EP0964085B1 - Modifizierte seidenmaterialen und herstellungsverfahren - Google Patents

Modifizierte seidenmaterialen und herstellungsverfahren Download PDF

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Publication number
EP0964085B1
EP0964085B1 EP98961455A EP98961455A EP0964085B1 EP 0964085 B1 EP0964085 B1 EP 0964085B1 EP 98961455 A EP98961455 A EP 98961455A EP 98961455 A EP98961455 A EP 98961455A EP 0964085 B1 EP0964085 B1 EP 0964085B1
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EP
European Patent Office
Prior art keywords
silk
denatured
degummed
heat
mixture
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
EP98961455A
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English (en)
French (fr)
Other versions
EP0964085A4 (de
EP0964085A1 (de
Inventor
Kozo Tsubouchi
Shoko Eaudeleman Co. Ltd. FUJIURA
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.)
National Institute of Agrobiological Sciences
Eaudeleman Co Ltd
Original Assignee
National Institute of Agrobiological Sciences
Eaudeleman Co Ltd
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
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Publication of EP0964085A1 publication Critical patent/EP0964085A1/de
Publication of EP0964085A4 publication Critical patent/EP0964085A4/de
Application granted granted Critical
Publication of EP0964085B1 publication Critical patent/EP0964085B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01B—MECHANICAL TREATMENT OF NATURAL FIBROUS OR FILAMENTARY MATERIAL TO OBTAIN FIBRES OF FILAMENTS, e.g. FOR SPINNING
    • D01B7/00—Obtaining silk fibres or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising

Definitions

  • the present invention relates to a variously useful denatured silk material obtained by heat-treating silk in a gas flow.
  • the silk material of the present invention can be used for a purpose as a raw material of an outer skin coating product for human use such as outer skin preparations, non-medical skin agents andbeauty products or as a medical material, for a purpose as a plant growth promoter, or for other purposes such as an absorbent, a filter material and an abrasive material.
  • a raw material of outer skin coating products such as an eyebrow pencil and a hair dye has conventionally prepared by heat treatment of organic materials and, in particular, by incomplete combustion of petroleum materials.
  • Carbonized materials obtained by heat treatment of plants are used as an absorbent and a filter material.
  • JP-A No. 8-59,219 An example of such a material other than petroleum products is described in JP-A No. 8-59,219 in which silk is subjected to heat treatment to prepare a carbonized product useful as an outer skin coating product or a filter material.
  • the above mentioned heat treatment of silk is conducted in an inert gas atmosphere at a temperature of 600 to 2,000 °C.
  • the heat treatment temperature of 600 °C or higher is selected to accomplish carbonization.
  • a carcinogenic substance such as benzopyrene
  • silk as a raw material is changed to a state of tar due to wax, etc. contained therein, which provides a carbonized product without yielding fine particle or granular products sufficiently useful for practical use.
  • the heat treatment temperature is limited up to 2,000 °C from a viewpoint of industrial cost-performance so as not to increase energy consumption at higher temperatures.
  • the raw material is excessively carbonized by the heat treatment so that a range of application thereof is limited to an extreme.
  • Tsukada et al. compare in "Structural Changes of Silk Fibers Induced by Heat Treatment", Journal of Applied Polymer Science 46 (1992) December 15, pages 1945-1953, the physical properties of silk from two different species, Bombix, mori (domestic) and Antheraea pernyi (wild).
  • the present invention is achieved in the technical background as described above.
  • Another object of the present invention is to provide an incompletely carbonized product (or denatured silk) useful for various purposes because of both inherent and carbonized properties thereof by heat-treating silk as a raw material under a mild condition so as to control an extent of carbonization.
  • Still another object of the present invention is to provide an industrially practical method for preparing a denatured silk material by controlling a cost of energy consumption due to heat treatment.
  • the present invention is achieved on the basis of the above mentioned information and, as will be described in the following, provides a method for preparing a denatured silk material by heat-treating silk under a specific condition, and a denatured silk material used for purposes as an outer skin coating product for human body, a medical material, a plant growth promoter an absorbent, a filter material and an abrasive material.
  • a method of preparing a denatured silk material of various colors by heat-treating natural silk, half-degummed silk or degummed silk or a mixture thereof in an atmosphere of air flow under 0.5 to 1.5 atmospheres at a temperature of 150. to 500 °C for a certain period of time.
  • atmosphere of inert gas flow selected independently from nitrogen, helium, neon, argon, krypton and xenon or mixture thereof under 0.5 to 1.5 atmospheres at a temperature of 150 to 500°C for a certain period of time.
  • a denatured silk material of various colors by heat-treating natural silk, half-degummed silk or degummed silk or a mixture thereof in an atmosphere of air flow under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 °C for a certain period of time.
  • a denatured silk material of various colors by heat-treating natural silk, half-degummed silk or degummed silk or a mixture thereof in an atmosphere of inert gas flow selected independently from nitrogen, helium, neon, argon, krypton and xenon or mixture thereof under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 °C for a certain period of time.
  • atmosphere of inert gas flow selected independently from nitrogen, helium, neon, argon, krypton and xenon or mixture thereof under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 °C for a certain period of time.
  • the outer skin coating product for human use is a medical material for outer skin, non-medical material for outer skin or beauty products.
  • denatured silk material described in any of the above item (7) to (10) wherein the denatured silk material is used for a purpose as a plant growth promoter.
  • denatured silk material described in any of the above item (7) to (10) wherein the denatured silk material is used for a purpose as an absorbent or a filter material.
  • a starting material of denatured silk material of the present invention includes natural silk, half-degummed silk, degummed silk or a mixture thereof.
  • the silk material is in the form of a powder, fiber, yarn, (such as knitted goods, woven and nonwoven fabrics,) braiding, or a mixture thereof.
  • silk is a generic term including cocoon yarn, raw silk, and silk thread and, for example, cocoon yarn comprises protein containing, about 28% of sericin which wraps up fibroin.
  • degummed silk used herein means those materials which are treated with hot water containing soap, surfactants such as an enzyme activator, or alkaline substances such as sodium carbonate, sodium, silicate, etc. (so-called “alkaline degumming”), treated with warm water containing enzymes such as chimotrypsin, alkalase, papain, etc. (so-called “enzyme degumming”), and biologically treated with microorganisms (so-called “biological degumming”) to remove sericin along with wax and inorganic substances.
  • alkaline degumming treated with warm water containing enzymes such as chimotrypsin, alkalase, papain, etc.
  • enzyme degumming enzymes
  • biological degumming biologically treated with microorganisms
  • natural silk used herein means those materials which are not degummed.
  • half-degummed silk means intermediate materials between degummed and natural silk which generally contain less than 15 % of sericin.
  • such a heat treatment is conducted at a temperature in the range of 150 to 500 °C.
  • the heat treatment can be conducted without residual impurities in a denatured silk material.
  • the denatured silk material thus heat-treated is dry enough to yield fine particle or granular products with ease.
  • the starting silk material can be heated stably and effectively in the range of atmosphere described above.
  • the denatured silk materials of fine particle or granular form is easily obtained by mechanically grinding the starting silk material in the form of film or fabric because tensile strength thereof is extremely decreased by the heat treatment.
  • the denatured silk material of the present invention changes colors thereof starting from white to pale yellow, yellow, brown, olive brown, blue, purple, brownish black and finally to black in order depending on an extent of the heat treatment. Accordingly, the denatured silk material in a powdery state, for example, is used as a basic material of outer skin coating products for human use such as foundation cream, an eyebrow pencil, hair dye, cheek rouge, manicure, lipstick, eye shadow, etc.
  • the heat treatment may be quickly terminated when a desired color appears, which provides the denatured silk material of various colors.
  • the heat treatment can be easily terminated at a temperature of 500 °C or less in the heating atmosphere.
  • the denatured silk material thus prepared assumes various colors depending on an amount of uncarbonized (silk) residue, which varies due to the extent of carbonization, and also partially possesses a biocompatible function intrinsic to silk.
  • the denatured silk material of the present invention positively exhibits both properties of carbonized substance and silk itself, which makes it possible to widen an applicability thereof for various purposes.
  • the present silk material may be used not only for purposes as a medical material and outer skin coating products for human use which are direct in contact with skins but also for purposes as a plant growth promoter, absorbent, filter material, abrasive material, etc.
  • the starting silk material of the present invention may be in the form of a film, powder, fiber, yarn, fabric (such as knitted goods, woven and nonwoven fabrics), braiding or mixture thereof.
  • the denatured silk material may be used as it is.
  • the thus formed product is quite suitable as a material of improved absorbing properties, because such a product has a larger surface area per unit volume due to characteristic three-dimensional twist structure of fabric fibers.
  • the denatured silk material of the present invention may be mechanically ground to form a powder having particle size of 0.01 to 10 micron.
  • the denature silk material having particle size less than 0.01 micron is costly to produce and, in addition, not necessarily fine for practical use.
  • Particles of 10 micron or more are generally hard to aggregate because of larger particle size so that the denature silk material does not sufficiently get to fit skins than expected or exhibits a sense of incompatibility toward skins for certain purposes thereof to be use.
  • preferable particle size is 0.01 to 20 mm.
  • a denature silk material useful for various purposes because of both inherent and carbonized properties thereof by heat-treating silk as a raw material under a mild condition, i.e., in a gas flow of 0.5 to 1.5 atmospheres at a temperature of 150. to 500 °C so as to control an extent of carbonization.
  • the heat treatment in a gas flow under 0.5 to 1.5 atmospheres allows to remove volatile components caused by heat decomposition of silk out of the reaction system by the gas flow without forming conventional tar-like products.
  • waste of silk products may also beused as the starting material.
  • crystalline silk powder similar one as described in Japanese Registered Patent No. 2,615,440 was charged in a horizontal glass tube, which was then horizontally placed in an electric furnace, [available from Shinyo Rikagaku Kizai Co., Ltd as Model KP-7] to subject the crystalline silk powder to a heat treatment by heating from room temperature at a heating rate of 10 °C / min. while flowing nitrogen gas from one end of the glass tube to the other so as to keep a gas pressure of 1 ⁇ 0.1 atm.
  • Raw silk was soaked in a 0.1 %-aqueous solution of sodium carbonate having a bath ratio of 1 : 50, boiled therein for one hour followed by further boiling in renewed aqueous sodium carbonate for additional one hour, washed with water and dried to yield silk yarn (fibroin fiber).
  • the silk yarn was then burned by heating using the apparatus in the example 1, i. e., in the electric furnace at 280 °C in an argon atmosphere at a gas pressure of about 0.5 atm. for 3 minutes, the silk yarn was partially carbonized to yield a reddish dark brown burned product or denatured silk material which partially exhibited properties of silk protein.
  • the thus denatured silk material was ground by means of a microjet grinder [available from Hosokawa Micron Co., Ltd.] followed by classification to yield particles having particle size of about 5 micron.
  • Results obtained were shown in the attached Tables 2 to 4. under an air flow of 1 atm. at a predetermined temperature of 170 °C time period 1 ⁇ 2 hours 2 ⁇ 5 hours 10 ⁇ 20 hours color of silk fabric pale yellow yellow brown under an air flow of 1 atm. at a predetermined temperature of 250 °C time period 0.3 ⁇ 2 minutes 8 ⁇ 20 minutes 0.5 ⁇ 1 hour 0.5 ⁇ 3 hours 4 ⁇ 6 hours more than 7 hours color of silk fabric pale yellow brown reddish dark brown purply brown blackish brown black under an air flow of 1 atm. at a predetermined temperature of 320 °C time period 20 ⁇ 40 seconds 1 ⁇ 2 minutes 2.5 ⁇ 4 minutes 5 ⁇ 10 minutes more than 13 minutes color of silk fabric brown reddish dark brown pale dark brown dark brown black
  • the thus heat-treated silk fabric especially those materials which were colored brown or darker colors than reddish dark brown, can be mechanically ground with ease, for example, by means a microjet grinder to yield colored silk powders.
  • Example 1 was repeated under a condition of 0.4 atm. As a result, it was found that stable rise in temperature of the crystalline silk powder can not be achieved in the glass tube.
  • Yamamai silk yarn was soaked in a 0.1 %-sodium carbonate aqueous solution having a bath ratio of 50 for one hour, washed with water and dried to yield degummed silk yarn as a material to be heat-treated.
  • the thus degummed silk yarn was burned in an atmosphere of 240 °C (burning time for 10 minuets) by means of the same apparatus used in the [Example 1] to yield a predominantly purple- and blue-colored mixture of denatured silk material as a burned product.
  • test samples A, B, C and D comprising different components as in the following.
  • samples B, C and D made the applied skin more smooth than that of an unapplied portion without causing itchiness.
  • the skin was comfortably wet and quite smooth with no itchiness.
  • the thus prepared mixture of the denatured silk material and water (in an amount of 100 g) was applied once a week to seedlings of a Madagascar periwinkle planted in a planter of about 20 cm wide, about 60 cm long and about 15 cm high.
  • the white (at treatment temperature of 100°C ) and brown (at treatment temperature of 270°C) crystalline silk powders obtained by the heat treatment of [Example 1] were used as an abrasive material.
  • the white crystalline silk powder obtained by the heat treatment of Example 1 at a treating temperature of 100 °C was used to test as a filter material.
  • the white silk powder was put between two flat boards and pressed under pressure of 20 kg / cm 2 to harden, thereby yielding a powder board of 2 mm in thick.
  • the powder board was sandwiched between filter paper to form a filter material.
  • Water collected from Lake Biwa was filtered under 0.5 atm. by means suction using the thus prepared filter material, thereby yielding water of considerably improved muddiness.
  • the silk material of the present invention can be used for a purpose as a raw material of an outer skin coating product for human use such as outer skin preparations, non-medical skin agents and beauty products or as a medical material, for a purpose as a plant growth promoter, or for other, purposes such as an absorbent, a filter material and an abrasive material. Further, this silk material has much possibility of utilization such as coating for material, dying of cloths.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Husbandry (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Cosmetics (AREA)
  • Materials For Medical Uses (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (16)

  1. Verfahren zur Herstellung eines denaturierten Seidenmaterials von verschiedenen Farben, dadurch gekennzeichnet, daß es die Hitzebehandlung von natürlicher Seide, halb-degummierter Seide oder degummierter Seite oder einem Gemisch davon in einer Atmosphäre von Luftfluß unter 0,5 bis 1,5 Atmosphären bei einer Temperatur von 150 bis 500°C für eine bestimmte Zeitdauer umfaßt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß eine Hitzebehandlungs-Zeitdauer im Bereich von 0,3 Minuten bis 20 Stunden liegt.
  3. Verfahren zur Herstellung eines denaturierten Seidenmaterials von verschiedenen Farben, dadurch gekennzeichnet, daß es eine Hitzebehandlung von natürlicherer Seide, halb-degummierter Seide oder degummierter Seide oder einem Gemisch davon in einer Atmosphäre von inertem Gasfluß, unabhängig voneinander ausgewählt aus Stickstoff, Helium, Neon, Argon, Krypton und Xenon oder einem Gemisch davon unter 0,5 bis 1,5 Atmosphären bei einer Temperatur von 150 bis 500°C für eine bestimmte Zeitdauer umfaßt.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Hitzebehandlungs-Zeitdauer im Bereich von 0,3 Minuten bis 20 Minuten liegt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die natürliche Seide, halb-degummierte Seide, degummierte Seide oder eine Gemisch davon in der Form eines Films, Puder, Faser, Garn, Gewebes, Geflecht oder Gemisch davon vorliegt.
  6. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß verschiedene Farben Schwarz, Gelb, Braun, Dunkelbraun, Rot, Violett, Blau und Grau oder natürliche Farbtöne davon einschließen.
  7. Denaturiertes Seidenmaterial von verschiedener Farbe, dadurch gekennzeichnet, daß es durch Hitzebehandlung von natürlicher Seide, halb-degummierter Seide oder degummierter Seide oder einem Gemisch davon in einer Atmosphäre von Luftfluß unter 0,5 bis 1,5 Atmosphären bei einer Temperatur von 150 bis 500°C für eine bestimmte Zeitdauer erhalten wurde.
  8. Denaturiertes Seidenmaterial nach Anspruch 7, dadurch gekennzeichnet, daß die Hitzebehandlungs-Zeitdauer im Bereich von 0,3 Minuten bis 20 Stunden liegt.
  9. Denaturiertes Seidenmaterial von verschiedener Farbe, dadurch gekennzeichnet, daß es durch Hitzebehandlung von natürlicher Seide, halb-degummierter Seide, degummierter Seide oder einem Gemisch davon in einer Atmosphäre von inertem Gasfluß, unabhängig voneinander ausgewählt aus Stickstoff, Helium, Neon, Argon, Krypton, Xenon oder einem Gemisch davon unter 0,5 bis 1,5 Atmosphären bei einer Temperatur von 150 bis 500°C für eine bestimmte Zeitdauer erhalten wurde.
  10. Denaturiertes Seidenmaterial nach Anspruch 9, dadurch gekennzeichnet, daß die Hitzebehandlungs-Zeitdauer im Bereich von 0,3 Minuten bis 20 Stunden liegt.
  11. Denaturiertes Seidenmaterial nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß das Material zum Zweck als ein äußeres Hautbeschichtungsprodukt zum menschlichen Gebrauch verwendet wird.
  12. Denaturiertes Seidenmaterial nach Anspruch 11, dadurch gekennzeichnet, daß das äußere Hautbeschichtungsprodukt für den menschlichen Gebrauch ein medizinisches Material für die äußere Haut, nicht medizinisches Material für die äußere Haut oder Schönheitsprodukt ist.
  13. Denaturiertes Seidenmaterial nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß das denaturierte Seidenmaterial zum Zweck als ein medizinisches Material verwendet wird.
  14. Denaturiertes Seidenmaterial nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß das denaturierte Seidenmaterial zum Zweck als ein Pflanzenwachstumspromotor verwendet wird.
  15. Denaturiertes Seidenmaterial nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß das denaturierte Seidenmaterial zum Zweck als ein absorbierendes oder ein Filtermaterial verwendet wird.
  16. Denaturiertes Seidenmaterial nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß das denaturierte Seidenmaterial zum Zweck als ein abrasives Material verwendet wird.
EP98961455A 1997-12-25 1998-12-21 Modifizierte seidenmaterialen und herstellungsverfahren Expired - Lifetime EP0964085B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP36739597 1997-12-25
JP36739597 1997-12-25
PCT/JP1998/005784 WO1999034038A1 (fr) 1997-12-25 1998-12-21 Matieres de soie modifiee et procede de production de celles-ci

Publications (3)

Publication Number Publication Date
EP0964085A1 EP0964085A1 (de) 1999-12-15
EP0964085A4 EP0964085A4 (de) 2002-03-06
EP0964085B1 true EP0964085B1 (de) 2004-02-25

Family

ID=18489211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98961455A Expired - Lifetime EP0964085B1 (de) 1997-12-25 1998-12-21 Modifizierte seidenmaterialen und herstellungsverfahren

Country Status (7)

Country Link
EP (1) EP0964085B1 (de)
KR (1) KR100393831B1 (de)
CN (1) CN1123656C (de)
BR (1) BR9807604A (de)
DE (1) DE69821916T2 (de)
HK (1) HK1024272A1 (de)
WO (1) WO1999034038A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4171491B2 (ja) * 2003-07-16 2008-10-22 シナノケンシ株式会社 絹焼成体の製造方法および絹焼成体からなる抗菌材の製造方法
EP1659218A1 (de) * 2004-11-19 2006-05-24 The Procter & Gamble Company Tissuepapier mit Seidefasern

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6115896A (ja) * 1984-07-02 1986-01-23 Jiro Asahina ▲おん▼度変化式▲きぬ▼粉体の製造方法
JPH04174763A (ja) * 1990-10-31 1992-06-22 Kanebo Ltd 絹繊維構造物の改質方法
JP2950729B2 (ja) * 1994-08-18 1999-09-20 上谷 昇一 絹素材の処理方法
JPH10266010A (ja) * 1997-03-25 1998-10-06 Kawamura:Kk 絹材料の炭化処理粉末、炭化処理物並びにそれらの製造方法
KR100402051B1 (ko) * 2000-10-18 2003-10-17 한국과학기술연구원 질소산화물 저감용 선택적 무촉매 환원제

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Publication number Publication date
BR9807604A (pt) 2000-03-21
KR100393831B1 (ko) 2003-08-06
DE69821916D1 (de) 2004-04-01
DE69821916T2 (de) 2004-12-23
KR20000075618A (ko) 2000-12-26
CN1123656C (zh) 2003-10-08
EP0964085A4 (de) 2002-03-06
WO1999034038A1 (fr) 1999-07-08
CN1250492A (zh) 2000-04-12
HK1024272A1 (en) 2000-10-05
EP0964085A1 (de) 1999-12-15

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