EP0824601A2 - Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises - Google Patents

Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises

Info

Publication number
EP0824601A2
EP0824601A2 EP96919662A EP96919662A EP0824601A2 EP 0824601 A2 EP0824601 A2 EP 0824601A2 EP 96919662 A EP96919662 A EP 96919662A EP 96919662 A EP96919662 A EP 96919662A EP 0824601 A2 EP0824601 A2 EP 0824601A2
Authority
EP
European Patent Office
Prior art keywords
leather
water
dispersing
agents
stabilizing
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.)
Withdrawn
Application number
EP96919662A
Other languages
German (de)
English (en)
Inventor
Manfred Kaussen
Helmut STÖLCKER
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.)
Stockhausen GmbH and Co KG
Original Assignee
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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 Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Stockhausen GmbH and Co KG
Publication of EP0824601A2 publication Critical patent/EP0824601A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • the invention relates to a process for the hydrophobization of leather, furs and other fibrous materials, in which the previously customary but undesirably high pH values are no longer required in order to achieve a good hydrophobizing effect by the addition of dispersing or stabilizing auxiliaries to the hydrophobizing agent.
  • the water-repellent finish is carried out today from the aqueous liquor.
  • the water-repellent effect can either be achieved by coating the fibrils and fibers of the leather with hydrophobic compounds or by incorporating special emulsifiers which are capable of forming stable water-in-oil emulsions. If water or moisture gets into or into the leather, a water-in-oil emulsion is formed inside the fiber interstices. There is swelling, which leads to sealing.
  • R. Nowak described the structure and mode of operation of different types of auxiliaries for hydrophobizing in "Leder- und Häute notice", 29 (1977), issue 24.
  • the hydrophobizing agents used today are in many cases representatives who obey the two mechanisms mentioned above. Through inversion, it is possible to convert products which belong to the class of water-in-oil emulsions into those which form oil-in-water emulsions. This can be done by adding certain emulsifiers, changing the pH, fixing with metal salts and other measures. Oil-in-water emulsions can be used in the licker process because of their arbitrary dilutability with water. The water repellents used in practice correspond to this type.
  • the leather cross-section must be completely penetrated by the hydrophobizing agent (Hodder, JJ, "Waterproof Leather Technologies and Processes", Waterproof Symposium on the occasion of the ALCA meeting, Poco Manors, USA, 1994, publication in JALCA in preparation).
  • a major handicap of the previous hydrophobizing agents is that their oil-in-water emulsions begin to break at acidic pH values from about 5. The result is smearing on the scar and meat side up to the complete precipitation of the product in the manner of a mayonnaise.
  • the broken emulsion shows a completely different emulsion or solution behavior, which can articulate, for example, in the precipitation described.
  • the mayonnaise-like fat body can no longer penetrate into the leather in a finely or finely divided form and pass through it evenly. This results in poorer water repellency.
  • the two test methods mentioned for determining the hydrophobicity of the leather are of a dynamic nature, ie the water absorption is determined under constant bending or compressive stress on the leather samples.
  • the indication of the compression amplitude, the time until water penetration and the water absorption within certain time intervals according to the Bally penetrometer measurement allow a valid assessment of the use value.
  • a hydrophobic leather finish As a result of increased requirements for good hydrophobization, Bally measured values at 7.5% compression of the leather are no longer up to date. Specifications for the compression of 10% to 15% must be met according to today's standards, the test times being between 6 and 24 hours and the water absorption should be below 20%. With regard to the "Maeserflexes", a value of at least 15,000 must be achieved for good hydrophobization.
  • Bay et al describes in DE 35 29 869 AI a process for hydrophobizing leather and furs, which in a simple procedure while avoiding organic solvents of silicone oil emulsions stabilized with N-acylamino acids (dimethylpolysiloxanes, page 3, line 41) at pH values of 4.5 - 8, preferably 4.8 - 5.5 works.
  • the application examples A - E are carried out in the pH range 5 - 6. According to page 4, lines 3 - 6, however, the hydrophobicization is not sufficient, since a significant improvement can only be achieved by the additional use of conventional hydrophobicizing agents of the paraffin or wax emulsions type.
  • Bay (Bay, H., "A contribution to the hydrophobization of various types of leather with higher demands on the water resistance of the leather", Leder & Häute-Markt, 38, (1986) 24, 29.08.86, 77-79) describes strong hydrophobized leather the use of a purely aqueous emulsion of special silicone oils (Densodrin® S, BASF, technical information May 1988) according to the above DE 35 29 869 AI as top hydrophobization after the basic hydrophobization has been carried out beforehand, e.g. with Densodrin® GF.
  • polymeric plasticizers as water repellents only achieve good penetration when used in pH - Range higher than 5-6 depending on the polymer in question. Although a certain water repellency can also be achieved at lower pH values, the high demands on Maeser flexes and water absorption require complete penetration, which requires a relatively high and complete neutralization of the chrome-tanned leather. In terms of leather technology, the high pH is undesirable because it leads to loose grain.
  • Friese and Prinz Feriese, H.-H. and W.
  • the former have the task of largely introducing the hydrophobizing agent or its emulsion into the interior of the leather despite the unfavorable pH conditions and ensuring a good distribution.
  • Stabilizers increase the stability of the emulsion, which offers an improved way of penetrating deeper into the leather interior.
  • substances that disperse or stabilize well but are not very hydrophilic are suitable. These include special copolymers. Fatliquor and also certain synthetic retanning agents, the so-called syntans. whose characteristics are their insensitivity to acids and salts.
  • syntans cannot be used Synthesize excessively pronounced hydrophilicity and use according to the invention.
  • Syntane are used in both liquid and powdery form, the powdery form being mostly contaminated by adjusting salts from the manufacturing process (spray drying).
  • alkoxy group-containing Polymers are described for example in the patents US 4,962,173, US 4,872,995, US 4,847,410 and DE 42 27 974 AI.
  • Suitable monomers of group a) are polymerizable, water-soluble, acid-group-bearing, ethylenically unsaturated monocarboxylic acids, their anhydrides and their salts; Sulphonic acids and unsaturated dicarboxylic acids, their anhydrides and their half esters or half amides.
  • Examples include (meth) acrylic acid, (meth) allylsulfonic acid, vinyl acetic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid, styryl sulfonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and the half esters and half amides of the aforementioned dicarboxylic acids, the half esters and half amides being accessible by reaction of the corresponding acid anhydrides with alcohols, amines and amino alcohols.
  • Preferred monomers are acrylic acid, methacrylic acid, maleic acid and maleic anhydride.
  • the monomers of group b) are obtained either by alkoxylation of ethylenically unsaturated compounds bearing at least one hydroxyl or amino group or by reacting the alkoxy adducts of saturated aliphatic, cycloaliphatic, aromatic alcohols, amines or thiols with ethylenically unsaturated Carboxylic acids, reactive carboxylic acid derivatives or allyl halides.
  • Carboxylic acids reactive carboxylic acid derivatives or allyl halides.
  • Examples include the ethylene and / or propylene oxide adducts of (meth) allyl alcohol, (meth) allylamine, and also hydroxyethyl (meth) carylate, if appropriate further reacted with reactive saturated acid derivatives.
  • All monomers copolymerizable with a) and b) can be used as monomers of group c). They are used for further modification of the polymers and thereby enable an optimal adaptation to the hydrophobizing agents to be used according to the invention. Accordingly, the monomers according to c) can have both a hydrophilic and a hydrophobic character.
  • Examples include (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid ester, hydroxyethyl (meth) acrylate, N-vinylpyr- rolidone, N-vinylimidazole, N-vinylacetamide, vinyl acetate, vinyl propionate, vinyl versatic acid, styrene.
  • the polymers are prepared by polymerization in bulk, in solution or as an emulsion under the conditions which are well known to those skilled in the art for such types of polymerization with regard to the choice of reactors, solvents, polymerization temperatures, initiators, regulators, stabilizers and other customary polymerization auxiliaries.
  • the average molecular weight of the polymers is in the range from 500 to 100,000 g / mol, a preferred molecular weight range is between 500 and 50,000 g / mol and particularly preferably between 500 and 20,000 g / mol.
  • the copolymers are preferably used in dissolved or emulsified form.
  • copolymers can be applied before or simultaneously with the hydrophobizing agent.
  • the synthetic products based on sulfochlorinated paraffins and chlorine paraffins in particular lead to deep greasing, which is articulated in a dry surface.
  • these types of greasing agents are preceded by the reputation of wetting leather due to their chemical structure and thus reducing the water repellent effect, surprisingly good water repellent values have been achieved.
  • the stabilization of the hydrophobizing agent overcompensates for the hydrophilic character. (Similar behavior is shown by highly dispersing syntans, provided their hydrophilicity is not extremely pronounced).
  • those based on natural raw materials can also be used in the process according to the invention.
  • fatty substances of animal origin such as fish oil, whale oil, cattle claw oil, tallow, and vegetable oils, such as those obtained from cottonseed, castor oil, sunflower, peanut or olives.
  • the water-miscible products are often modified by hydrophilic sulfone groups. They are obtained by sulfation, sulfitation or formation of sulfonic acids.
  • the use of a mixture of various synthetic and natural fatliquoring agents in the process according to the invention has also proven to be advantageous. Synthetic fatliquors based on copolymers can also be used according to the invention. use according to, but here too the condition applies that they must have a sufficient stabilizing effect at pH values of 5 or lower.
  • the use of the dispersing or stabilizing products according to the invention in addition to the advantageous method of working at a reduced pH, also allows the majority of the hydrophobicizing agent to be used in the neutralization / retanning and thus to achieve simplified formulations.
  • the absorption capacity of the leather for the hydrophobizing agent is also greater than later in the "actual" hydrophobization.
  • so-called compact working methods are favored or only made possible, which reduce the number of processing stages (basic greasing - basic hydrophobization - top hydrophobization) in leather production.
  • the biggest advantage is the possibility of not having to expose sensitive raw materials to a high pH value and thus deliberately provoking lower quality.
  • the lower working liquor pH values of the process according to the invention which are in the range from 3.5 to 5, preferably from 4 to 5 and particularly preferably from 4.3 to 4.7, there are no precipitations with the resulting ones Smearing observed.
  • the leathers are normally dry on the surface and show excellent hydrophobic properties.
  • the pH in the leather can be 0.2 to 0.3 pH units lower than in the liquor.
  • the amount of dispersing aid used is between 2-10% and preferably between 2-5% based on the shaved weight of the wet-blue material used or the wet weight of the furs.
  • the invention also relates to leather, furs and other fibrous materials which have been rendered hydrophobic by the process according to the invention.
  • the leather can be hydrophobized both in the multi-stage and in the compact mode of operation (direct mode of operation) by the process according to the invention.
  • the excellent hydrophobicity of the leather is demonstrated by measurements with the Bally Penetrometer or with the Maeser test. example 1
  • HYDROPHOBICATION 4.0% copolymer according to a) 1: 5 20 min.
  • HYDROPHORTF.RT TNG 1 HO 0% water 55 ° C
  • the leather showed water penetration in the Bally penetrometer at 10% compression after> 420 minutes with a water absorption of 11%.
  • the leather showed water penetration in the Bally penetrometer at 10% compression after> 420 minutes with a water absorption of 9%.
  • the leather showed water penetration in the Bally penetrometer at 10% compression after> 420 minutes with a water absorption of 9%.
  • the leather showed water passage in the Bally penetrometer at 10% compression after> 420 minutes with a water absorption of 13%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Selon ce procédé d'imperméabilisation de cuirs, de fourrures et d'autres matériaux fibreux, on procède à l'imperméabilisation avec des agents imperméabilisants usuels en présence d'adjuvants dispersants ou stabilisants, sous des valeurs de pH comprises entre 3,5 et 5. On utilise de préférence comme adjuvants dispersants ou stabilisants des copolymères contenant des groupes alcoxy, des agents nourrissants synthétiques ou naturels ou des agents synthétiques de retannage (syntans)
EP96919662A 1995-05-12 1996-05-03 Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises Withdrawn EP0824601A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19516961 1995-05-12
DE19516961A DE19516961A1 (de) 1995-05-12 1995-05-12 Verfahren zur Hydrophobierung von Leder bei niedrigen pH-Werten und damit hergestellte Leder
PCT/EP1996/001851 WO1996035815A2 (fr) 1995-05-12 1996-05-03 Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises

Publications (1)

Publication Number Publication Date
EP0824601A2 true EP0824601A2 (fr) 1998-02-25

Family

ID=7761444

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96919662A Withdrawn EP0824601A2 (fr) 1995-05-12 1996-05-03 Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises

Country Status (6)

Country Link
US (1) US5980578A (fr)
EP (1) EP0824601A2 (fr)
AR (1) AR001904A1 (fr)
AU (1) AU5813296A (fr)
DE (1) DE19516961A1 (fr)
WO (1) WO1996035815A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395040B1 (en) * 2000-04-28 2002-05-28 Wolverine World Wide, Inc. Process for producing leather
DE10250111A1 (de) * 2002-10-28 2004-05-06 Bayer Ag Chromfreies, wasserdichtes Leder
US20060288494A1 (en) * 2005-06-24 2006-12-28 Wolverine World Wide, Inc. Process for producing leather
US20060288493A1 (en) * 2005-06-24 2006-12-28 Wolverine World Wide, Inc. Process For Producing Leather Footwear Lining

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3304120A1 (de) * 1983-02-08 1984-08-09 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung wasserdichter leder und pelze
DE3620780A1 (de) * 1986-06-20 1987-12-23 Henkel Kgaa Fettungsmittel auf basis von sulfobernsteinsaeuremonoamiden
DE3717961C2 (de) * 1986-10-27 1994-05-26 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Gemischen von N,N-disubstituierten ß-Aminopropionsäurederivaten, bestimmte Gemische von N-Alkyl-N(2-carboxyethyl)sulfonamiden und N-Alkyl-N(2-carboxyethyl)harnstoffen und Verwendung der genannten Verbindungen
TNSN89128A1 (fr) * 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West Traitement du cuir avec des copolymeres amphiphites choisis
DE3926167A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen olefinen und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen
DE3926168A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen alkylvinylethern und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen
DE3931039A1 (de) * 1989-09-16 1991-03-28 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen
DE4103456A1 (de) * 1991-02-06 1992-08-13 Henkel Kgaa Salze phosphatierter oh-gruppenhaltiger glycerintri-c(pfeil abwaerts)8(pfeil abwaerts)(pfeil abwaerts)-(pfeil abwaerts)2(pfeil abwaerts)2(pfeil abwaerts)-fettsaeureester als fettungsmittel fuer leder und pelze
DE4129244A1 (de) * 1991-09-03 1993-03-04 Henkel Kgaa Waessrige dispersionen von neuen amphiphilen co-oligomeren fuer die wasch- und reinigungsbestaendige fettende ausruestung von leder und pelzfellen sowie ihre verwendung
DE4139090A1 (de) * 1991-11-28 1993-06-03 Stockhausen Chem Fab Gmbh Verwendung von copolymerisaten mit polysiloxan-einheiten zur behandlung von leder und pelzen
DE4207243A1 (de) * 1992-03-07 1993-09-09 Basf Ag Poroese formteile
DE4214011C1 (de) * 1992-04-29 1993-11-04 Muenzing Chemie Gmbh Copolymerisate
DE4227974C2 (de) * 1992-08-26 1996-04-18 Stockhausen Chem Fab Gmbh Alkoxygruppenhaltige Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung zum Nachgerben von Leder
DE4236556A1 (de) * 1992-10-29 1994-05-05 Stockhausen Chem Fab Gmbh Verfahren zur Weichmachung/Fettung von Ledern und Pelzen
DE4300772C2 (de) * 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9635815A2 *

Also Published As

Publication number Publication date
US5980578A (en) 1999-11-09
WO1996035815A2 (fr) 1996-11-14
AR001904A1 (es) 1997-12-10
AU5813296A (en) 1996-11-29
WO1996035815A3 (fr) 1996-12-12
DE19516961A1 (de) 1996-11-28

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