EP0324734B1 - A process for the production of leather intended for making uppers of footwears and the product thereof - Google Patents

A process for the production of leather intended for making uppers of footwears and the product thereof Download PDF

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Publication number
EP0324734B1
EP0324734B1 EP87902692A EP87902692A EP0324734B1 EP 0324734 B1 EP0324734 B1 EP 0324734B1 EP 87902692 A EP87902692 A EP 87902692A EP 87902692 A EP87902692 A EP 87902692A EP 0324734 B1 EP0324734 B1 EP 0324734B1
Authority
EP
European Patent Office
Prior art keywords
resin
bath
skin
footwears
leather
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
Application number
EP87902692A
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German (de)
English (en)
French (fr)
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EP0324734A1 (en
Inventor
Antonio Luciani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to AT87902692T priority Critical patent/ATE62277T1/de
Publication of EP0324734A1 publication Critical patent/EP0324734A1/en
Application granted granted Critical
Publication of EP0324734B1 publication Critical patent/EP0324734B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C14C11/00—Surface finishing of leather
    • 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

Definitions

  • the present invention relates to a process for the production of leather intended for making uppers of footwears as well as to the products thereof. More particularly, the present invention relates to a process for treating wool-bearing sheep skins in order to obtain punctured or pierced leather having the compactness and strength features which are needed to employ the same for making footwear uppers having wool on their inner surface, said uppers being intended for footwears to be worn during the spring-summer period.
  • Such process distinguishes with respect to the traditional operations performed on wool-bearing sheep skins by the operations of treating said skins with acrylic and methacrylic resins respectively after the retanning and the puncturing steps.
  • Footwears are known at the present time which are suitable for hot months, more particularly for summertime, and employ pierced or punctured uppers obtained from calfskin and unlined on their inside, which uppers have the compactness and strength features required for that specific employment.
  • the present invention suggests the employment, as the raw material for making uppers of summer footwears of punctured or pierced hides obtained from wool-bearing sheep skins, which are capable because of the presence of a wool layer on their inside surface to form a coating that is suitable because of its very nature to keep a constant inner temperature as well as to assure the circulation of air so avoiding overheating of feet and hence the sweating of the same, and, because of its intrinsic antistatic character, to reduce the introduction of dust.
  • the leather suggested according to the present invention has the characteristic property of giving rise to no compression areas localized at any part of the foot so that a uniform comfort is assured and the leather in question finally shows advantageously suitabIe as a stimulator of the peripheral circulation of blood and useful as an agent capable of absorbing the electrostatic energy built up in the body.
  • the present invention suggests to perform acrylic and methacrylic resin treatment operations respectively at the end of the retanning step and after the puncturing or piercing step.
  • the basis operations of the process according to the present invention consist in the application and the subsequent two-stage polymerization of an acrylic resin inside the fibrous texture of the skin and in the application and subsequent polymerization of a methacrylic resin at points corresponding to the inner surfaces of the holes or punctures during a tanning treatment with retanning and finishing according to the procedure of the traditional type.
  • the traditional flowsheet of treatment of the skins normally provides different steps of working in a bath as well as different steps of dry working.
  • the second operation which is characteristic of the process according to the present invention is performed during the dry working, after the piercing or puncturing step and it consists in treating the exposed surface of the hide, inside the holes, with methacrylic resin in order to increase the surface strength of the hide at the points corresponding to the inner walls of the holes, so as to avoid as much as possible the risk of dilating and tearing the hide during employed.
  • a specific object of the present invention is a process for the production of leather intended for making the uppers of footwears to be worn during the spring summer period wherein the wool bearing sheep skin is bath worked and then dry worked, wherein said bath working comprises the steps of leaking, fleshing, washing, pickling, tanning, acid removing and retanning and wherein said dry working comprises a first finnishing step; a piercing or puncturing step and a second finishing step, characterized in that in the final part of the retanning step the skin are treated with an acrylic ester based resin in water solution and then said resin is made to polymerize so as to cause the original fibber lattice to become thicker and in that after said piercing or puncturing step, the skins are treated with a methacrylic resin in water solution and then said resin is polymerized at the point corresponding to the inner surface of the holes.
  • the melamine and the ureic resins also have to be excluded because of the same reason, though such resins show the advantage of giving the hides quite good properties of feel and softness.
  • the resins of the dicyandiamide type that on the contrary could give the desired properties of strength, are unsuitable to satisfy the objects of the present invention as they spoil at a remarkable extent the characteristics of the chrome tanning step and, above all the adaptability of the hides to the dyeing step.
  • the acrylic ester polymeric compound is added to a neutralization bath consisting of water at 50° C and of an acid removal agent (for instance the CORATIL ND mentioned above), in which bath the hides have been dipped and adjusted to a pH of about 6.
  • a neutralization bath consisting of water at 50° C and of an acid removal agent (for instance the CORATIL ND mentioned above), in which bath the hides have been dipped and adjusted to a pH of about 6.
  • the acrylic ester resin is added preferably to the neutralization bath after about 1 hour, after the neutralization has occurred completely, at the concentration of 7 g/l, in order to give the possibilility of penetration into the hide fibers at a larger extent at the points where the hide itself is less strong and, more precisely, in the side parts where the structure is less relaxed and the fibers are longer.
  • the acrylic ester resin after a period ranging from 30 minutes to 2 hours, when the resin itself has completely gone into the hide, is caused to polymerize first with a slight addition of formic acid, so that the resin becomes bound to the fibers of the hide, and next it is caused to polymerize a second time in the dry state direct on the hides which now are completely dry, under a pressure of 19.62 ⁇ 105 Pa (20 kg/cm2) and at a temperature of about 100-120°C for a period of 4-8 seconds.
  • the treatment with a methacrylic resin is carried out according to the procesure disclosed above
  • Preferably said treatment is performed by dipping the pierced hide into a water bath at 50-60°C in which a prepolymerized resin of methacrylic acid has been introduced (for example, DRASIL-ANG available from the Henkel Company) at the concentration of about 4-6 g/l and making the resin to polymerize definitively with the aid of the addition of formic acid for a period of about 30-45 minutes at a temperature of about 60°C.
  • a prepolymerized resin of methacrylic acid for example, DRASIL-ANG available from the Henkel Company
  • the resin becomes deposited on the surface of the pierced hide at the points corresponding to the inner walls of the holes, where the resin itself becomes absorbed by the fibers uncovered as an effect of the piercing step, so that the advantageous effect, already mentioned above, of the increase in the surface strength of the hide is obtained.
  • the object of the present invention concerns also the hides obtained by means of the process mentioned above.
  • a biological phase of the treatment comprising the soaking step, the fleshing and the washing step, a transition step consisting in the pickling operation and an anabiological step comprising the tanning, acid removal and retanning operations.
  • the dry working (B) comprises the finishing, piercing, treatment with an methacrylic polymeric compound which is a feature of the invention, and the successive finishing step.
  • Figure 2 shows an application of the leather obtained according to the present invention for the production of the upper of a footwear; the wool layer 1 can be seen on the inner side of the footwear, while the velvet leather or the napped leather 2 provided with holes 3 can be seen on the outer part of the same.
  • the specimens opportunely conditioned undergo a tensile stress to failure on a tensile test device.
  • the tensile strength is obtained dividing the breaking or failure load by the cross section area of the specimen and is given as N/mm2.
  • the ultimate elongation is calculated by the difference between the initial length of the specimen and its ultimate length. Such difference is expressed as the percentage with respect to the initial length of the specimen.
  • a rectangular specimen in which a slit has been out of the prescribed shape is hooked on the protruding ends of a pair of specimen holders fastened between the clamps of a tensile test device.
  • the maximum elongation stress required for causing said specimen holders to separate is considered as the value of the tearing strength.
  • a steel ball is pressed onto the central part of the flesh side of a leather specimen cut in the shape of a disk which is firmly fastened along its peripheral part.
  • the ball pressure and the consequent stretching of the specimen are recorded at the very moment when the leather grain becomes cracked and bursting of leather (possibly) occurs.
  • Standard procedure UNI 8433/TUP 20 _ determination of repeated employment resistance (the employment consisting in continuous folding) of light leather and leather surface sizing.
  • Such determination is performed by clamping each specimen to the two terminals of the testing apparatus.
  • One of the two clamping terminals is kept stationary while the other one is caused to oscillate with 22.5° amplitude at the frequency of 100 + 5 cycles/minute, so carrying with itself the folded specimen.
  • the specimens undergo after conditioning a tensile stress till failure on a tensile strength test machine.
  • the tensile strength is calculated by dividing the ultimate tensile load by the cross section area of the specimen and is expressed as N/mm2.
  • the ultimate elongation is obtained by calculating the difference between the initial length of the specimen and its ultimate length. Such difference is expressed as the percentage with respect to the initial length of the specimen.
  • a rectangular specimen in which a slit has been cut of the prescribed shape is hoocked on the protruding ends of a pair of specimen holders fastened between the clamps of a tensile test machine.
  • the maximum elongation load required for causing the specimen holders to separate is considered as the tearing strength.
  • a steel ball is pressed against the central part of the flesh side of a leather specimen cut in the shape of a disk and firmly fastened along its peripheral part.
  • the pressure of the steel ball and the stretching of the specimen are recorded at the very moment when the leather grain becomes cracked and the bursting (possibly) occurs.
  • Such determination is carried out by fastening each specimen to the two clamps of the testing apparatus.
  • One of the two clamps is kept stationary whereas the other one is made to oscillate with amplitude of 22.5° at the frequency of 100 ⁇ 5 cycles/minute so carrying with itself the folded leather specimen.

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  • 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)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
EP87902692A 1986-11-18 1987-04-13 A process for the production of leather intended for making uppers of footwears and the product thereof Expired - Lifetime EP0324734B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87902692T ATE62277T1 (de) 1986-11-18 1987-04-13 Verfahren zur herstellung von schuhoberleder und produkt daraus.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT48666/86A IT1199294B (it) 1986-11-18 1986-11-18 Procedimento per la produzione di pelli destinate alla fabbricazione di tomaie per calzature e relativo prodotto
IT4866686 1986-11-18

Publications (2)

Publication Number Publication Date
EP0324734A1 EP0324734A1 (en) 1989-07-26
EP0324734B1 true EP0324734B1 (en) 1991-04-03

Family

ID=11267929

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87902692A Expired - Lifetime EP0324734B1 (en) 1986-11-18 1987-04-13 A process for the production of leather intended for making uppers of footwears and the product thereof

Country Status (22)

Country Link
EP (1) EP0324734B1 (enrdf_load_stackoverflow)
JP (1) JPH02500444A (enrdf_load_stackoverflow)
KR (1) KR890700169A (enrdf_load_stackoverflow)
CN (1) CN1013205B (enrdf_load_stackoverflow)
AU (1) AU606059B2 (enrdf_load_stackoverflow)
BG (1) BG50390A3 (enrdf_load_stackoverflow)
CS (1) CS275887B6 (enrdf_load_stackoverflow)
DD (1) DD279691A5 (enrdf_load_stackoverflow)
FI (1) FI892363A0 (enrdf_load_stackoverflow)
HU (1) HU203386B (enrdf_load_stackoverflow)
IL (1) IL84437A (enrdf_load_stackoverflow)
IT (1) IT1199294B (enrdf_load_stackoverflow)
MA (1) MA21110A1 (enrdf_load_stackoverflow)
NZ (1) NZ222559A (enrdf_load_stackoverflow)
PL (1) PL156512B1 (enrdf_load_stackoverflow)
PT (1) PT86161B (enrdf_load_stackoverflow)
RO (1) RO103963B1 (enrdf_load_stackoverflow)
RU (1) RU1777608C (enrdf_load_stackoverflow)
TR (1) TR23044A (enrdf_load_stackoverflow)
WO (1) WO1988003958A1 (enrdf_load_stackoverflow)
YU (1) YU209087A (enrdf_load_stackoverflow)
ZA (1) ZA878523B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103866053A (zh) * 2014-04-02 2014-06-18 宁夏盐池美雅滩羊裘皮有限公司 一种无盐鞣制滩羊二毛裘皮的工艺

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5172228B2 (ja) 2007-06-28 2013-03-27 ミドリホクヨー株式会社 革
JP5272478B2 (ja) * 2008-04-02 2013-08-28 トヨタ紡織株式会社 皮革の孔開け加工方法
RU2494151C2 (ru) * 2008-05-16 2013-09-27 Мидори Хокуйо Ко., Лтд. Верхнее покрытие
CN105296690B (zh) * 2013-10-21 2018-06-22 晋江市香江皮革有限公司 一种耐曲折皮革的生产方法
KR101686896B1 (ko) * 2016-08-31 2016-12-15 허민수 양모섬유를 이용한 신발 및 신발의 제조에 이용되는 갑피의 제조방법
CN119144772A (zh) * 2024-11-14 2024-12-17 德州兴隆皮革制品有限公司 一种带有通风功能的沙发革及制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843320A (en) * 1972-05-31 1974-10-22 Us Agriculture Graft polymerization of vinyl monomers onto chrome-tanned hides and skins

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843320A (en) * 1972-05-31 1974-10-22 Us Agriculture Graft polymerization of vinyl monomers onto chrome-tanned hides and skins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
US, A, 3843320 (S.H. Feairheller et al.) 22 October 1974 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103866053A (zh) * 2014-04-02 2014-06-18 宁夏盐池美雅滩羊裘皮有限公司 一种无盐鞣制滩羊二毛裘皮的工艺
CN103866053B (zh) * 2014-04-02 2015-09-30 宁夏盐池美雅滩羊裘皮有限公司 一种鞣制滩羊二毛裘皮的工艺

Also Published As

Publication number Publication date
JPH02500444A (ja) 1990-02-15
ZA878523B (en) 1988-10-26
TR23044A (tr) 1989-02-13
YU209087A (en) 1988-12-31
PL156512B1 (en) 1992-03-31
FI892363L (fi) 1989-05-17
FI892363A7 (fi) 1989-05-17
CS275887B6 (en) 1992-03-18
AU7302587A (en) 1988-06-16
IL84437A (en) 1991-05-12
IT1199294B (it) 1988-12-30
KR890700169A (ko) 1989-03-10
HUT50362A (en) 1990-01-29
BG50390A3 (bg) 1992-07-15
IL84437A0 (en) 1988-04-29
WO1988003958A1 (en) 1988-06-02
EP0324734A1 (en) 1989-07-26
NZ222559A (en) 1990-01-29
DD279691A5 (de) 1990-06-13
AU606059B2 (en) 1991-01-31
HU203386B (en) 1991-07-29
IT8648666A0 (it) 1986-11-18
PL268885A1 (en) 1988-08-18
PT86161B (pt) 1990-11-20
RO103963B1 (en) 1993-12-22
RU1777608C (ru) 1992-11-23
MA21110A1 (fr) 1988-07-01
CN87107924A (zh) 1988-06-01
PT86161A (en) 1987-12-01
JPH0569879B2 (enrdf_load_stackoverflow) 1993-10-01
CN1013205B (zh) 1991-07-17
FI892363A0 (fi) 1989-05-17

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