US3479127A - Process for the unhairing of skins and hides with peracids or their salts - Google Patents
Process for the unhairing of skins and hides with peracids or their salts Download PDFInfo
- Publication number
- US3479127A US3479127A US563060A US3479127DA US3479127A US 3479127 A US3479127 A US 3479127A US 563060 A US563060 A US 563060A US 3479127D A US3479127D A US 3479127DA US 3479127 A US3479127 A US 3479127A
- Authority
- US
- United States
- Prior art keywords
- hides
- skins
- salts
- unhairing
- hair
- 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
Links
- 150000003839 salts Chemical class 0.000 title description 17
- 238000000034 method Methods 0.000 title description 10
- 230000008569 process Effects 0.000 title description 8
- 150000004965 peroxy acids Chemical class 0.000 title description 5
- 210000004209 hair Anatomy 0.000 description 15
- 238000011282 treatment Methods 0.000 description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 12
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000004155 Chlorine dioxide Substances 0.000 description 5
- 235000019398 chlorine dioxide Nutrition 0.000 description 5
- 239000010985 leather Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 102000011782 Keratins Human genes 0.000 description 2
- 108010076876 Keratins Proteins 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
Definitions
- the present invention relates to a process for unhairing skins and hides with oxidizing agents which renders possible a reduction in the time required for the unhairing considerably, as well as, a dissolution of the hair to biologically degradable products.
- leather may be bleached with percompounds, such as, for instance, peracetic acid.
- percompounds such as, for instance, peracetic acid.
- the object of the present invention is to provide a process for unhairing skins and hides with oxidizing agents which renders it possible to effect a substantial reduction in the time required for the unhairing operation and thereby to avoid the aforementioned disadvantage and which also renders it possiblev to dissolve the hair to provide biologically degradable products.
- this object can be achieved when the skins and hides to be unhaired are first subjected to the action of peracids or their salts and then subjected to an aftertreatment with neutral salts or weak or strong alkaline acting salts or bases.
- an aftertreatment with neutral salts or weak or strong alkaline acting salts or bases.
- aqueous solutions of, for instance, ammonium sulfate, trisodium phosphate, disodium phosphate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, -borax or ammonia.
- the after treatment serves to dissolve the tough partially oxidifizd hair and renders them such that the decomposition products can easily be removed by rinsing with water.
- a substantial advantage of the process according to the invention is that the unhaired hides and skins are simultaneously bleached so that after the unhairing pure white unhaired hides are obtained which are exceptionally suited for aniline dying.
- the process according to the invention renders it possible to reduce the time required for dissolving of the hair carried by skins and hides considerably.
- 3,479,127 Patented Nov. 18, 1969 previously employed treatment with chlorine dioxide reaction periods of about 20-26 hours were required.
- the reaction period required for example, with monopersulfuric acid (H Caros acid) or its salts is 3-15 hours and with peracetic acid about 2-8 hours.
- Herisonous health debilitating fumes such as are apt to occur with unhairing treatments with C10 do not occur in the process according to the invention.
- Precise times for the duration of the preliminary treatment of the skins or hides to be unhaired with the peracids or their salts cannot be given as this depends upon the type and condition of the skins and hides treated, as well as the concentrations involved.
- the time when the preliminary oxidative treatment has been of sufficient duration is easily determined by removal of a sample of the treated skins or hides and testing the solubility of the hair in the aqueous salt or base solution to be employed in the after treatment.
- the quantity of salt or base in the aqueous solution employed for the aftertreatment for example, can be between 0.5 and 4% by weight with reference to the hides.
- the time required for the unhairing of long haired hides can be reduced by subjecting such hides to a preliminary mechanical or chemical (for instance, with Na S enzyme) unhairing treatment before it is subjected to the treatment according to the invention.
- Monopersulfuric acid and it equivalent Water soluble salts and peracetic acid have been found particularly suited as the oxidizing percompounds employed in the first stage of the process according to the invention.
- Permonosulfuric acid and its salts as well as peracetic acid only attack the keratin of the hair and degrade it by oxidation.
- the skin pigments are simultaneously bleached so that with proper treatment pure white unhaired skins and hides are obtained and the yield of uniformly dyeable leather is increased. It, furthermore, is noteworthy that the skins and hides do not swell during the treatment with peracetic acid, and permonosulfuric acid or its salts so that a smooth and firm grained leather can be obtained.
- EXAMPLE 1 1000 kg. of hides or skins '(cowhides, calfskins, sheepskins or goatskins) were fleshed and treated in a drum rotating at 2-5 r.p.m. with 50l00% by weight, with reference to the skins or hides treated, of aqueous 5-15 Caros acid. After the hair had been sufficiently attacked and the skins and hides bleached, the skins and hides were drained, rinsed with water and then treated in the drum with 1000 liters of a 4% by weight of an aqueous solution of sodium carbonate for 1 hour.
- the oxidation products of the hair were water soluble and biologically degradable. After rinsing the skins and hides were pickled and tanned.
- the time required for the, preliminary treatment with Caros acid depended upon the hides and skins treated and the concentration employed. It varied between 5 and 15 hours.
- EXAMPLE 2 1000 kg. of softened and fleshed cowhides were treated with 50200% by weight of an aqueous liquor with reference to the hides treated, containing 0.5-5% pH 2-5.5) or peracetic acid in a slowly rotating drum. After three hours the attack on the hair was such that they dissolve after drawing off the original liquor and rinsing with water when treated for 1 hour with 1000 liters of a 4% by weight aqueous solution of (NH SO After rinsing and removal of any oxidizing agent eventually still present by reduction the unhaired hides which were smooth and pure white were pickled and tanned. Similar results were obtained when the (NH SO solution employed was replaced by analogous aqueous NaHCO or Na CO solutions.
- a method of unhairing hair bearing cowhides, calfskins, sheepskins or goatskins comprising contacting such skins or hides with an aqueous solution of an oxidizing agent selected from the group consisting of permono- References Cited UNITED STATES PATENTS 593,660 11/1897 Holmes 8-94.16
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)
- Detergent Compositions (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED47709A DE1281093B (de) | 1965-07-10 | 1965-07-10 | Verfahren zur oxydativen Enthaarung von Haeuten oder Fellen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3479127A true US3479127A (en) | 1969-11-18 |
Family
ID=7050617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US563060A Expired - Lifetime US3479127A (en) | 1965-07-10 | 1966-07-06 | Process for the unhairing of skins and hides with peracids or their salts |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3479127A (en, 2012) |
| BE (1) | BE683688A (en, 2012) |
| DE (1) | DE1281093B (en, 2012) |
| GB (1) | GB1114068A (en, 2012) |
| NL (1) | NL6609455A (en, 2012) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9102563A (pt) * | 1991-06-19 | 1993-02-09 | Brasil Peroxidos | Processo aperfeicoado para depliacao de peles animais |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US593660A (en) * | 1897-11-16 | Half to william evans | ||
| GB692478A (en) * | 1949-09-15 | 1953-06-10 | Wolsey Ltd | A process for the treatment of keratinous materials and production of articles from the treated materials |
| FR1485439A (fr) * | 1965-07-10 | 1967-06-16 | Gold Und Silaber Scheideanstal | Procédé pour l'épilation des peaux et fourrures avec des agents d'oxydation, ainsi que les produits conformes à ceux obtenus par le présent procédé ou procédé similaire |
| DE1246155B (de) * | 1965-05-13 | 1967-08-03 | Basf Ag | Verfahren zur oxydativen Enthaarung von Haeuten und Fellen |
-
1965
- 1965-07-10 DE DED47709A patent/DE1281093B/de active Pending
-
1966
- 1966-06-30 GB GB29431/66A patent/GB1114068A/en not_active Expired
- 1966-07-05 BE BE683688D patent/BE683688A/xx unknown
- 1966-07-06 NL NL6609455A patent/NL6609455A/xx unknown
- 1966-07-06 US US563060A patent/US3479127A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US593660A (en) * | 1897-11-16 | Half to william evans | ||
| GB692478A (en) * | 1949-09-15 | 1953-06-10 | Wolsey Ltd | A process for the treatment of keratinous materials and production of articles from the treated materials |
| DE1246155B (de) * | 1965-05-13 | 1967-08-03 | Basf Ag | Verfahren zur oxydativen Enthaarung von Haeuten und Fellen |
| FR1485439A (fr) * | 1965-07-10 | 1967-06-16 | Gold Und Silaber Scheideanstal | Procédé pour l'épilation des peaux et fourrures avec des agents d'oxydation, ainsi que les produits conformes à ceux obtenus par le présent procédé ou procédé similaire |
Also Published As
| Publication number | Publication date |
|---|---|
| NL6609455A (en, 2012) | 1967-01-11 |
| DE1281093B (de) | 1968-10-24 |
| BE683688A (en, 2012) | 1966-12-16 |
| GB1114068A (en) | 1968-05-15 |
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