US2577033A - Tanning of hides and skins with formals - Google Patents
Tanning of hides and skins with formals Download PDFInfo
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- US2577033A US2577033A US13330A US1333048A US2577033A US 2577033 A US2577033 A US 2577033A US 13330 A US13330 A US 13330A US 1333048 A US1333048 A US 1333048A US 2577033 A US2577033 A US 2577033A
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- 239000002904 solvent Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 69
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000011282 treatment Methods 0.000 description 15
- 235000010755 mineral Nutrition 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 239000010985 leather Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- QLCJOAMJPCOIDI-UHFFFAOYSA-N 1-(butoxymethoxy)butane Chemical compound CCCCOCOCCCC QLCJOAMJPCOIDI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- -1 for example Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002195 soluble material Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
Definitions
- My invention relates to the treatment of hides and skins.
- a skin or hide pretreated to remove hair and treated by various other steps such as bating and pickling, is immersed for an extended period in a solution of basic chromium sulphate.
- this chromium treatment of the skin or hide is carried on in a paddle or a drum during the chrome treating period and is then removed from the paddle or drum and aged for a period of from several hours up to two days.
- dehaired and otherwise pretreated skins or hides are subjected to various steps including a prolonged soaking treatment in a solution containing various vegetable extracts.
- Tanning by the vegetable method occupies a period of several weeks and involves extensive handling of the hides.
- skins or hides may be converted to this novel, leather-like material by drying the skin or hide material and contacting the dried material with an organic solvent solution of a formal containing a limited amount of a strong mineral acid.
- bated or pickled skins or hides for example calfskins or steer hides, are satisfactory. Skins or hides in other conditions may also be used.
- Skins or hides of animals generally used for the making leather may be treated according to the process of the present invention.
- skin and skin material are to be understood in their broad sense as including these materials.
- hides in the claims is intended to include both hides and skins in condition for conventional tanning.
- a pickled material is used, it is first subjected to a conventional depickling operation.
- the depickled skin is then immersed in water with agitationto remove dissolved salts and other soluble materials.
- a suitable treatment period may range from around two hours for calfskin to four hours for a steer skin.
- the depickled and soaked skin is then dried to a moisture content which may be between about 10 and about 15%.
- This moisture content is determined by comparison with the weight of the skin when subjected to a further drying for sixteen hours in air at 105 C. It has been found that drying is most satisfactorily accomplished by the action of solvents, for example, acetone, methyl acetate, isopropyl alcohol, dioxane, methyl Cellosolve acetate or other solvent which will remove the water without seriously harming the skin.
- solvents for example, acetone, methyl acetate, isopropyl alcohol, dioxane, methyl Cellosolve acetate or other solvent which will remove the water without seriously harming the skin.
- This drying may be effected by leaving the skin immersed in an agitated bath of the solvent overnight.
- the solvent is then removed from the skin, suitably by evaporation in a stream of dry, warm air.
- the dried skin is immersed in a body of the liquid treating agent and is maintained in the liquid for a sufficient period to convert the skin to the new leather-like condition.
- the liquid treating agents according to my invention comprise organic solvent solutions of a strong mineral acid and a formal.
- Formals whichhave been used for the treatment of skin material in accordance with my invention include the formal of the monomethyl ether of diethylene glycol, the formal of the monomethyl ether of ethylene glycol, the formal of the monobutyl ether of diethylene glycol, di-chlorethyl formal,
- formals may be considered as having the formula wherein R is an aliphatic organic radical containing more than one carbon atom.
- the formals may be used to the extent of about 2% to by volume, based on the volume of the solution.
- strong mineral acids which may be used are sulfuric acid, hydrochloric acid, hydrobromic acid, and perchloric acid.
- Other strong mineral acids may be used. These acids may be employed in the proportions of about 0.3% to about 4% of a concentrated solution of the strong mineral acid base on the total volume of the treating agent.
- Concentrated hydrochloric acid Will contain about 38% of HCl; concentrated sulfuric acid will contain about 90% of H2804; concentrated hydrobromic acid will contain about of I-IBr;. and concentrated perchloric acid will contain about HC1O4.
- concentrated aqueous solutions of strong mineral acids refers to aqueous solutions containing the above noted percentages of these acids.
- the required volume of concentrated acid may be diluted before mixture with the remaining components where it is desirable to avoid excessive interaction with the remainder of the treating agent.
- the formal is employed in the ratio of about 5 to 15 parts by volume to one part by volume of the concentrated strong mineral acid.
- Suitable solvents for use in the treating agent include acetone, di-oxane, and trichlorethylene. Other similar neutral organic solvents such as methyl, n-propyl ketone or other solvent for the formal may be used.
- the time of immersion of the skin in the treating agent varies with the weight and type of skin treated. Preferred times of treatment may be from about one-half hour to about five hours.
- Preferred times of treatment may be from about one-half hour to about five hours.
- satisfactory action has been obtained by immersion of the prepared, dried, calfskin for about two hours at room temperature in a solution comprising 1% by volume of a 38% hydrochloric acid solution, 9% by volume of the formal of the monomethyl ether of diethylene glycol, and 90% by volume of acetone.
- the temperature of the treating bath may vary. Factors controlling the temperature include the boiling points and vapor pressure of the solvents and of the treating agents and the rate of treating action desired.
- the skin is removed from the treating bath and is immersed in a solvent to remove soluble materials such as excess agent, reaction products and the like.
- Suitable solvents for this use are tri-chlorethylene, acetone and toluene.
- the skin is removed from the solvent bath and is permitted to dry.
- the dried skin is then placed in a neutralizing bath, which may be a depickling solution, until it reaches a pH of about 7 or other value depending upon the properties desired. This step is desirable in that it also serves. to neutralize or decompose acid compounds within the skin.
- the skin is finally washed to remove salts, and is then removed from the washing bath.
- the treated skin may be subjected to such fur- 90 parts by volume of acetone.
- ther treatments as desired, for example, dyeing, fat liquoring or stuffing, drying and surface finishing.
- Example 1 --A bated and pickled calfskin was depickled by immersion for one'hour in a 5% aqueous solution of sodium bicarbonate. The depickled calfskin was then washed in running water for an hour and dried overnight in acetone. The calfskin was then removed from the acetone, subjected to a blast of warm air to evaporate the acetone and then immersed for two hours in a treating bath at 130 F., the treating bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of the formal of the monomethyl ether of diethylene glycol and The treated material was then removed from the bath, washed in acetone for two hours, removed from the acetone and allowed to dry.
- the treating bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of the formal of the monomethyl ether of diethylene glycol and The treated material was then removed from the bath, washed in acetone for two hours, removed
- Emmple 2 A bated calfskin was immersed overnight in acetone to dry it to a moisture content of about 10% determined as noted above. The dried calfskin was then removed and the acetone was evaporated by a blast of warm air. After evaporation of the acetone the calfskin was immersed in a treating bath at 130 F. for two hours, the bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of 2,2 dichlorethyl formal and parts by volume of acetone. The treated skin was then removed and washed for two hours in a bath consisting only of acetone.
- the skin was then removed from the acetone, the acetone evaporated and the skin then immersed in a bath of 5% solution of sodium bicarbonate in water until the skin reached a pH of about 7..
- the neutralized skin was removed from the sodium bicarbonate solution and placed in a bath of running water for two hours, at which time it was removed and found to be in a condition resembling leather in which it could be subjected to the usual operations following tanning.
- Example 3 A bated and pickled steer hide was immersed overnight in acetone to dry the hide to a moisture content of about 10% calculated as noted above. It was then removed and the acetone evaporated. by a blast of warm air. The dried hide was then treated in a bath consisting of 10 parts by volume of concentrated (38%) hydrochloric acid, 30 parts by volume of the formal of the monomethyl ether of diethylene glycol and 60 parts by volume of acetone. The treatment was carried out at F. for aperiod of five hours. The treated hide was removed from the bath and washed for two hours in acetone and was then removed and the acetone allowed to evaporate.
- the hide was neutralized by soaking in a bath of 5% sodium bicarbonate in water until the skin reached a pH of about '7. The neutralized side was removed and soluble materials removed by washing it in a bath of running water for two hours. The hide was found to be in a stable and nonputrescible condition suitable for conventional after-tanning treatment.
- Example 4.-A bated and pickled calfskin was immersed overnight in acetone to dry the skin to moisture content of about 10% calculated as noted above. It was then removed and the acetone evaporated by a blast of warm air.
- the dried skin was then treated in a bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of dibutoxymethane, and 90 parts by volume of acetone.
- the treatment was carried out for a period of two hours at 130 F.
- the treated skin was removed from the bath and washed for two hours in acetone and was then removed and the acetone allowed to evaporate.
- the skin was neutralized by soaking in a bath of a 5% solution of sodium bicarbonate in water until the skin reached a pH of about 7.
- the neutralized skin was removed from the sodium bicarbonate and placed in a bath of running water for about two hours, at which time it was removed and found to be in a condition in which it could be subjected to the usual operations following tanning.
- Example 5 A bated and pickled steer hide was immersed overnight in acetone to dry the hide to a moisture content of about calculated as noted above. The dried hide was then removed and the acetone evaporated by a blast of warm air. After evaporation of the acetone, the steer hide was immersed in a treating bath at 130 F. for about five hours, the bath consisting of 1 part by volume of concentrated sulfuric acid, 9 parts by volume of the formal of the monomethyl ether of ethylene glycol and 90 parts by volume of acetone. The treated hide was then removed from the treating bath and washed for two hours in acetone.
- the hide was then removed from the acetone, the acetone evaporated and the skin then immersed in a bath of 5% solution of sodium bicarbonate in water until the hide reached a pH of about '7.
- the neutralized hide was removed from the sodium bicarbonate solution and placed in running water for two hours, at which time it was removed and found to be in a condition in which it could be subjected to the usual operations following tanning.
- the method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to based on the dry weight of the hides and immersing the hides in a solution containing an inert organic solvent, from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, and at least 2% by volume of a formal having the formula wherein R is an aliphatic radical containing more than one carbon atom, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
- the method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry Weight of the hides and immersing the hides in 6 a solution comprising an inert organic solvent, from 2% to 30% by volume of a formal having the formula /O-R HgC wherein R is an aliphatic radical containing more than one carbon atom, and from 0.3% to 4.0% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
- the method of tanning hides which comprises drying the hides by immersing the hide in a water miscible inert organic volatile solvent. then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of the formal of the monomethyl ether of diethylene glycol, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
- the method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of the formal of the monomethyl ether of ethylene glycol, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
- the method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of dibutoxy methane, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the dibutoxy methane being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
- Themethod of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of a formal having the formula wherein R is an aliphatic radical containing more than one carbon atom, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid, for a period corre sponding to from about two hours for calfskin to about four hours for a steer hide, removing uncombined compounds by the action of a solvent,
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Description
Patented Dec. 4, 1951 TANNING OF HIDES AND SKINS WITH FORMALS Robert C. Putnam, Marblehead, Mass., assignor to United Shoe Machinery Corporation, Flemington, N. J., a corporation of New Jersey No Drawing. Application March 5, 1948, Serial No. 13,330
6 Claims.
My invention relates to the treatment of hides and skins.
In the well-known chrome tanning process, a skin or hide pretreated to remove hair and treated by various other steps such as bating and pickling, is immersed for an extended period in a solution of basic chromium sulphate. Ordinarily this chromium treatment of the skin or hide is carried on in a paddle or a drum during the chrome treating period and is then removed from the paddle or drum and aged for a period of from several hours up to two days.
In the vegetable tanning process, dehaired and otherwise pretreated skins or hides are subjected to various steps including a prolonged soaking treatment in a solution containing various vegetable extracts. Tanning by the vegetable method occupies a period of several weeks and involves extensive handling of the hides.
By either of these common methods of tanning, extended periods of time are required so that to insure continuous production of leather a very large number of skins or hides must be maintained in various stages of tanning. Investment in skins or hides and in treating tanks, vats, or
other treating equipment is large so that cost of the ultimate leather is high.
It is an important feature of my invention to convert skin and hide material to a stable nonputrescible leather-like condition by a short and simple treatment of the skin or hide materials with a new type of reagent. By my new process there is formed a tough, pliable product similar to leather in appearance and in many other properties. The new product will withstand prolonged soaking in water without marked shriveling or hardening even at relatively high temperatures, and is exceptionally resistant to mold growth.
' I have discovered that skins or hides may be converted to this novel, leather-like material by drying the skin or hide material and contacting the dried material with an organic solvent solution of a formal containing a limited amount of a strong mineral acid.
For treatment according to the process of the present invention, I have found that bated or pickled skins or hides, for example calfskins or steer hides, are satisfactory. Skins or hides in other conditions may also be used.
Skins or hides of animals generally used for the making leather may be treated according to the process of the present invention. In the specification, the terms skin and skin material are to be understood in their broad sense as including these materials. The term hides in the claims is intended to include both hides and skins in condition for conventional tanning.
Where a pickled material is used, it is first subjected to a conventional depickling operation. The depickled skin is then immersed in water with agitationto remove dissolved salts and other soluble materials. A suitable treatment period may range from around two hours for calfskin to four hours for a steer skin.
The depickled and soaked skin is then dried to a moisture content which may be between about 10 and about 15%. This moisture content is determined by comparison with the weight of the skin when subjected to a further drying for sixteen hours in air at 105 C. It has been found that drying is most satisfactorily accomplished by the action of solvents, for example, acetone, methyl acetate, isopropyl alcohol, dioxane, methyl Cellosolve acetate or other solvent which will remove the water without seriously harming the skin. This drying may be effected by leaving the skin immersed in an agitated bath of the solvent overnight. The solvent is then removed from the skin, suitably by evaporation in a stream of dry, warm air.
The above is but one of many conceivable methods for treatment of a skin prior to the treatment with my new agents. Modifications will be readily apparent to persons familiar with the handling of skins. For example, a bated skin need not be subjected to the depickling and washing operations above outlined.
The dried skin is immersed in a body of the liquid treating agent and is maintained in the liquid for a sufficient period to convert the skin to the new leather-like condition.
The liquid treating agents according to my invention comprise organic solvent solutions of a strong mineral acid and a formal. Formals whichhave been used for the treatment of skin material in accordance with my invention include the formal of the monomethyl ether of diethylene glycol, the formal of the monomethyl ether of ethylene glycol, the formal of the monobutyl ether of diethylene glycol, di-chlorethyl formal,
methoxy methylal, ethyl formal, butyl formal, dibutoxy methane and glycol formal. These formals may be considered as having the formula wherein R is an aliphatic organic radical containing more than one carbon atom. For efficient operation in my process, the formals may be used to the extent of about 2% to by volume, based on the volume of the solution.
Among the strong mineral acids which may be used are sulfuric acid, hydrochloric acid, hydrobromic acid, and perchloric acid. Other strong mineral acids may be used. These acids may be employed in the proportions of about 0.3% to about 4% of a concentrated solution of the strong mineral acid base on the total volume of the treating agent. Concentrated hydrochloric acid Will contain about 38% of HCl; concentrated sulfuric acid will contain about 90% of H2804; concentrated hydrobromic acid will contain about of I-IBr;. and concentrated perchloric acid will contain about HC1O4. The term in the claims, concentrated aqueous solutions of strong mineral acids, refers to aqueous solutions containing the above noted percentages of these acids. The required volume of concentrated acid may be diluted before mixture with the remaining components where it is desirable to avoid excessive interaction with the remainder of the treating agent. In the treating agent, the formal is employed in the ratio of about 5 to 15 parts by volume to one part by volume of the concentrated strong mineral acid.
Suitable solvents for use in the treating agent include acetone, di-oxane, and trichlorethylene. Other similar neutral organic solvents such as methyl, n-propyl ketone or other solvent for the formal may be used.
The time of immersion of the skin in the treating agent varies with the weight and type of skin treated. Preferred times of treatment may be from about one-half hour to about five hours. In the case of a calfskin, satisfactory action has been obtained by immersion of the prepared, dried, calfskin for about two hours at room temperature in a solution comprising 1% by volume of a 38% hydrochloric acid solution, 9% by volume of the formal of the monomethyl ether of diethylene glycol, and 90% by volume of acetone.
The temperature of the treating bath may vary. Factors controlling the temperature include the boiling points and vapor pressure of the solvents and of the treating agents and the rate of treating action desired.
After the above treatment, the skin is removed from the treating bath and is immersed in a solvent to remove soluble materials such as excess agent, reaction products and the like. Suitable solvents for this use are tri-chlorethylene, acetone and toluene.
The skin is removed from the solvent bath and is permitted to dry. The dried skin is then placed in a neutralizing bath, which may be a depickling solution, until it reaches a pH of about 7 or other value depending upon the properties desired. This step is desirable in that it also serves. to neutralize or decompose acid compounds within the skin. The skin is finally washed to remove salts, and is then removed from the washing bath.
The treated skin may be subjected to such fur- 90 parts by volume of acetone.
ther treatments as desired, for example, dyeing, fat liquoring or stuffing, drying and surface finishing.
The following examples are given as illustrative of processes in accordance with the present invention. It is to be understood that the invention is not restricted to the reagents and procedural details disclosed in these examples.
Example 1.--A bated and pickled calfskin was depickled by immersion for one'hour in a 5% aqueous solution of sodium bicarbonate. The depickled calfskin was then washed in running water for an hour and dried overnight in acetone. The calfskin was then removed from the acetone, subjected to a blast of warm air to evaporate the acetone and then immersed for two hours in a treating bath at 130 F., the treating bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of the formal of the monomethyl ether of diethylene glycol and The treated material was then removed from the bath, washed in acetone for two hours, removed from the acetone and allowed to dry. It was then immersed in a 5% solution of sodium bicarbonate in water until the skin reached a pH of about 7. The neutralized skin was removed from the neutralizing oath and washed in running Water for two hours. At this time the calfskin was found to be in a stable, nonputrescible condition in which it could be subjected to the usual operations following tanning.
Emmple 2.A bated calfskin was immersed overnight in acetone to dry it to a moisture content of about 10% determined as noted above. The dried calfskin was then removed and the acetone was evaporated by a blast of warm air. After evaporation of the acetone the calfskin was immersed in a treating bath at 130 F. for two hours, the bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of 2,2 dichlorethyl formal and parts by volume of acetone. The treated skin was then removed and washed for two hours in a bath consisting only of acetone. The skin was then removed from the acetone, the acetone evaporated and the skin then immersed in a bath of 5% solution of sodium bicarbonate in water until the skin reached a pH of about 7.. The neutralized skin was removed from the sodium bicarbonate solution and placed in a bath of running water for two hours, at which time it was removed and found to be in a condition resembling leather in which it could be subjected to the usual operations following tanning.
Example 3.A bated and pickled steer hide was immersed overnight in acetone to dry the hide to a moisture content of about 10% calculated as noted above. It was then removed and the acetone evaporated. by a blast of warm air. The dried hide was then treated in a bath consisting of 10 parts by volume of concentrated (38%) hydrochloric acid, 30 parts by volume of the formal of the monomethyl ether of diethylene glycol and 60 parts by volume of acetone. The treatment was carried out at F. for aperiod of five hours. The treated hide was removed from the bath and washed for two hours in acetone and was then removed and the acetone allowed to evaporate. The hide was neutralized by soaking in a bath of 5% sodium bicarbonate in water until the skin reached a pH of about '7. The neutralized side was removed and soluble materials removed by washing it in a bath of running water for two hours. The hide was found to be in a stable and nonputrescible condition suitable for conventional after-tanning treatment. Example 4.-A bated and pickled calfskin was immersed overnight in acetone to dry the skin to moisture content of about 10% calculated as noted above. It was then removed and the acetone evaporated by a blast of warm air. The dried skin was then treated in a bath consisting of 1 part by volume of concentrated (38%) hydrochloric acid, 9 parts by volume of dibutoxymethane, and 90 parts by volume of acetone. The treatment was carried out for a period of two hours at 130 F. Then the treated skin was removed from the bath and washed for two hours in acetone and was then removed and the acetone allowed to evaporate. The skin was neutralized by soaking in a bath of a 5% solution of sodium bicarbonate in water until the skin reached a pH of about 7. The neutralized skin was removed from the sodium bicarbonate and placed in a bath of running water for about two hours, at which time it was removed and found to be in a condition in which it could be subjected to the usual operations following tanning.
Example 5.A bated and pickled steer hide was immersed overnight in acetone to dry the hide to a moisture content of about calculated as noted above. The dried hide was then removed and the acetone evaporated by a blast of warm air. After evaporation of the acetone, the steer hide was immersed in a treating bath at 130 F. for about five hours, the bath consisting of 1 part by volume of concentrated sulfuric acid, 9 parts by volume of the formal of the monomethyl ether of ethylene glycol and 90 parts by volume of acetone. The treated hide was then removed from the treating bath and washed for two hours in acetone. The hide was then removed from the acetone, the acetone evaporated and the skin then immersed in a bath of 5% solution of sodium bicarbonate in water until the hide reached a pH of about '7. The neutralized hide was removed from the sodium bicarbonate solution and placed in running water for two hours, at which time it was removed and found to be in a condition in which it could be subjected to the usual operations following tanning.
Having thus described my invention, what I claim as new and desire to secure by Letters Patent of the United States is:
l. The method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to based on the dry weight of the hides and immersing the hides in a solution containing an inert organic solvent, from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, and at least 2% by volume of a formal having the formula wherein R is an aliphatic radical containing more than one carbon atom, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
2. The method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry Weight of the hides and immersing the hides in 6 a solution comprising an inert organic solvent, from 2% to 30% by volume of a formal having the formula /O-R HgC wherein R is an aliphatic radical containing more than one carbon atom, and from 0.3% to 4.0% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
3. The method of tanning hides which comprises drying the hides by immersing the hide in a water miscible inert organic volatile solvent. then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of the formal of the monomethyl ether of diethylene glycol, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
4. The method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of the formal of the monomethyl ether of ethylene glycol, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
5. The method of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of dibutoxy methane, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the dibutoxy methane being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid.
6. Themethod of tanning hides which comprises drying the hide by immersing the hide in a water miscible inert organic volatile solvent, then removing the solvent to obtain a moisture content of from 10% to 15% based on the dry weight of the hides and immersing the hides in a solution comprising an inert organic solvent, from 2% to 30% by volume of a formal having the formula wherein R is an aliphatic radical containing more than one carbon atom, and from 0.3% to 4% by volume of a concentrated aqueous solution of a strong mineral acid, the formal being present in the ratio of from 5 to 15 parts by volume to 1 part by volume of the acid, for a period corre sponding to from about two hours for calfskin to about four hours for a steer hide, removing uncombined compounds by the action of a solvent,
ROBERT C. PUTNAM.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number FOREIGN PATENTS Country v Date France Nov. 2, 1908 Great Britain Mar. 23, 1938 Australia Jan. 9, 1943 OTHER REFERENCES "Journal of American Leather Chemists vol. 38, May 1943, page 185. Article by Roddy.
Formaldehyde, by Walker, page 139 (Rhei'n hold Pub. C0rp., N. Y. C.), 1944. Copy in Division 31.
Organic Chemistry, Whitmore, page 255, D. Van Nostrand 00. N. Y. C., 1937, Copy in Division Number
Claims (1)
1. THE METHOD OF TANNING HIDES WHICH COMPRISES DRYING THE HIDE BY IMMERSING THE HIDE IN A WATER MISCIBLE INERT ORGANIC VOLATILE SOLVENT, THEN REMOVING THE SOLVENT TO OBTAIN A MOISTURE CONTENT OF FROM 10% TO 15% BASED ON A MOISTURE WEIGHT OF THE HIDES AND IMMERSING THE HIDES IN A SOLUTION CONTAINING AN INERT ORGANIC SOLVENT, FROM 0.3% TO 4% BY VOLUME OF A CONCENTRATED AQUEOUS SOLUTION OF A STRONG MINERAL ACID, AND AT LEAST 2% BY VOLUME OF A FORMAL HAVING THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13330A US2577033A (en) | 1948-03-05 | 1948-03-05 | Tanning of hides and skins with formals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13330A US2577033A (en) | 1948-03-05 | 1948-03-05 | Tanning of hides and skins with formals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2577033A true US2577033A (en) | 1951-12-04 |
Family
ID=21759411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13330A Expired - Lifetime US2577033A (en) | 1948-03-05 | 1948-03-05 | Tanning of hides and skins with formals |
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| Country | Link |
|---|---|
| US (1) | US2577033A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3006714A (en) * | 1956-10-01 | 1961-10-31 | Nathan W Levin | Treatment of animal skins |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR391474A (en) * | 1907-08-30 | 1908-11-02 | Henri Morin | Skin tanning process |
| US2005499A (en) * | 1929-08-03 | 1935-06-18 | Ici Ltd | Resinous compounds |
| GB482286A (en) * | 1936-09-23 | 1938-03-23 | George Freeman Lloyd | Improved process of tanning skins and hides and the product thereof |
| US2395472A (en) * | 1942-02-25 | 1946-02-26 | Du Pont | Tanning compositions and their manufacture |
| US2427097A (en) * | 1944-08-23 | 1947-09-09 | Kamlet Jonas | Shrinkproofing and feltproofing of keratinous textile fibers |
| US2435554A (en) * | 1945-08-31 | 1948-02-03 | Norton Co | Phenolic-alkyd resins |
-
1948
- 1948-03-05 US US13330A patent/US2577033A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR391474A (en) * | 1907-08-30 | 1908-11-02 | Henri Morin | Skin tanning process |
| US2005499A (en) * | 1929-08-03 | 1935-06-18 | Ici Ltd | Resinous compounds |
| GB482286A (en) * | 1936-09-23 | 1938-03-23 | George Freeman Lloyd | Improved process of tanning skins and hides and the product thereof |
| US2395472A (en) * | 1942-02-25 | 1946-02-26 | Du Pont | Tanning compositions and their manufacture |
| US2427097A (en) * | 1944-08-23 | 1947-09-09 | Kamlet Jonas | Shrinkproofing and feltproofing of keratinous textile fibers |
| US2435554A (en) * | 1945-08-31 | 1948-02-03 | Norton Co | Phenolic-alkyd resins |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3006714A (en) * | 1956-10-01 | 1961-10-31 | Nathan W Levin | Treatment of animal skins |
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