poids de composant (C), et le complément à 100 % en poids d'eau.
  6. Sels de lithium de tannins aromatiques anioniques synthétiques, choisis dans le groupe constitué par :
    (A) un sel de lithium d'un tannin synthétique aromatique anionique, choisi dans le groupe constitué par :
    (I) les produits de condensation à base de formaldéhyde et de phénol ou de crésol sulfoné,
    (II) les produits de condensation à base d'acide naphtalènesulfonique et de formaldéhyde,
    (III) les produits de condensation au formaldéhyde de 4,4'-dihydroxydiphénylsulfones avec des acides (hydroxy)arylsulfoniques,
    (IV) les produits de condensation au formaldéhyde de composés hydroxy-aromatiques sulfonés avec des halogénures d'aralkyle,
    (V) les produits de condensation au formaldéhyde et à l'urée de phénols et d'acides phénolsulfoniques,
    (VI) les produits de réaction d'un phénol et d'un agent de sulfonation, le rapport molaire phénol/SO₃ valant de 1/1,1 à 1/2,2,
    (VII) les produits de condensation à base d'éthers diaryliques sulfonés et de formaldéhyde,
    (VIII)les produits de condensation à base de diphénylènes ou de terphénylènes sulfonés et de formaldéhyde,
    (IX) les produits de condensation à base de 4,4'-dihydroxydiphénylsulfone et de 4,4'-dihydroxydiphénylsulfone sulfonée avec du formaldéhyde, et
    (X) les produits de condensation au formaldéhyde d'acide diaryléthersulfonique et de 4,4'-dihydroxydiphénylsulfone.
  7. Utilisation d'une solution aqueuse conforme à la revendication 1, pour tanner des peaux ou pour retanner du cuir.
  8. Utilisation d'un sel de lithium conforme à la revendication 6, comme agent de protection contre les taches pour des fibres de polyamide.
  9. Utilisation d'un sel de lithium conforme à la revendication 6, pour améliorer la solidité au mouillé de teintures sur fibres de polyamide.
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 EP0347373A1 (fr) 1989-12-20
EP0347373B1 true EP0347373B1 (fr) 1993-10-13

Family

ID=4226735

Family Applications (1)

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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

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA941105A (en) * 1970-01-29 1974-02-05 Celanese Corporation Process for improving the dyeability of polyester
NL7107708A (fr) * 1971-05-07 1972-11-09
DE2549533A1 (de) * 1975-11-05 1977-05-18 Cassella Farbwerke Mainkur Ag Hilfsmittel und verfahren zur verbesserung der nassechtheiten von polyamidfaerbungen
US4110367A (en) * 1976-02-02 1978-08-29 Diamond Shamrock Corporation Sulfonated alkylphenoxy acetones
DE2743066C3 (de) * 1977-09-24 1981-02-19 Bayer Ag, 5090 Leverkusen Farbstoffpräparationen
DE2856883A1 (de) * 1978-12-30 1980-07-17 Hoechst Ag Verfahren zum abtrueben von lederfaerbungen
DE2932688A1 (de) * 1979-08-11 1981-02-26 Bayer Ag Verfahren zum nachgerben mineralisch gegerbter leder mit aromatischen sulfonsaeuren
US4830632A (en) * 1986-05-05 1989-05-16 Ciba-Geigy Corporation Aqueous composition from a sulfonated phenol, an amine and a tanning salt, process for the production thereof and use thereof as a tanning agent

Also Published As

Publication number Publication date
PT90724A (pt) 1989-12-29
AR245224A1 (es) 1993-12-30
DE58905881D1 (de) 1993-11-18
EP0347373A1 (fr) 1989-12-20
BR8902615A (pt) 1990-01-23
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

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