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WO1996006953A1 - Picklage des peaux - Google Patents

Picklage des peaux Download PDF

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Publication number
WO1996006953A1
WO1996006953A1 PCT/AU1995/000566 AU9500566W WO9606953A1 WO 1996006953 A1 WO1996006953 A1 WO 1996006953A1 AU 9500566 W AU9500566 W AU 9500566W WO 9606953 A1 WO9606953 A1 WO 9606953A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
phenol
treatment agent
treatment
pickling
Prior art date
Application number
PCT/AU1995/000566
Other languages
English (en)
Inventor
Peter Michael Pojer
Chi Phuong Huynh
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
The Federated Tanners Association Of Australia
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 Commonwealth Scientific And Industrial Research Organisation, The Federated Tanners Association Of Australia filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to AU33766/95A priority Critical patent/AU703154B2/en
Priority to EP95930337A priority patent/EP0778900A4/fr
Priority to NZ292070A priority patent/NZ292070A/xx
Priority to TW084109264A priority patent/TW336955B/zh
Publication of WO1996006953A1 publication Critical patent/WO1996006953A1/fr

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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing

Definitions

  • the present invention relates generally to natural products, particularly natural products requiring treatment before they may be used in a functional manner. More particularly, the present invention relates to natural products obtained from animals, such as for example skins, hides and the like. Even more particularly, the present invention relates to a process for pickling hides and skins as part of the tanning process, and to a method for preparing a pickling solution. The present invention finds particular application in pickling and tanning naturally occurring hides or skins to produce durable leather.
  • leather is a natural product which is derived from the hides or skins of many animals. However, before the hides or skins are useful, they must be treated.
  • One such treatment is tanning. Hides and skins need to be tanned in order to produce leather which has the durability and thermal stability normally required of leather goods, which is to say that the properties of the hides and skins need to be modified before they are useful, which modification is achieved by tanning.
  • the most widely practised tanning procedure involves treatment of the hides and skins with chromium salts. However, to promote uniform penetration of the chromium salts into the collagen matrix of the skins and hides without precipitation, the hides and skins require a pickling or acidification treatment or pretreatment.
  • the pickling or acidification treatment involves the use of a mineral acid, such as for example hydrochloric acid, sulphuric acid or the like, or an organic acid, such as formic acid, or more commonly a mixture of sulphuric and formic acids, together with the addition of a salt, usually sodium chloride, to prevent swelling of the hides or skins which would otherwise occur when the collagen is exposed to an acid medium.
  • a salt usually sodium chloride
  • hides pickled with sulphuric acid alone will swell in excess of 50% of the delimed weight of the hide whereas when a salt/sulphuric acid mixture is used not only is there no swelling but there is also deswelling to about -10% of the original delimed weight of the hide.
  • phenol mono-, di- and trisulphonic acids of the present invention could be added rapidly to the skins or hides being treated without swelling taking place since such materials rapidly penetrated the collagen matrix and were effective at a pH below 3 without causing swelling of the skin or hides.
  • a method of treating a naturally derived product prior to performing a subsequent treatment wherein the naturally derived product is treated with an agent to modify a property or characteristic of the naturally derived product, characterised in that the treatment by the agent is effective at a final pH of or below 3.4 and in that the agent comprises at least one or more of phenol mono-, di- or trisulphonic acid or derivatives thereof, either singly or in combination, including combination with other materials.
  • a method of preparing a treatment agent suitable for use in treating a naturally derived product comprising contacting a phenol mono-, di- or trisulphonic acid or derivative thereof, either singly or in combination, including combination with other materials including oleum or a sulphuric acid, characterised in that the agent is effective in use at a final pH of 3.4 or less.
  • the naturally derived product is a hide or skin, more typically a hide or skin useful in producing leather or a leather product.
  • the treatment agent for use with the hide or skin is a pickling or acidifying agent.
  • the subsequent treatment is a tanning treatment.
  • the tanning treatment can be any type of tanning treatment or more particularly a chromium tanning treatment or vegetable tanning treatment.
  • the agent is a pickling agent and comprises essentially pure phenol mono-, di- or trisulphonic acid or derivatives thereof. More typically, the pickling agent comprises a further acidic material. Typically, the further acidic material is sulphuric acid or oleum or a material derived from them.
  • a phenol sulphonic acid agent which before application to the hides or skins is associated with up to and no more than about 1 g, preferably less than about 0.6 g, more preferably less than about 0.4 g of sulphuric acid, oleum or equivalent thereof per 1 g of the phenol sulphonic acid or mixture thereof.
  • derivatives any salt or partial salt or compound of the phenol sulphonic acids, or any such derivatives having functional groups equivalent to the phenol sulphonic acids, such as for example compounds having a benzene ring substituted with a sulphonic acid, carboxylate, ester, alkyl, hydroxyl or thiol group.
  • the pickling agent comprises a mixture of monosulphonic acid and disulphonic acid, optionally together with trisulphonic acid, or any combination thereof.
  • the amount of disulphonic acid in the agent is maximised in order to facilitate reduction in the amount of swelling.
  • the ratio of monosulphonic acid to disulphonic acid is from about 100:1 to 1:100, preferably about 50:1 to 1:50, more preferably about 1:1 by weight.
  • the relative ratios of disulphonic to monosulphonic acid can deviate from these ranges.
  • phenol trisulphonic acid can be present as well as phenol monosulphonic acid and disulphonic acid.
  • phenol sulphonic acids or mixtures of the present invention contain less than 1 g sulphuric acid or oleum per gram of phenol sulphonic acid, and are readily prepared when phenols are sulphonated with oleum and/or sulphuric acid.
  • the pickling treatment can have a duration of up to about 48 hours or more, typically up to about 24 hours.
  • the concentration of the sulphonic acid in the resultant product mix is increased. It is to be noted that the amount of phenol di- and trisulphonic acid relative to the amount of monosulphonic acid is increased. However, the amount of phenol trisulphonic acid is relatively small compared to the amounts of phenol mono- and disulphonic acids.
  • the concentration of sulphur trioxide in the oleum can, of course, be varied, and while the use of oleum containing, say, 65% sulphur trioxide will give a very effective pickling agent, it has to be kept in mind that because the product will contain less associated sulphuric acid, more of the pickling agent will have to be used in the pickling treatment to achieve the desired level of acidification. In practice, for most purposes, oleum typically containing about 20% to 25% sulphur trioxide is effective.
  • reaction temperatures for producing the pickling agent of the present invention will typically be in the range of from 0°C to 200°C, preferably in the range 80°C to 140°C.
  • the final pH of the pickled hides or skins is about 3.0 or below.
  • the method of treatment and the pickling agent of the present invention may be applied to any of the types or hides or skins currently being processed by conventional techniques, such as for example ovine, porcine, bovine, caprine or like hides or skins, whether green or preserved in any known manner. More typically, the hide or skin may be treated by the pickling agent of the present invention either before or after the hair, wool or other covering or associated material has been removed. Even more typically, the process of the present invention can be used in conjunction or in combination with other technologies or processes conventionally used to prepare hides and skins for tanning.
  • the amount of phenol sulphonic acid or acids or mixtures thereof or derivatives thereof to be used may vary widely, but as in conventional acid/salt treatments, the amount used will depend to some extent on the state of the hide or skin to be pickled, the amount of mineral acid or separately introduced organic acid in the preparation, and the desired end pH or the like.
  • 1% to 10% by weight, based on the weight of the delimed hide, of the sulphonic acid or mixture will give satisfactory pickling.
  • the hide or skin may be in contact with the phenol sulphonic acid or acids or mixtures thereof for any suitable period, depending on requirements and/or be at any suitable or convenient temperature.
  • the phenol sulphonic acid or acids or mixtures thereof for any suitable period, depending on requirements and/or be at any suitable or convenient temperature.
  • delimed hides treated with a pickling solution containing from about 1% to 10% by weight acid will lead to equilibrium pickles exhibiting no swelling in less than 24 hours.
  • uniform and even chromium penetration and no swelling of the hides or skins will be exhibited when the chromium or chromium-containing tanning material is applied simultaneously or substantially simultaneously or sequentially with the sulphonic acid or acids or mixtures thereof.
  • a pickling agent prepared in accordance with the preceding examples was employed to pickle a full thickness hides.
  • a solution of water (35% by weight based on the weight of the delimed hides as indicated previously) and sodium formate (0.5% by weight based on the weight of the delimed hides as indicated previously) was added to delimed hides, which were then drummed for 5 minutes in a suitable drum before adding the solution containing the pickling agent of phenol sulphonic acid mixture as prepared in accordance with Example 1 or Example 2 at a concentration of 4% of the formulation based on the weight of the delimed hides in 10% water by weight based on the weight of the delimed hides as indicated previously.
  • Drumming was continued for 2 to 3 hours, after which formic acid (0.85% by weight based on the weight of the delimed hides as indicated previously) and a suitable amount of sulphuric acid depending on the final pH desired was added. Drumming was continued for a further 12 hours .
  • the pH of the pickling liquor was from about 1.5 to 3, depending on the extent of deliming of the hides and the amount of sulphuric acid added previously. A sample cut was taken from the hide which showed that full penetration of the pickling agent had been achieved. No swelling of the hide was observed.
  • a solution of water and sodium formate was prepared and added to delimed hides as in Example 4, followed by the addition of the phenol sulphonic acid solution to the hides also in accordance with Example 4. After drumming for 30 minutes, formic acid (0.85%) was added and sulphuric acid as in Example 4 and drumming continued for a further 30 minutes. 8% by weight of a "33% basic" chromium tanning material (i.e. a tanning powder comprising chromium sulphate in which one third of the sulphate ion content had been replaced by hydroxyl ion) was then added to the drumming vessel and the mixture further drummed. Full penetration was noted after 5 to 7 hours by observing a sample removed from the hide. The pH of the tanning solution was raised to 3.5 to 4.2 by adding magnesium oxide (0.5% to 1.5% depending on the final pH desired). The hides were drained and washed. Shrinkage temperature of the tanned material was >100°C.
  • Delimed pelts were drummed with water and sodium formate, then treated with phenol sulphonic acid solution as in Example 6. Drumming was continued for 2 hours and sulphuric acid (0.5%) was added. After further drumming for 4 hours, antifungal agent was added, and the pelts were drummed for a further 1 hour. At a final pH of 1.2 no swelling was discernible.
  • the present invention has largely been described with reference to chromium tanning, the invention can be expected to offer advantages when employed in association with other tanning regimes, such as other mineral tannages, vegetable tanning, aldehyde tanning, Syntans tannages, where pickling is required.
  • other tanning regimes such as other mineral tannages, vegetable tanning, aldehyde tanning, Syntans tannages, where pickling is required.
  • TDS Total Dissolved Solids
  • the addition of the pickling agent and the formation of the pickling agent is less hazardous and more convenient since only routine precautions need be taken. No specialised handling precautions or specialised training and experience is required of operators.
  • the agent penetrates hides and skins as rapidly as or more rapidly than the commercial salt alternatives referred to above.
  • the agents can readily be used with the acids of the conventional salt/acid process.
  • the agents are exhausted up to 70% or more.
  • the pickled stock is compatible with conventional chromium or pickle recycling regimes, or tanning processes.
  • the agents are inexpensive and easy to make.
  • the final product obtained by the process of the present invention is just as good as the final product produced by conventional tanning since the quality of the leather produced by the method of the present invention is indistinguishable to that produced in conventional salt/acid tanning.
  • the pickling formulation and pickling agent of the present invention are biodegradable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

Procédé de traitement préalable ou tannage, tandant à modifier les propriétés d'une peau d'animal. Ce traitement préalable consiste à soumettre la peau à une solution de picklage constituée d'un agent de picklage renfermant au moins un ou plusieurs acides phénoliques mono- di- ou tri- sulphoniques ou ses dérivés, soit isolément soit en combinaison, y compris les combinaisons avec d'autres matières. Ce traitement est efficace à un pH final égal ou inférieur à 3,4. Il donne une pénétration régulière de la solution de picklage dans la peau sans que cette dernière ne subisse de gonflement en l'absence d'adjonction de sel. L'avantage de cette solution de picklage et de ce procédé de traitement réside dans le fait que les effluents ont une faible teneur en sel.
PCT/AU1995/000566 1994-09-01 1995-09-01 Picklage des peaux WO1996006953A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU33766/95A AU703154B2 (en) 1994-09-01 1995-09-01 Pickling of hides and skins
EP95930337A EP0778900A4 (fr) 1994-09-01 1995-09-01 Picklage des peaux
NZ292070A NZ292070A (en) 1994-09-01 1995-09-01 Pickling hides and skins by treating the hides or skins with phenol mono-, di- or tri-sulphonic acid in pretreatment to tanning
TW084109264A TW336955B (en) 1994-09-01 1995-09-05 Method of pickling hides or skins and method of preparing the pickling agents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPM7804 1994-09-01
AUPM7804A AUPM780494A0 (en) 1994-09-01 1994-09-01 Pickling of hides and skins

Publications (1)

Publication Number Publication Date
WO1996006953A1 true WO1996006953A1 (fr) 1996-03-07

Family

ID=3782325

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1995/000566 WO1996006953A1 (fr) 1994-09-01 1995-09-01 Picklage des peaux

Country Status (5)

Country Link
EP (1) EP0778900A4 (fr)
AU (1) AUPM780494A0 (fr)
NZ (1) NZ292070A (fr)
WO (1) WO1996006953A1 (fr)
ZA (1) ZA957334B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004015148A1 (fr) * 2002-08-09 2004-02-19 Rhodia Poliamida E Especialidades Ltda. Procede de tannage de peaux
CN115505651A (zh) * 2022-09-20 2022-12-23 南京哈恩达斯体育用品有限公司 一种篮球生产用皮革浸酸装置及方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794920A (en) * 1926-08-30 1931-03-03 Chem Fab Pott & Co Method of moistening and wetting out leather and dried hides
DE1222618B (de) * 1961-08-08 1966-08-11 Basf Ag Herstellung von Trockenpickelbloessen
AU8082975A (en) * 1974-05-06 1976-11-11 Diamond Shamrock Corp Brine free pcikling composition
AU1668888A (en) * 1987-05-27 1988-12-01 Hoechst A.G. Process for short-term preservation of rawhides and skins
AU3207093A (en) * 1992-01-28 1993-07-29 Ciba Specialty Chemicals Holding Inc. Process for pickling and pretanning raw hides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794920A (en) * 1926-08-30 1931-03-03 Chem Fab Pott & Co Method of moistening and wetting out leather and dried hides
DE1222618B (de) * 1961-08-08 1966-08-11 Basf Ag Herstellung von Trockenpickelbloessen
AU8082975A (en) * 1974-05-06 1976-11-11 Diamond Shamrock Corp Brine free pcikling composition
AU1668888A (en) * 1987-05-27 1988-12-01 Hoechst A.G. Process for short-term preservation of rawhides and skins
AU3207093A (en) * 1992-01-28 1993-07-29 Ciba Specialty Chemicals Holding Inc. Process for pickling and pretanning raw hides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0778900A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004015148A1 (fr) * 2002-08-09 2004-02-19 Rhodia Poliamida E Especialidades Ltda. Procede de tannage de peaux
CN115505651A (zh) * 2022-09-20 2022-12-23 南京哈恩达斯体育用品有限公司 一种篮球生产用皮革浸酸装置及方法
CN115505651B (zh) * 2022-09-20 2023-10-20 南京哈恩达斯体育用品有限公司 一种篮球生产用皮革浸酸装置及方法

Also Published As

Publication number Publication date
AUPM780494A0 (en) 1994-09-22
EP0778900A1 (fr) 1997-06-18
NZ292070A (en) 1999-01-28
ZA957334B (en) 1996-03-28
EP0778900A4 (fr) 1997-11-26

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