EP0253828B1 - Modifizierte bastfasern und verfahren zur gewinnung derselben - Google Patents

Modifizierte bastfasern und verfahren zur gewinnung derselben Download PDF

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Publication number
EP0253828B1
EP0253828B1 EP87900173A EP87900173A EP0253828B1 EP 0253828 B1 EP0253828 B1 EP 0253828B1 EP 87900173 A EP87900173 A EP 87900173A EP 87900173 A EP87900173 A EP 87900173A EP 0253828 B1 EP0253828 B1 EP 0253828B1
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European Patent Office
Prior art keywords
flax
fibrous
modified
bleached
less
Prior art date
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Expired - Lifetime
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EP87900173A
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English (en)
French (fr)
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EP0253828B2 (de
EP0253828A1 (de
Inventor
Serge Chaunis
Pierre Monzie
Jean Prunier
Marc Ferrari
Michel Sotton
Alain Satta
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CENTRE TECHNIQUE DE L'INDUSTRIE DES PAPIERS CARTONS ET CELLULOSE
Institut Textile de France
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CENTRE TECHNIQUE DE L'INDUSTRIE DES PAPIERS CARTONS ET CELLULOSE
Institut Textile de France
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Application filed by CENTRE TECHNIQUE DE L'INDUSTRIE DES PAPIERS CARTONS ET CELLULOSE, Institut Textile de France filed Critical CENTRE TECHNIQUE DE L'INDUSTRIE DES PAPIERS CARTONS ET CELLULOSE
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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
    • D01C1/00—Treatment of vegetable material

Definitions

  • the present invention relates to modified vegetable bast fibers, in particular flax, usable in particular in the textile industry; It also relates to a process for obtaining such fibers.
  • Liberian vegetable fibers fibers from the plant liber, such as those of flax, hemp, jute, kenaf, ramie ..., or families such as alfa, sisal, that is ie fibers having a similar structure in a bundle of fibers with cements.
  • the fibers are arranged in bundles of elementary fibers at the periphery of the rod between the bark and the wood.
  • pectins, hemicellulose, lignin organic cements
  • pectins, hemicellulose, lignin organic cements
  • bleached flax Effectively compared to unbleached fibrous flax, degummed and bleached flax, hereinafter called bleached flax, has greater finesse, but still has a non-negligible number of bundles in the process of cleavage and sometimes intact; it also has less encrusting material, as can be seen from infrared spectroscopy and differential enthalpy analysis, but it still has a significant part. But in the opposite direction, it can be seen that bleaching degrades the crystalline structure of the cellulose.
  • This modified fibrous linen is, after carding and before spinning, essentially made up of elementary fibers, possibly with some remains of bundles but in negligible proportion compared to the constitution of bleached fibers and all the more unbleached.
  • it in transmission electron microscopy, it has almost no apparent annular structure, said annular structure being representative of the presence of encrusting materials.
  • this index is less than 14.6, that is to say it is less than at least fifteen percent to the fineness index of bleached linen which is 17.2 in the example given later and at least thirty percent compared to unbleached linen.
  • the preferred modified fibrous linen is characterized by a very high purity of the cellulose, marked both by a small residual amount of non-cel.lu- losiques encrusting materials and by an undegraded crystal structure, or even improved by the treatment she underwent.
  • the residual quantity of non-cellulosic encrusting materials is determined by various analyzes, either direct, for example the measurement of the total mass of extractable sugars after gentle hydrolysis and assayable by ion exchange chromatography, or indirect, for example the measurement of the number of ketone groups, significant of encrusting materials such as lignin and pectins, by infrared spectroscopy, or comparative for example the examination of fine sections by transmission electron microscopy and the examination of the shape of so-called depolymerization peaks in analysis differential enthalpy.
  • the non-cellulosic encrusting materials of flax include various compounds which, upon hydrolysis, generate sugars such as galactose, xylose, arabinose, rhamnose, mannose, glucose; pectins; lignin.
  • the preferred modified fibrous linen has a significantly lower residual sugar content than that of unbleached and bleached linen; in fact, the assay of these sugars by the ion exchange chromatography technique after flax attack for four hours with molar sulfuric acid at 105 ° C. revealed that the total mass of sugars extracted from the flax modified according to the invention was less than 4.25%, that is to say at least two times less important than that extracted from unbleached flax, which is 8.5% in the example given later, or from bleached flax.
  • the other analyzes all lead to the conclusion that the flax modified according to the invention overall contains a smaller amount of non-cellulosic encrusting materials.
  • the modified fine fibrous material according to the invention has a crystalline structure which has not been altered by the treatment undergone, unlike bleached linen. Indeed, by X-ray diffractometry, it is observed on the one hand that the degree of crystallinity relative to a standard of amorphous cellulose is the same for the unbleached, bleached and modified linens according to the invention, but on the other hand that the size of the crystallites, measured in a direction perpendicular to the crystal plane 002, which decreases by more than ten percent during bleaching is equal to or greater than 5.14 nm, that is to say of the same order or even greater in the flax modified according to the invention compared to unbleached flax, according to the example given later.
  • Patents GB-A-388561, GB-A-476-569 and US-A-2633421 disclose treatments according to which a fiber plant is subjected to the action of steam under high pressure and then expanded to atmospheric pressure. and finally washed. These known treatments relate to the dehulling of fiber plants in the form of straw, leaves, grass, that is to say the separation of the bark or the woody part of the fibers themselves. To obtain such a result, the pressures used are between 38 and 62 bars in one step according to the patents GB-A-388561 and GB-A-476569 and in two steps according to the patent US-A-2633421.
  • the modified linen according to the invention can be obtained by a process of the aforementioned known type; typically the fiber plant is a previously stained linen under flax and the action of steam is carried out at a pressure of the order of thirty bars for a period of the order of ten seconds.
  • the modified flax according to the invention can also be obtained by subjecting a dyed, under-rye flax to a first treatment consisting of impregnation with a basic or acid solution, then to a hydrolysis treatment in water vapor at a lower pressure. high, for example of the order of fifteen bars, for a slightly longer time, for example of the order of ninety seconds, followed by a sudden expansion at atmospheric pressure, then a subsequent washing.
  • the impregnation solution of the first treatment is an alkaline solution containing from four to six percent by weight of soda.
  • Unbleached short fiber flax is a flax which, after scutching, has undergone a mechanical refining treatment, using different materials of the fine working type.
  • This ecru short fiber linen is a linen produced industrially and marketed for several years. It is used by the textile industry for the production of threads containing flax mixed with synthetic fibers, these threads always being a minority in flax, with a proportion of flax which generally does not exceed twenty five percent.
  • the bleached flax used is a mechanically refined flax, as above, which has been subjected to a degumming and bleaching treatment known as four quarters, representative of the purest products existing on the market.
  • modified flax A The first modified flax according to the invention, hereinafter called modified flax A, was obtained from an under-rye scorched flax, which was introduced into a reactor after having been cut into lengths of seventy millimeters, then subjected to a hydrolysis treatment in steam at 30 bar pressure for a period of ten seconds; at the expiration of this period, the opening of the discharge port of the reactor causes a sudden expansion on passage from high pressure to atmospheric pressure and therefore the ejection by said orifice of flax in a tank containing water slightly alkaline (0.4% soda) where it is washed and then rinsed.
  • modified B flax The second modified flax according to the invention, hereinafter called modified B flax, was obtained from a dyed under rolled flax, which, cut into lengths of 70 millimeters, underwent a first treatment of impregnation by a alkaline solution containing 4% by weight of soda.
  • the linen thus impregnated was introduced into the reactor as above and subjected to a hydrolysis treatment in steam, of water at 15 bars of pressure for ninety seconds.
  • the subsequent operations are the same as for modified flax A.
  • the measurement of the standard fineness index is carried out from a pad of material of constant mass, which is compressed in a mold under a predetermined pressure.
  • IFS standard fineness index
  • the flax is first attacked for four hours with molar sulfuric acid at 105 °, then the extract obtained is analyzed according to the method of chromatographic analysis of sugars perfected by the Boulogne laboratory of the Textile Institute of France and described in the Scientific Bulletin of the Textile Institute of France volume 6, N ° 23, third quarter 1977.
  • This method makes it possible to calculate in percentage the total mass of the extracted sugars, after the action of hydrolyzed managed carried out by l molar sulfuric acid.
  • These sugars are representative of hemicelluloses and pentosans accessible in technical flax. These are in particular arabinose, xylose with the weakest glycosidic bonds, galactose, rhamnose, mannose and glucose.
  • the values obtained, as to the total mass of sugars extracted as a percentage relative to the mass of flax analyzed, are respectively 8.5% for unbleached flax, 11% for bleached flax, 2.9% for modified flax A and 3% for modified flax B.
  • the values obtained, as regards the mass of galactose extracted as a percentage relative to the mass of flax analyzed, are respectively 3.0% for unbleached flax, 3.5% for bleached flax, 0.4% for modified flax A and 0.6% for modified flax B.
  • the flax sample is powdered and then pelletized with anhydrous potassium bromide before recording its absorption spectrum.
  • the flax is successively treated with a 0.1 M solution of sodium periodate for one hour at 20 ° C, with a saturated thiocarbohydrate solution for one hour at 20 ° C and with a solution of osmium tetraoxide for 12 hours at 20 ° C. After rinsing with water and drying, the flax is included in an epoxy resin and cut into fine sections with an ultramicrotome before observation on an electron microscope.
  • the measurement is made by increasing the linear temperature, at a rate of 20 ° C. per minute, from 1 to 5 milligrams of material under a flow of nitrogen and by recording the difference between the temperatures of the crucible containing the material and a witness crucible.
  • the so-called depolymerization peak is significant both by the temperature at which it is located, and by its intensity.
  • Bleached flax has a depolymerization peak of medium intensity, placed at a temperature of 369 ° C (fig. 10).
  • Modified flax has a high intensity peak, placed at 373.5 ° C ( Figure 11), and the modified flax B has an even greater peak in intensity, placed at 378.5 ° C ( Figure 12).
  • the flax is cut into 80 ⁇ m segments, disoriented and pelletized under a pressure of 350 kg / cm 2 .
  • the recording of the diffracted spectrum is done in an angular domain 20 from 10 to 40 °. Measuring the areas of the diffracted peaks makes it possible to assess the crystallinity of the sample compared to an amorphous cellulose standard.
  • the values obtained are substantially the same for the four flaxes, the crystallinity being 40% for unbleached flax and the modified flaxes A and B, and 39% for bleached flax.
  • a strand of fibers is diffracted and the thickness of the diffracted lines is measured.
  • the line chosen corresponds to an angle 20 of 22.5 ° and is related to the crystalline plane 002 of the cellulose.
  • the sizes of the crystallites measured in a direction perpendicular to the crystal plane 002 are respectively 5.14 nm for unbleached flax, 4.05 nm for bleached flax, 5.45 nm for modified flax A and 6 nm for modified flax B.
  • the bleaching treatment degraded the crystalline structure of the cellulose, while the flax according to the invention has a crystal structure as, or even more, ordered than unbleached flax.
  • the material which served as a basis for the modified linen according to the invention is an under-rotted flax, for example a flax which has been prematurely gathered in the case of retting on the ground.
  • Under-rotted flax transformed in the classic processes, is always coarser than a normally rotted flax, insofar as the cements which bind the fibers between them and the bundles between them could not be sufficiently degraded by the agents bacteriological retting.
  • Modified flax A was used in spinning to produce a flax yarn mixed with synthetic fibers, for example acrylic fibers. Comparatively son of the same type was produced with a mechanically refined linecru, as described in the embodiment example above. It is observed that, for a 75% acrylic / 25% linen mixed yarn, the yarn made from modified flax A is more regular than its counterpart made from unbleached flax. Furthermore, it has been possible to produce with modified flax A a majority thread of flax, which is not possible in industrial market with unbleached flax.
  • the fibers treated according to the invention in particular linen, can be used in all conventional textile applications, in particular in admixture with other natural or chemical fibers in the most varied proportions, but also for other applications.

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  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Preparation Of Fruits And Vegetables (AREA)
  • Seasonings (AREA)

Claims (8)

1. Modifizierte Flachsfasern, dadurch gekennzeichnet, daß sie nach dem Kardieren und vor dem Spinnen im wesentlichen aus Grundfasern bestehen, und daß sie im Elektronenmikroskop im Durchlicht nahezu keine klare Ringstruktur aufweisen, die typisch für sich ansetzende Stoffe ist.
2. Flachsfasern nach Anspruch 1, dadurch gekennzeichnet, daß die relative Gesamtmasse ihrer extrahierbaren Zucker nach ausgeführter und durch Chromatographie mittels lonenaustausch dosierbarer Hydrolyse, wobei die genannte Masse typisch für die Menge an sich absetzenden, nicht aus Zellulose bestehenden Stoffen ist, unter 4,25% liegt, das heißt mindestens zwei mal niedriger ist als die aus rohem Flachs extrahierte Masse.
3. Flachsfasern nach Anspruch 2, dadurch gekennzeichnet, daß die relative Gesamtmasse an Galaktose unter einem 1% liegt, also mindestens drei mal so niedrig ist als die aus rohem Flachs extrahierte Masse.
4. Flachsfasern nach Anspruch 1, dadurch gekennzeichnet, daß der Standard-Feinheitswert unter 14,6 liegt, also mindestens um 15% unter dem Wert von gebleichtem Flachs liegt.
5. Flachsfasern nach Anspruch 1, dadurch gekennzeichnet, daß die Größe der in einer zur kristallinischen Ebene 002 senkrechten Richtung gemessenen Kristallite gleich oder größer 5,14 mm ist, also der Größ der Kristallite des rohen Flaches entspricht.
6. Herstellungsverfahren für Flachsfasern nach Anspruch 1, das darin besteht, eine Faserpflanze unter hohem Druck einer Dampfbehandlung zu unterziehen, dann den Druck auf Luftdruck zu senken und sie schließlich zu waschen, dadurch gekennzeichnet, daß die Faserpflanze ein vorher geschwingelter gerotteter Flachs ist, und daß die Dampfbehandlung während einer Dauer von zehn Sekunden bei einem Druck von dreißig Bar durchgeführt wird.
7. Herstellungsverfahren für Flachsfasern nach Anspruch 1, das darin besteht, eine Faserpflanze unter hohem Druck einer Dampfbehandlung zu unterziehen, dann den Druck auf Luftdruck zu senken und sie schließlich zu waschen, dadurch gekennzeichnet, daß die Faserpflanze ein vorher geschwingelter gerotteter Flachs ist, daß der Flachs durch Imprägnieren durch eine basische oder saure Lösung vorbehandelt wird, und daß die Hydrolyse-Behandlung bei einem Druck von fünfzehn Bar während einer Dauer von neunzig Sekunden stattfindet.
8. Herstellungsverfahren nach Anspruch 7, dadurch gekennzeichnet, daß die zur Vorbehandlung verwendete Lösung 4 bis 6% Natriumkarbonat enthält.
EP87900173A 1985-12-27 1986-12-23 Modifizierte bastfasern und verfahren zur gewinnung derselben Expired - Lifetime EP0253828B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8519526A FR2592400B1 (fr) 1985-12-27 1985-12-27 Fibres vegetales liberiennes modifiees et procede d'obtention.
FR8519526 1985-12-27

Publications (3)

Publication Number Publication Date
EP0253828A1 EP0253828A1 (de) 1988-01-27
EP0253828B1 true EP0253828B1 (de) 1990-10-24
EP0253828B2 EP0253828B2 (de) 1993-11-18

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ID=9326389

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EP87900173A Expired - Lifetime EP0253828B2 (de) 1985-12-27 1986-12-23 Modifizierte bastfasern und verfahren zur gewinnung derselben

Country Status (8)

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EP (1) EP0253828B2 (de)
JP (1) JPS63502520A (de)
KR (1) KR940005920B1 (de)
CN (1) CN1015652B (de)
BR (1) BR8607038A (de)
DE (1) DE3675213D1 (de)
FR (1) FR2592400B1 (de)
WO (1) WO1987004194A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0608949B1 (de) * 1993-01-25 1998-05-06 Ceres B.V. Verfahren zur Herstellung von feuchtigkeitsbeständigen Pflanzenfasern
WO1998027269A1 (en) * 1996-12-17 1998-06-25 Kimberly-Clark Worldwide, Inc. Treatment process for cellulosic fibers
CN1302160C (zh) * 2005-01-04 2007-02-28 陈建旭 一种用植物茎杆生产纤维的方法
ITCZ20060006A1 (it) * 2006-03-06 2007-09-07 Univ Calabria Processo chimico-fisico per la produzione di fibre vegetali

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB476569A (en) * 1936-06-05 1937-12-06 Albert Taylor Ratliff Process of decortication of fibrous plants
GB388561A (en) * 1932-02-08 1933-03-02 Charles Victor Rowell Process for decorticating vegetable fibre and the manufacture of products therefrom
US2633421A (en) * 1947-10-23 1953-03-31 Elmer R Perkins Fiber liberation by steam expansion

Also Published As

Publication number Publication date
KR870006241A (ko) 1987-07-10
KR940005920B1 (ko) 1994-06-24
CN86108934A (zh) 1987-07-15
FR2592400B1 (fr) 1988-08-26
BR8607038A (pt) 1987-12-22
EP0253828B2 (de) 1993-11-18
CN1015652B (zh) 1992-02-26
FR2592400A1 (fr) 1987-07-03
EP0253828A1 (de) 1988-01-27
DE3675213D1 (de) 1990-11-29
WO1987004194A1 (fr) 1987-07-16
JPS63502520A (ja) 1988-09-22

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