EP3369859A1 - Fibre de soie naturelle de haute performance et son procédé de préparation - Google Patents

Fibre de soie naturelle de haute performance et son procédé de préparation Download PDF

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Publication number
EP3369859A1
EP3369859A1 EP15906939.2A EP15906939A EP3369859A1 EP 3369859 A1 EP3369859 A1 EP 3369859A1 EP 15906939 A EP15906939 A EP 15906939A EP 3369859 A1 EP3369859 A1 EP 3369859A1
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Prior art keywords
silk
acid
silk fiber
natural silk
natural
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EP15906939.2A
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German (de)
English (en)
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EP3369859A4 (fr
EP3369859B1 (fr
Inventor
Feng Zhang
Baoqi ZUO
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Nantong Textile and Silk Industrial Technology Research Institute
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Nantong Textile and Silk Industrial Technology Research Institute
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
    • 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
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • 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
    • D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • 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
    • D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • 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
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • 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
    • 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
    • D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
    • 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
    • D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/67—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 nitrogen or compounds thereof, e.g. with nitrides with cyanogen or compounds thereof, e.g. with cyanhydric acid, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid or their salts, or with cyanamides; with carbamic acid or its salts
    • 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
    • D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • 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
    • D06M11/73—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 carbon or compounds thereof
    • D06M11/76—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 carbon or compounds thereof with carbon oxides or carbonates
    • 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

Definitions

  • the invention belongs to the field of natural polymer materials, and in particular relates to a high-performance natural silk fiber and a preparation method thereof.
  • Silk is a continuous long fiber made from the coagulation of silk glands secreted from jujube when silkworm is cooked and is one of the earliest animal fibers to be used in human beings. According to different foods, silk is divided into mulberry silk, tussah silk, silk and eri silk.
  • the strands drawn from a single silkworm cocoon are called cocoon filaments, which consist of two monofilaments that are adhesively coated with sericin.
  • the silkworms of several silkworm cocoons were withdrawn, and the silks wrapped by silk adhesive were called raw silk.
  • Several raw silks are processed through the process of collateral, twisting, weaving, or weaving to become twisted or braided stitches. As a high-grade textile raw material, silk products are deeply loved by consumers at home and abroad.
  • spider silk As a non-physiological structural protein macromolecule, the mechanical properties of silk are closely related to the aggregation structure. Spider silk has particularly excellent mechanical properties, such as high strength, high modulus, high elongation, high fracture work, and has great application value and prospects in high-tech fields such as body armor and sutures. Therefore, it has become a hot topic for material scientists today. It was found that the fiber of the best mechanical property is spider silk, which is also a non-physiologically active structural protein polymer.
  • the researchers implanted genes of spider which produces spider silk into silkworm to produce silk containing spider silk protein.
  • the mechanical properties improved significantly, such as the strength increase of about 20%, the elongation rate increased by about 30%.
  • the high-performance silk fiber has broad application prospects in body armor, high-strength ultra-fine sutures, artificial ligaments, and tendons.
  • the purpose of the transgenic technology is to transform the primary structure of silk. Although progress has been made in this area, major breakthroughs have not yet been made and industrialization cannot be achieved.
  • NATURE magazine published in 2002 published the papers of Professor Shao Zhengzhong from Fudan University and Professor Vollrath from Oxford University in the UK.
  • the difference in the speed of silk threading mainly affects the molecular orientation structure and part of the crystal structure of the silk protein, resulting in a change in the mechanical properties of the silk.
  • Natural silk fiber thanks to its unique multi-level structure, has excellent mechanical properties in itself. The performance improvement based on this is the best way to prepare high-performance silk protein fibers. The results of strong spinning should be obtained as well theoretically by reorganization of the natural silk structure and further transformation of the silk by the stretching and setting process.
  • the formed natural silk fibers are mainly anti-parallel ⁇ -sheet crystal structures, and their aggregation structure is very stable, which is difficult to change, perform physical stretching post-treatment cannot be used in the prior art.
  • the natural silk is generally dissolved and then spun to obtain a product with higher performance; however, due to the irreversible destruction of the multi-stage structure of the silk by the dissolving solvent and the spinning solvent, such as a decrease in the molecular weight, disintegration of the fibril structure, etc., caused the fiber structure of regenerated silk is unstable and the mechanical properties are poor.
  • the mechanical properties of the regenerated silk fiber can be improved by post-stretching, the performance improvement is limited, not to mention that it is a fiber with better mechanical properties than the natural silk fiber. Therefore, the search for a method for reconstructing natural silk structure to obtain high-performance natural silk fibers has important value and significance for the application of silk in high-tech fields.
  • the object of the invention is to provide a high-performance natural silk fiber and a preparation method thereof.
  • the fiber is obtained by direct treatment of natural silk and has excellent mechanical properties, and can be widely used in civilian and military protection fields.
  • a method for preparing high-performance natural silk fiber is characterized by comprising the following steps:
  • the acid is one or more of formic acid, trifluoroacetic acid, acetic acid, hydrofluoric acid, phosphoric acid, and sulfuric acid; the concentration of the acid is 10% to 99% by weight.
  • the acid is one of formic acid, hydrofluoric acid, phosphoric acid, and sulfuric acid; the concentration of the acid is 25% to 98% by weight.
  • the silk swelling liquid further comprises an inorganic salt; the concentration of the inorganic salt is 0.1% to 10% by weight; the inorganic salt is one or more of sodium chloride, potassium chloride, lithium bromide, calcium chloride, zinc chloride, magnesium chloride, lithium thiocyanate, sodium thiocyanate, magnesium thiocyanate, calcium nitrate, copper nitrate, calcium carbonate, and calcium phosphate.
  • the silk swelling liquid further comprises an inorganic salt; the inorganic salt is one of the lithium bromide, calcium chloride, magnesium chloride, and lithium thiocyanate; the concentration of the inorganic salt is 0.5% to 5% by weight.
  • the silk in the invention is a natural silk, which is unregenerated treatment, and it is selected from one or more of mulberry silk, tussah silk, yamamai silk, and eri silk.
  • the natural silk fiber is one or more of silk, raw silk, twisted silk, and braided silk.
  • the shrinkage during the shrinkage is 1% to 80% and the draw-ratio during the stretching is 1.1 to 5.
  • the natural silk fiber can be stretched or shrunk while being soaked, or it can be stretched or shrunk after the natural silk fiber is soaked.
  • the shrinkage during the shrinkage is 20% to 70%; and the draw-ratio during the stretching is 1.1 to 3.2; the soaking time is 5 seconds to 5 minutes.
  • the invention performs physical stretching/shrinkage modification on natural silk fibers (including silk, raw silk, twisted silk, braided silk, etc.), breaks through the technical problem that natural silk fibers cannot be stretched, and achieves a huge leap of the mechanical properties of natural silk fibers, to meet the application requirements of silk in special areas such as body armor, artificial ligaments, and ophthalmic sutures. Therefore, the invention also discloses a high performance natural silk fiber prepared according to the above preparation method.
  • the processing method to improve the strength of natural fiber is simple and efficient, and can be directly connected with the production line of the existing product to realize large-scale production of high performance natural silk fiber. Description of the drawings
  • Table 1 shows the mechanical tensile data of mulberry silk before and after treatment. According to the technical scheme provided by the present invention, the cocoon silk after treatment has excellent ductility, and the elongation at break reaches more than 50%. Table 1 Mechanical tensile data of mulberry silk before and after processing Sample Elongation at Break (%) Fracture work (MJ/m 3 ) Original mulberry silk 21.1 64.5 Handle mulberry silk 52.3 72.8
  • FIG. 1, FIG. 2 and Table 1 are scanning electron microscope and mechanical tensile properties data of the above-mentioned high performance natural silk fiber before and after treatment.
  • the arrow of the solid line is the fiber direction.
  • the highly ordered nanofibril orientation structure inside the silk is destroyed; as can be seen from Fig. 2 , the nanofibrillar structure inside the silkworm cocoon becomes fluffy and clearly visible; the invention effectively removes the natural silk ⁇ -sheet structure, thereby greatly improving the performance of the natural silk fiber.
  • Table 1 after treatment, the elongation of natural mulberry silk is significantly increased to more than 50%, and the work of fracture is improved by about 10%.
  • Table 2 shows the mechanical tensile data of the mulberry silk before and after the treatment. According to the technical scheme provided by the present invention, the silk has excellent strength and the breaking strength reaches 900 MPa or more. Table 2 Mechanical tensile data before and after processing Sample Breaking strength (MPa) Original mulberry silk 450 Stretching mulberry silk 920
  • FIG. 3, FIG. 4 and Table 2 are the infrared spectra, Raman spectra and mechanical properties of the above-mentioned high-performance natural silk fiber before and after the treatment.
  • Fig. 3 after treatment, the crystallinity inside the silk was destroyed, which was significantly reduced compared with that before treatment.
  • Fig. 4 it can be seen that the molecular orientation degree of the silk fiber is significantly increased after stretched; this is favorable for the improvement of mechanical properties of natural silk.
  • the breaking strength of the silk was significantly improved, and the breaking strength was 800 MPa or more.
  • Table 3 shows the mechanical tensile data of the raw silk before and after the treatment. According to the technical scheme provided by the present invention, the raw silk processed has excellent ductility, the elongation at break reaches above 50%, and the work of fracture increases by about 20%. Table 3 Mechanical tensile data of raw silk before and after treatment Sample Elongation at Break (%) Fracture work (MJ/m 3 ) Original raw silk 21.1 354.2 Handle raw silk 58.5 412.8
  • Table 4 shows the mechanical tensile data of the raw silk before and after the treatment. According to the technical scheme provided by the present invention, the raw silk processed has excellent strength, and the breaking strength is more than 800 MPa. Table 4 Mechanical tensile data of raw silk before and after treatment Sample Breaking strength (cN) Raw silk 81.2 Stretching silk 105.6
  • Table 6 shows the mechanical tensile data of the tussah silk before and after the treatment. According to the technical scheme provided by the present invention, the tensile strength of the stretched tussah silk is significantly improved and reaches above 1000 MPa. Table 6 Mechanical tensile data of tussah silk before and after treatment Sample Breaking strength (MPa) Original tussah silk 430 Stretching tussah silk 1100
  • Table 7 shows the mechanical tensile data of the eri silk before and after the treatment. According to the technical scheme provided by the present invention, the breaking tussah silk filament rupture strength is significantly improved and reaches 780 MPa or more. Table 7 Mechanical tensile data of eri silk before and after treatment Sample Breaking strength (MPa) Original eri silk 463 Stretching eri silk 783
  • the concentrations in this example are all mass concentrations.
  • the present invention can modify the mechanical properties of existing natural silk fiber products (including silk, raw silk, twisted silk, and braided silk etc.) to construct a natural silk fiber with high performance and high elongation.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Husbandry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP15906939.2A 2015-10-28 2015-10-28 Fibre de soie naturelle de haute performance et son procédé de préparation Active EP3369859B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/093139 WO2017070873A1 (fr) 2015-10-28 2015-10-28 Fibre de soie naturelle de haute performance et son procédé de préparation

Publications (3)

Publication Number Publication Date
EP3369859A1 true EP3369859A1 (fr) 2018-09-05
EP3369859A4 EP3369859A4 (fr) 2019-06-19
EP3369859B1 EP3369859B1 (fr) 2023-09-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022085880A1 (fr) * 2020-10-21 2022-04-28 서울대학교산학협력단 Procédé de traitement de fibres de soie, et fibres de soie modifiées en utilisant un tel procédé

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113279282A (zh) * 2021-06-25 2021-08-20 陕西科技大学 一种蚕丝增强的芳纶纳米纤维薄膜及其制备方法
CN115354408A (zh) * 2022-08-17 2022-11-18 西南大学 一种纳米柞蚕丝纤维的制备方法、制品及应用

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
BE347870A (fr) * 1927-01-10
US2072155A (en) * 1936-02-14 1937-03-02 Warwick Chemical Co Compositions and processes for soaking silk and textile materials
GB485398A (en) * 1936-12-11 1938-05-19 Warwick Chemical Company Improvements in or relating to the soaking of natural or artificial silk
JPH01132877A (ja) * 1987-11-18 1989-05-25 Norinsuisansho Sanshi Shikenjo 絹製品の加工方法
CN101545146A (zh) * 2009-05-04 2009-09-30 西南大学 提高蚕丝纤维强度的方法
CN103469563B (zh) * 2013-09-13 2015-09-09 句容市后白镇迎瑞印花厂 一种真丝织物的精练方法
CN105256544B (zh) * 2015-10-28 2018-06-29 南通纺织丝绸产业技术研究院 一种高性能天然蚕丝纤维及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022085880A1 (fr) * 2020-10-21 2022-04-28 서울대학교산학협력단 Procédé de traitement de fibres de soie, et fibres de soie modifiées en utilisant un tel procédé
KR20220052639A (ko) * 2020-10-21 2022-04-28 서울대학교산학협력단 견사의 가공 방법 및 이를 이용하여 개질된 견사

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WO2017070873A1 (fr) 2017-05-04
EP3369859B1 (fr) 2023-09-20

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