US2018588A - Process of filling leather and the resulting product - Google Patents
Process of filling leather and the resulting product Download PDFInfo
- Publication number
- US2018588A US2018588A US737290A US73729034A US2018588A US 2018588 A US2018588 A US 2018588A US 737290 A US737290 A US 737290A US 73729034 A US73729034 A US 73729034A US 2018588 A US2018588 A US 2018588A
- Authority
- US
- United States
- Prior art keywords
- leather
- tanning
- fibrils
- extract
- fibres
- 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
- 239000010985 leather Substances 0.000 title description 57
- 238000000034 method Methods 0.000 title description 27
- 239000000284 extract Substances 0.000 description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 20
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 20
- 150000001299 aldehydes Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 229920001864 tannin Polymers 0.000 description 17
- 239000001648 tannin Substances 0.000 description 17
- 235000018553 tannin Nutrition 0.000 description 17
- 235000013311 vegetables Nutrition 0.000 description 17
- 150000003863 ammonium salts Chemical class 0.000 description 16
- 239000002198 insoluble material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 239000001166 ammonium sulphate Substances 0.000 description 8
- 235000011130 ammonium sulphate Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 235000017343 Quebracho blanco Nutrition 0.000 description 6
- 241000065615 Schinopsis balansae Species 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000035515 penetration Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- 244000283070 Abies balsamea Species 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 244000036978 Caesalpinia bonduc Species 0.000 description 1
- 235000014145 Caesalpinia bonduc Nutrition 0.000 description 1
- 235000009133 Caesalpinia coriaria Nutrition 0.000 description 1
- 235000005082 Caesalpinia paraguariensis Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 240000009120 Phyllanthus emblica Species 0.000 description 1
- 235000007748 Quercus prinus Nutrition 0.000 description 1
- 244000025767 Quercus prinus Species 0.000 description 1
- 241000381592 Senegalia polyacantha Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241001478802 Valonia Species 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- XQVYLHKEWUACHO-UHFFFAOYSA-N azane;benzene-1,2-diol Chemical compound N.OC1=CC=CC=C1O XQVYLHKEWUACHO-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 210000000051 wattle Anatomy 0.000 description 1
- 244000089265 zong er cha Species 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/04—Fixing tanning agents in the leather
Definitions
- My invention relates to an improved leather product and to the process of making it, and more particularly it relates to an improved leather product, especially applicable as a heavy sole 3 leather.
- One object of my invention is to provide a leather product of increased solidity, and increased thickness and weight, which properties are obtained in the leather without the necessity of loading the product with a water-soluble filler as has previously been the case.
- a further object of my invention is to furnish to the trade a leather, particularly adapted for use as sole leather, which possesses high wearresistant qualities and high resistance to water penetration and to the softening efiects normally encountered in the presence of moisture or high humidities.
- Still another object of my invention is to provide a leather with a marked decrease in the tendency of the product to air-burn during the drying operation and for the tanning extracts to bleed to surface during drying or when the I product is worked in a damp condition.
- the process of the present invention overcomes or reduces to a minimum all of the disadvantages of the previous processes, and the product possesses properties which have previously been sought but have only been obtained to a small degree.
- the active tanning agents of the extracts are converted chemically into insoluble products which a are then retained permanently between and on the fibres and fibrils of the leather.
- the chemical conversion of the tanning agents into insoluble material is brought about by a reaction between them, an aldehyde and an ammonium l0 salt. Since the active tanning agent after periormlng its tanning function is rendered insoluble, there is no tendency for the leather to bleed or to air-burn.
- the finished product due to the presence of the insoluble material therein, possesses increased weight, thickness, solidity. and resistance to wear. The product also oflers a higher resistance to water penetration and to softening in the presence of moisture or high humidities.
- the reaction of the tanning 10 agents with the aldehyde and the ammonium salt also gives an antiseptic efiect to the leather which reduces the growth of molds normally encountered with damp leather.
- a leather is easily obtained having a degree of tannage of to or even higher based on the relation between combined tannin and hide substance as determined by the oflicial method of the American Leather Chemists Association, which as higher than that previously such products.
- the process of the present invention may be carried out with any type of hide and any of the usual vegetable tanning extracts, particularly 3 those containing catechol tannins, may be used as the tanning material.
- any of the usual vegetable tanning extracts particularly 3 those containing catechol tannins, may be used as the tanning material.
- the following materials or extracts have been found to be applicable for use:-mangrove, wattle, quebracho 3% blsulphlted, quebracho 6% bisulphited; gambier, hemlock, cutch, chestnut, chestnut oak, myrabolans, valonia, divi-divi, and the like.
- the aldehyde which is employed preferabLv is formaldehyde due to its availability and cheapness but other aldehydes including acetaldehyde, turfuraldehyde, and benzaldehyde may be used. Any salt containing the ammonium radical will satisfactorily react, for example, ammonium sulphate, ammonium chloride, ammonium oxalate, or ammonium phosphate. to
- reaction of the aldehyde and the ammonium salt with the tanning agents to deposit insoluble material between and on the fibers and fibrils of the leather is not strictly speaking a tanning process but rather a filling or finishing encountered in will be recognized 80 sirable that the treatment with the aldehyde.
- the amount of tanning agent employed and the steps of the tanning process may be the same as has previously beenthe practice with the particular type of hide to be tanned and the particular type of leather to be manufactured.
- the order of addition of the materials is immaterial but it is deshall take place after the leather has been tanned, at least to some extent, and the process is particularly applicable for the treatment of tanned leather.
- the three reactants may be add ed simultaneously but preferably the aldehyde is not added until the tanning extracts have been absorbed by the hide or leather.
- the ammonium salt may be added with the tanning agent, simultaneously with the aldehyde, or thereafter.
- the aldehyde and/or ammonium salt may be reacted with the tanning extract in the wheel, drum, temper bath, dry dip, or elsewhere in the process.
- tanning extract aldehyde, and ammonium salt employed are not critical and depend upon the degree of improvement desired.
- Example I Leather is drummed in the usual manner with quebracho extract to which has been added 5% of ammonium sulphate on the dry basis.- The stock is piled down over night to absorb the load and bleached to clear the surface of the leather. It is then dipped fifteen minutes in a solution of formaldehyde containing 20% of this ingredient,
- Example II Rough dry leather which has had one wheel load is dry dipped in a '15 Barkometer dry dip consisting of 95 parts of clarified quebracho and 5 parts of anmionium sulphate on a dry basis. Coming from the dry dip, the leather is dipped fifteen minutes in a solution of 20% formaldehyde and is then given an oil wheel load of Ep-,
- som salts, sugar, and 011 set out, and finished in accordance with the usual practice.
- Example III Leather from the yard may be drummed with dipped if desired in the usual manner to give additional water soluble load, after which it is finished as usual. 1 1
- I claim: 1. The process of filling leather which comprises reacting a vegetable tanning extract, aldehyde', and an ammonium salt together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and thereon.
- the process of filling leather which comprises reacting a vegetable tanning extract containing a catechol tannin, formaldehyde, and ammonium sulphate together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and thereon, the aldehyde being present in the neighborhood of 3% to 4% and the ammonium sulphate being present in the neighborhood of 5% based on the dry extract.
- Filled leather having a degree of tannage 5 on the fibres and fibrils thereof. of at least 110 determined by the ofllcial method 10. Filled leather containing the insoluble reof the American Leather Chemists Association,
- a vegetable tannin extract containing a catechol Filled leather having a degree of tarmage tannin, formaldehyde, and ammonium sulphate of at least 110 determined by the oflicial method between and on the fibres and fibrils thereof.
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)
Description
Patented Oct. 22, 1935 UNITED STATES raoc'nss or FILLING LEATHER mm m ansonrmc raonuc'r Lester M. Whitmore, Salem, Va, asslgnor to Lea and Mcvitty, Inc., Philadelphia, Pa.I a corporation of Delaware No Drawing. Application July 2'3, W84, Serial No. 737,290
14 Claims.
My invention relates to an improved leather product and to the process of making it, and more particularly it relates to an improved leather product, especially applicable as a heavy sole 3 leather.
One object of my invention is to provide a leather product of increased solidity, and increased thickness and weight, which properties are obtained in the leather without the necessity of loading the product with a water-soluble filler as has previously been the case.
A further object of my invention is to furnish to the trade a leather, particularly adapted for use as sole leather, which possesses high wearresistant qualities and high resistance to water penetration and to the softening efiects normally encountered in the presence of moisture or high humidities.
Still another object of my invention is to provide a leather with a marked decrease in the tendency of the product to air-burn during the drying operation and for the tanning extracts to bleed to surface during drying or when the I product is worked in a damp condition.
These and other objects including the provision of a novel process of preparing the leather product will be apparent hereinafter from a consideration of the specification and claims.
Heretofore in the tanning of leather with the natural vegetable tanning extracts, particularly those containing catechol tanning materials, diificulties have been encountered in the process, and in the manufacture of heavy leathers, particularly sole leather, various water soluble materials as fillers have been added to the leather during the process in an attempt to increase the solidity, thickness, weight, and resistance to wear and water penetration. Due to the solubility of the vegetable tanning agents in water-and of the water soluble fillers, these materials during manufacture tend to bleed to the surface, particularly during drying or when the leather is worked in a damp condition. Additionally,the leather tends to air-bum during the drying resulting in an inferior product. Furthermore, the finished product, due to the presence of watersoluble material therein, is not characterized by high resistance to wear or water penetration since in the presence of moisture or high humidities,
50 a dissolving action on the watersoluble material takes place.
The process of the present invention overcomes or reduces to a minimum all of the disadvantages of the previous processes, and the product possesses properties which have previously been sought but have only been obtained to a small degree.
In the process of the present invention, the active tanning agents of the extracts are converted chemically into insoluble products which a are then retained permanently between and on the fibres and fibrils of the leather. The chemical conversion of the tanning agents into insoluble material is brought about by a reaction between them, an aldehyde and an ammonium l0 salt. Since the active tanning agent after periormlng its tanning function is rendered insoluble, there is no tendency for the leather to bleed or to air-burn. Furthermore, the finished product, due to the presence of the insoluble material therein, possesses increased weight, thickness, solidity. and resistance to wear. The product also oflers a higher resistance to water penetration and to softening in the presence of moisture or high humidities. The reaction of the tanning 10 agents with the aldehyde and the ammonium salt also gives an antiseptic efiect to the leather which reduces the growth of molds normally encountered with damp leather. By the process of the present invention, a leather is easily obtained having a degree of tannage of to or even higher based on the relation between combined tannin and hide substance as determined by the oflicial method of the American Leather Chemists Association, which as higher than that previously such products.
The process of the present invention may be carried out with any type of hide and any of the usual vegetable tanning extracts, particularly 3 those containing catechol tannins, may be used as the tanning material. For example, the following materials or extracts have been found to be applicable for use:-mangrove, wattle, quebracho 3% blsulphlted, quebracho 6% bisulphited; gambier, hemlock, cutch, chestnut, chestnut oak, myrabolans, valonia, divi-divi, and the like. The aldehyde which is employed preferabLv is formaldehyde due to its availability and cheapness but other aldehydes including acetaldehyde, turfuraldehyde, and benzaldehyde may be used. Any salt containing the ammonium radical will satisfactorily react, for example, ammonium sulphate, ammonium chloride, ammonium oxalate, or ammonium phosphate. to
The, reaction of the aldehyde and the ammonium salt with the tanning agents to deposit insoluble material between and on the fibers and fibrils of the leather is not strictly speaking a tanning process but rather a filling or finishing encountered in will be recognized 80 sirable that the treatment with the aldehyde.
process since the hide is tanned as previously with the tanning agent. The amount of tanning agent employed and the steps of the tanning process may be the same as has previously beenthe practice with the particular type of hide to be tanned and the particular type of leather to be manufactured. The order of addition of the materials is immaterial but it is deshall take place after the leather has been tanned, at least to some extent, and the process is particularly applicable for the treatment of tanned leather. The three reactants may be add ed simultaneously but preferably the aldehyde is not added until the tanning extracts have been absorbed by the hide or leather. The ammonium salt may be added with the tanning agent, simultaneously with the aldehyde, or thereafter. The aldehyde and/or ammonium salt may be reacted with the tanning extract in the wheel, drum, temper bath, dry dip, or elsewhere in the process.
The amounts of tanning extract, aldehyde, and ammonium salt employed are not critical and depend upon the degree of improvement desired.
In general, it has been found advisable to use at least 3% to 4% of aldehyde, and about 5% of the ammonium salt on the basis of dry extract to obtain the optimum results, but additional amounts of these materials are not detrimental to the leather. As examples, the following proportions have been found to give satisfactory results:
50 cubic centimeters of 40 Twaddell clarified quebracho extract, 1 gram of ammonium chloride, and 4 cubic centimeters of commercial 40% formaldehyde solution; or 50 cubic centimeters of 40 Twaddell clarified quebracho extract, .5 grams of ammonium chloride, and 5 cubic centimeters of commercial 40% formaldehyde solution.
The following specific examples are given merely by way of illustration, and it will be obvious that many variations may be made therein without departing from the essential features of the invention.
Example I Leather is drummed in the usual manner with quebracho extract to which has been added 5% of ammonium sulphate on the dry basis.- The stock is piled down over night to absorb the load and bleached to clear the surface of the leather. It is then dipped fifteen minutes in a solution of formaldehyde containing 20% of this ingredient,
piled over night to react and fix, and then oiled off and finished in the usual manner.
Example II Rough dry leather which has had one wheel load is dry dipped in a '15 Barkometer dry dip consisting of 95 parts of clarified quebracho and 5 parts of anmionium sulphate on a dry basis. Coming from the dry dip, the leather is dipped fifteen minutes in a solution of 20% formaldehyde and is then given an oil wheel load of Ep-,
som salts, sugar, and 011, set out, and finished in accordance with the usual practice.
Example III Leather from the yard may be drummed with dipped if desired in the usual manner to give additional water soluble load, after which it is finished as usual. 1 1
In some instances, it will be found desirable to react the formaldehyde remaining in contact with 5 the leather after the completion of the reaction "with a compound capable of converting it into pound or an amonia derivative such as urea may be mentioned.
I claim: 1. The process of filling leather which comprises reacting a vegetable tanning extract, aldehyde', and an ammonium salt together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and thereon.
2. The process of filling leather which comprises reacting a vegetable tanning extract containing a catechol tannin, formaldehyde, and
an ammonium salt together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and th'ereon.
3. The process of filling leather which comprises reacting a vegetable tanning extract con- 80 taining a catechol tannin, formaldehyde, and ammonium sulphate together between and on the fibres and fibrils of leather to deposit "an insoluble material therebetween and thereon.
4. The process of filling leather which com- 86 prises reacting a vegetable tanning extract, aldehyde, and an ammonium salt together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and thereon, the aldehyde being present in the 40 neighborhood of 3% to 4% and the ammonium salt being present in the neighborhood of 5% 4 figured as ammonium sulphate and based on the dryextract.
5. The process of filling leather which oomprises reacting a vegetable tanning extract containing a catechol tannin, formaldehyde, and an ammonium salt. together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and thereon, the 60 formaldehyde being present in the neighborhood of 3% to 4% and the ammonium salt being present in the neighborhood of 5% figured as ammonium sulphate and based on the dry extract.
6. The process of filling leather which comprises reacting a vegetable tanning extract containing a catechol tannin, formaldehyde, and ammonium sulphate together between and on the fibres and fibrils of leather to deposit an insoluble material therebetween and thereon, the aldehyde being present in the neighborhood of 3% to 4% and the ammonium sulphate being present in the neighborhood of 5% based on the dry extract.
7. The process of filling leather which comprises absorbing a vegetable tanning extract between and on the fibres and fibrils of leather, and thereafter reacting an aldehyde and an ammonium salt therewith to deposit an insoluble material between and on said fibres and fibrils. 10
8. The process of filling leather which comprises absorbing a vegetable tanning extract containing a catechol tannin between and on the fibres and fibrils of leather, and thereafter reacting formaldehyde and an ammonium salt thereamazes 3 with to deposit an insoluble material between and containing the insoluble reaction product of 1 and on said fibres and fibrils. a vegetable tannin extract, an aldehyde, and an 9. Filled leather containing the insoluble reammonium salt between and on the fibres and action product of a vegetable tannin extract, an fibrils thereof.
aldehyde, and an ammonium salt between and 13. Filled leather having a degree of tannage 5 on the fibres and fibrils thereof. of at least 110 determined by the ofllcial method 10. Filled leather containing the insoluble reof the American Leather Chemists Association,
action product of a vegetable tannin extract conand containing the insoluble reaction product of taining a catechol tannin, formaldehyde, and an a vegetable tannin extract containing a catechol ammonium salt between and on the fibres and tannin, formaldehyde, and an ammonium salt be- 10 fibrils thereof. tween and on the fibres and fibrils thereof.
11. Filled leather containing the insoluble re- 14. Filled leather having a degree of tannage of action product of a vegetable tannin extract conat least 110 determined by the ofiicial method taining a catechol tannin, formaldehyde,andamof the American Leather Chemists Association, monium sulphate between and on the fibres and and containing the insoluble reaction product of i5 fibrils thereof. a vegetable tannin extract containing a catechol 12. Filled leather having a degree of tarmage tannin, formaldehyde, and ammonium sulphate of at least 110 determined by the oflicial method between and on the fibres and fibrils thereof.
of the American Leather Chemists Association, LESTER M. WHITMORE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US737290A US2018588A (en) | 1934-07-27 | 1934-07-27 | Process of filling leather and the resulting product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US737290A US2018588A (en) | 1934-07-27 | 1934-07-27 | Process of filling leather and the resulting product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2018588A true US2018588A (en) | 1935-10-22 |
Family
ID=24963316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US737290A Expired - Lifetime US2018588A (en) | 1934-07-27 | 1934-07-27 | Process of filling leather and the resulting product |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2018588A (en) |
-
1934
- 1934-07-27 US US737290A patent/US2018588A/en not_active Expired - Lifetime
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