WO2019119009A1 - Procédé de fabrication d'un succédané de cuir - Google Patents

Procédé de fabrication d'un succédané de cuir Download PDF

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Publication number
WO2019119009A1
WO2019119009A1 PCT/AT2018/060309 AT2018060309W WO2019119009A1 WO 2019119009 A1 WO2019119009 A1 WO 2019119009A1 AT 2018060309 W AT2018060309 W AT 2018060309W WO 2019119009 A1 WO2019119009 A1 WO 2019119009A1
Authority
WO
WIPO (PCT)
Prior art keywords
wool
keratin
cwet
leather
leather substitute
Prior art date
Application number
PCT/AT2018/060309
Other languages
German (de)
English (en)
Inventor
Thomas Bechtold
Christa Fitz-Binder
Markus Krüger
Original Assignee
Universität Innsbruck
Schoeller Gmbh & Co Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universität Innsbruck, Schoeller Gmbh & Co Kg filed Critical Universität Innsbruck
Priority to EP18829188.4A priority Critical patent/EP3728724A1/fr
Publication of WO2019119009A1 publication Critical patent/WO2019119009A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic System
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/06—Animal fibres, e.g. hair, wool, silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/02—Natural macromolecular compounds or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • the invention relates to a method for producing a leather substitute and to a leather substitute produced by this method.
  • leather or imitation leather products are used in many fields, such as used as clothing or for the interior. While genuine leather is a natural product that has many excellent properties, there are ethical concerns associated with the rearing and killing of animals to obtain leather. For artificial leather, plastics such as PVC are used, which are also of concern for environmental protection. Also, the properties in terms of moisture absorption, comfort or stability of such artificial leather are not comparable with natural leather. Finally, there are reservations about wearing synthetic, PVC-based artificial leather.
  • the object of the present invention is therefore to provide a leather substitute which has comparable properties to genuine leather and is ethically harmless.
  • the swelling agent is a mixture of calcium chloride, water, ethanol.
  • the swelling of the Keratins from the wool In the treatment of wool with a mixture of swelling agents, in particular a mixture of calcium chloride, water and ethanol, the swelling of the Keratins from the wool.
  • the addition of the reducing agent results in disruption of intra- and intermolecular disulfide bonds between the -SH groups of the cysteine residues of keratin.
  • the regeneration of the keratin is preferably carried out by adding water so that the dissolved keratin protein forms again as a solid. By appropriate shaping, the keratin can be brought into the desired shape.
  • the molar mixture between calcium chloride: water: ethanol (CWE) is preferably between 1 (CaCL): 5 to 7 (water): 1 to 3 (ethanol), preferably about 1: 6: 2.
  • An alternative mixture as swelling agent includes LiBr and urea.
  • Suitable reducing agents are all reducing agents in question, which disulfide bridges can break open.
  • the reducing agent may have an -SH group.
  • it is mercaptoacetic acid or a salt thereof (thiol glycolate).
  • a filtration step may be provided to separate insoluble matter.
  • the undissolved part of the wool can then form a matrix for the leather substitute.
  • the matrix may be obtained by suitable arrangement of the fibers of the wool, e.g. by crossing the fibers, give a corresponding stability.
  • a non-wool matrix may also be used (eg, a fabric or the like).
  • the non-wool matrix is incorporated into the composite.
  • the matrix may be a nonwoven, a cloth, a woven fabric, a knit or a sheet.
  • a fiber mixture may be present.
  • an oxidation step is provided with or after the regeneration. This serves to form the free -SH groups in the regenerated keratin again -S-S-disulfide bridges.
  • the oxidation can be carried out by atmospheric oxygen or by the addition of an oxidizing agent.
  • the invention also relates to a leather substitute obtainable by the aforementioned method.
  • the invention relates to a leather substitute comprising regenerated keratin of wool.
  • the leather substitute may comprise a matrix of wool, wherein the matrix is embedded in the regenerated keratin.
  • the leather substitute may alternatively or in combination have a non-wool matrix embedded in the regenerated keratin.
  • a plasticizer is preferably added to make the leather substitute supple.
  • the plasticizer may e.g. Glycerol and / or oils.
  • a synergistic mixture of CWE and a reducing agent such as thioglycolic acid (CWET) is suitable for the dissolution of wool keratin and allows regeneration and shaping the production of an all-keratin composite.
  • the dissolution of wool in the system CWE and thioglycolic acid was characterized as a function of pH, temperature and time.
  • Regenerated keratin was characterized by FTIR spectroscopy and water sorption properties.
  • the process of dissolution and regeneration was then used in combination with wool fibers to produce all-keratin composites characterized by laser scanning microscopy, FTIR and mechanical properties, moisture sorption and water uptake.
  • thioglycolic acid > 98% wt, Merck Schuchhardt OHG, Hohenbrunn, Germany
  • CaCl 2 ⁇ 2H 2 O > 99% by weight
  • bromothymol blue and ethanol > 99.9% by weight, Merck Darmstadt, Germany
  • calcium thioglycolate trihydrate > 98% by weight
  • ammonium thioglycolate about 60% by weight.
  • a light microscope CX41, Olympus, Tokyo, Japan
  • a 3D laser scanning confocal microscope VK-X200 Keyence, Osaka, Japan
  • Infrared spectra were recorded by attenuated total reflection (ATR) with an FTIR spectrometer (Bruker Vector 22 FTIR spectrometer, Spectra I range 4000 to 400 cm -1 ) equipped with a diamond crystal unit.
  • the redox potential was measured with a Pt electrode and an Ag / AgCl, 3 M KCl reference electrode (Sen Tix ORP 3M KCl, WTW, Weilheim, Germany).
  • a ferrocyanide redox buffer was prepared (0.528 g K4 [Fe (CN) e], 0.411 g of K 3 [Fe (CN) 6], 0.180 g KH 2 P0 4, 0.390 g Na 2 hPoE 4 in 100 ml).
  • Solvent system stability in the presence of wool 100 ml of CWE thioglycolic acid solvent CWET (37.3 g CaCl 2 -2H 2 O, 27.4 g H2O, 23.4 g ethanol, 2 ml color indicator (bromothymol blue solution, 0.1 g per 100 ml), 4 ml of thiogylic acid) were heated to 40 ° C or 60 ° C. The pH was adjusted to pH 7 ⁇ 0.3 by addition of NH 3 and 0.5 g of wool was added to the solvent. The pH and redox potential were measured at regular intervals for a period of 90 minutes.
  • CWE thioglycolic acid solvent CWET 37.3 g CaCl 2 -2H 2 O, 27.4 g H2O, 23.4 g ethanol, 2 ml color indicator (bromothymol blue solution, 0.1 g per 100 ml), 4 ml of thiogylic acid) were heated to 40 ° C or 60
  • the soluble protein was determined by photometry using Coomassie Blue G-250 staining.
  • the Coomassie Blue G-250 reagent solution was prepared by dissolving 100 mg of dye in 50 ml of ethanol (95% by weight). After adding 100 ml of H 3 PO 4 (85 w / v%), the solution was filtered through a Whatman # 1 paper filter. To analyze the protein content remaining in solution, 0.5 g of a CWET wool blend was diluted with 50 ml of deionized water and filtered to remove precipitated keratin. A volume of 10 ml of filtrate was then diluted to 50 ml with water and 1 ml of this solution was mixed with 1 ml of Coomassie's reagent. The absorbance was measured at 595 nm. Freshly prepared CWET solution was used to make a blank.
  • a mass of 0.5 g wool was treated in 20 ml CWET and samples were taken at defined times up to a maximum duration of 3 hours. Comparative experiments were carried out in which the addition of thiogylciolic acid was carried out after a pre-swelling in CWE for 3 hours and in a second batch the amount of thioglycolic acid in CWET was doubled. The results are given as an average for a double determination.
  • Woolen fiber tape (2.0 to 4.3 g) was placed in a PE plastic bag and a volume of 5 to 20 ml of CWET was added. The sample bag was then placed in another bag to avoid the release of solvent and to reduce the access of atmospheric oxygen. To aid penetration of the solvent into the wool fiber tape, the sample was squeezed three times with a laboratory float (0.5 m min -1 , 3 bar). The solvent / wool samples were compressed in a laboratory press (Serivtec, Polystat 200 T) for 10 to 20 minutes at 60 ° C. and 10 bar. After pressing, the samples were removed from the bag and rinsed in excess water to coagulate dissolved keratin and remove the solvent. The wet samples were then fixed between absorbent soft paper and dried at room temperature overnight.
  • Tensile strength and elongation at break were determined with a universal testing machine (Instron Universal Tester, Instron, Norwood, USA). The composite materials were used to produce samples measuring 4 cm in length and 1 cm in width. Tensile strength experiments were performed at a rate of 1 cm min -1 , with no bias (tests were performed at least as a duplicate). The thickness of the samples was measured by means of a sliding caliper. Results and discussion
  • the potentiometric titration of the CWET was performed to examine the interaction between the pH of the solutions and the reduction potential of thioglycolic acid and to analyze the sensitivity of the solvent to oxidation.
  • reductive cleavage of the disulfide groups of keratin is initiated.
  • a solution of bromothymol blue as a color indicator was added to the CWET solvent. The color of bromothymol blue changes from yellow to blue at the pH interval of 5.8-7.6, so that green color was used to indicate a near neutral solvent pH of 6-7.
  • Fig. 1 shows the regeneration of keratin as a function of dissolution time.
  • Figure 2 shows FITR spectra of untreated wool, CWET after 1 h and
  • Fig. 3 shows WRV and MC in composites as a function of the mass of CWET used per 1 g of wool.
  • FIG. 4 shows FTIR-ATR spectra of keratin composites and wool in FIG.
  • Fig. 6 shows a microphotograph of a composite with glycerol as
  • Fig. 7 shows a microphotograph of a composite with oil as a plasticizer
  • Fig. 8 shows a microphotograph of a composite with oil as a plasticizer
  • the amount of unresolved fiber components decreases with the treatment time to less than 20%, but no further increase in the regenerated keratin is observed after 3-4 hours, with a maximum of dissolved and regenerated keratin reaching 50-55% of the total weight of the wool becomes.
  • the amount of non-regenerable protein remains below 20% of the total mass of the wool fiber and begins to increase after 4 hours of treatment, indicating the tendency for hydrolytic degradation of keratin in CWET.
  • the protein staining assay with Coomassie Blue G-250 was used as a soluble material during regeneration for further analysis of protein losses.
  • relative protein content as a function of treatment time in CWET was investigated.
  • experiments with 3 hours of previous swelling in CWE and double-amount of thioglycolic acid experiment are also shown.
  • the FTIR analysis of the regenerates and insoluble parts was performed to examine possible changes in protein structure during the dissolution experiments and to identify differences between the regenerated keratin and the insoluble parts of the wool sample.
  • the FTIR spectrum of the untreated wool is also shown ( Figure 2).
  • an offset in the direction of the y-axis was performed.
  • the FTIR spectra show no significant changes between the untreated wool and the regenerates. Even after a 20-hour treatment in CWET, only minor differences between the wool fibers and the undissolved parts are detectable. The reasons for the observed incomplete dissolution of wool are still unclear. Saturation effects can be excluded since the insoluble part of the wool fibers is independent of the wool to be dissolved and the dissolution time.
  • the coagulated keratin serves as a binder between the wool fibers and an all-keratin composite is obtained.
  • the mass of the CWET used was varied with respect to the wool fibers and the time of solidification under pressure to identify the particular impact on the physical properties of the composite (Table 1).
  • samples were also made with 90 ° crossed fiber direction. The samples were characterized by laser scanning microscopy and in terms of physical strength and elongation. Keratin composite FTIR spectra, moisture sorption, and water retention value were also recorded.
  • a special feature of keratin-based material is the ability to absorb significant amounts of moisture and swell in water. Thus, possible changes in moisture sorption and water retention value were analyzed.
  • the WRV is an indicator of liquid water that is stored in heavily swollen parts of the material.
  • the results show a significant increase in water retention value (WRV) despite the fact that the untreated wool fibers were centrifuged at lower centrifugal force.
  • WRV water retention value
  • For the wool reference fibers a value of about 37.9 ⁇ 1.1% was found, which after treatment in CWET increases to 54 - 70%. This can be explained by a higher amount of small pores that can collect liquid water and with higher swelling of the more accessible keratin structure.
  • the higher accessibility of the structure also results in increased moisture sorption under standard climate conditions (20 ° C 65% RH).
  • FTIR-ATR spectra of the keratin composites were performed to identify possible changes in the chemical structure of keratin ( Figure 4).
  • Figure 4 the FTIR-ATR spectrum of the untreated wool is also shown. It No significant difference in spectra was observed with respect to the appearance of peaks or a significant shift in extinction.
  • the dissolution of wool fibers was achieved in a concentrated CaCl / water / ethanol solution containing thioglycolic acid at neutral pH. Similar to the dissolution of fibroin in Ajisawa's reagent, the concentrated saline solution stabilizes the solubilized protein by forming an ion-rich hydration layer and interacting with charged and polar groups of keratin. The presence of thioglycic acid is required to cleave the disulfide bonds present in wool. Redox potential measurements showed sufficient stability of the solvent to oxidative effects for the duration of the dissolution experiment.
  • a total of 50% of the wool fibers are dissolved after 3 hours of treatment at 60 ° C, regardless of the amount of wool, with a share of 30% of the wool fibers has remained as an insoluble residue. Dilution of the keratin solution with water results in protein regeneration, however, 20% most likely remained in solution with lower molecular weight proteins.
  • an all-keratin composite can be obtained by consolidation under pressure.
  • the composite materials are built up as a combination of regenerated keratin and insoluble wool fibers.
  • FTIR analysis indicates that no significant changes in protein occurred, a significant increase in water retention and moisture sorption was observed, which can be explained by the highly porous structure of the composite and the increased surface area of regenerated keratin.
  • the technique indicates a new method of shaping 100% keratin-based material, both as a sustainable biodegradable material and as a material with potentially high biocompatibility for medical applications, such as scaffolds and implants.
  • wool fleeces or fabrics are compacted with a solvent or swelling agent at 60 ° C. under 10 bar pressure in a heatable press.
  • the mixture is pressed through a roller squeezing in the goods, then compressed for 20 min at 60 ° C and 10 bar pressure.
  • the parts are washed out with water and treated in different ways with softening substances.
  • glycerol or oils e.g., WD-40
  • the application can take place after drying or already in the wet state.
  • the samples were cut into 1 cm strips and conditioned in normal climate (20 ° C., 65% relative humidity). The clamping length was 20mm.
  • the following table summarizes the results of the tensile tests.
  • the aftertreatment processes with glycerin in the wet state, or with oil (WD 40) in the dried state allow the production of a leathery state.
  • leather-like composites can be produced by compaction of worsted material with woolen fabrics.
  • the pattern is then divided and treated with the softening agents as in Application Example 1, a leathery character is achieved.
  • the composite material has a brittle and hard character.

Abstract

L'invention concerne un procédé de fabrication d'un succénadé de cuir, comprenant les étapes suivantes : traitement de la laine dans un mélange qui comprend du chlorure de calcium, de l'eau, de l'éthanol et un agent de réduction et qui présente un pH compris entre 6 et 8, au moins une partie de la kératine de la laine étant dissoute ; régénération de la kératine par ajout d'un excédent d'eau ; mise en forme de la kératine jusqu'à obtention de la forme souhaitée.
PCT/AT2018/060309 2017-12-19 2018-12-19 Procédé de fabrication d'un succédané de cuir WO2019119009A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18829188.4A EP3728724A1 (fr) 2017-12-19 2018-12-19 Procédé de fabrication d'un succédané de cuir

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA51050/2017A AT520764B1 (de) 2017-12-19 2017-12-19 Verfahren zur Herstellung eines Lederersatzstoffes
ATA51050/2017 2017-12-19

Publications (1)

Publication Number Publication Date
WO2019119009A1 true WO2019119009A1 (fr) 2019-06-27

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Application Number Title Priority Date Filing Date
PCT/AT2018/060309 WO2019119009A1 (fr) 2017-12-19 2018-12-19 Procédé de fabrication d'un succédané de cuir

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AT (1) AT520764B1 (fr)
WO (1) WO2019119009A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE373201C (de) * 1920-05-11 1923-04-09 Leo Grossmann Verfahren zur Herstellung von kuenstlichem Leder
JPH04281856A (ja) * 1991-03-11 1992-10-07 Ajinomoto Takara Corp:Kk ケラチン微細粉末の製造方法
JPH04339827A (ja) * 1991-05-16 1992-11-26 Fujikoo:Kk 蛋白含有廃棄物からケラチン部分分解物の析出方法
JPH11217506A (ja) * 1998-02-04 1999-08-10 Idemitsu Petrochem Co Ltd シルク含有溶液、シルク含有樹脂組成物、シルク含有成形品及びシルク含有溶液の調製方法
JP2004161907A (ja) * 2002-11-13 2004-06-10 Nagoya City ケラチンブレンドポリマー

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Publication number Priority date Publication date Assignee Title
US2436156A (en) * 1943-08-19 1948-02-17 Du Pont Preparation of shaped objects, filaments, and the like
JP2527120B2 (ja) * 1992-12-24 1996-08-21 共栄社化学株式会社 硬ケラチン物質粉末の製造方法
CN1435516A (zh) * 2002-12-12 2003-08-13 内蒙古鄂尔多斯羊绒集团有限责任公司 一种再生角蛋白功能纤维的加工技术

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE373201C (de) * 1920-05-11 1923-04-09 Leo Grossmann Verfahren zur Herstellung von kuenstlichem Leder
JPH04281856A (ja) * 1991-03-11 1992-10-07 Ajinomoto Takara Corp:Kk ケラチン微細粉末の製造方法
JPH04339827A (ja) * 1991-05-16 1992-11-26 Fujikoo:Kk 蛋白含有廃棄物からケラチン部分分解物の析出方法
JPH11217506A (ja) * 1998-02-04 1999-08-10 Idemitsu Petrochem Co Ltd シルク含有溶液、シルク含有樹脂組成物、シルク含有成形品及びシルク含有溶液の調製方法
JP2004161907A (ja) * 2002-11-13 2004-06-10 Nagoya City ケラチンブレンドポリマー

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HA-THANH NGO ET AL: "Sorption behavior of reactive dyed labelled fibroin on fibrous substrates", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 133, no. 35, 24 May 2016 (2016-05-24), US, XP055560690, ISSN: 0021-8995, DOI: 10.1002/app.43880 *

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EP3728724A1 (fr) 2020-10-28
AT520764A1 (de) 2019-07-15
AT520764B1 (de) 2021-12-15

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