EP0253828B2 - Modifizierte bastfasern und verfahren zur gewinnung derselben - Google Patents

Modifizierte bastfasern und verfahren zur gewinnung derselben Download PDF

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Publication number
EP0253828B2
EP0253828B2 EP87900173A EP87900173A EP0253828B2 EP 0253828 B2 EP0253828 B2 EP 0253828B2 EP 87900173 A EP87900173 A EP 87900173A EP 87900173 A EP87900173 A EP 87900173A EP 0253828 B2 EP0253828 B2 EP 0253828B2
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Prior art keywords
flax
modified
fibrous
linen
solution
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English (en)
French (fr)
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EP0253828B1 (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 a modified fibrous linen, usable in particular in the textile industry; It also relates to a process for obtaining such linen.
  • 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.
  • modified fibrous linen as defined in claim 1 which, compared to the current unbleached or bleached linen, has a greater fineness, a lower amount of non-cellulosic materials and a crystal structure at least as ordered.
  • 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-cellulosic encrusting materials and by an undegraded crystal structure, or even improved by the treatment. that she suffered.
  • 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 chromatography of ion exchanges, 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 dosage of these sugars by the ion exchange chromatography technique after attack on the flax 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 flax modified according to the invention generally contains a smaller amount of non-cellulosic encrusting materials.
  • the fine cuts of unbleached flax show a very apparent concentric ring structure: this structure is slightly weakened for bleached flax, on the other hand, for flax modified according to the invention, this annular structure has almost disappeared, only one or two rings persist closest to the lumen.
  • the so-called depolymerization peak has a very great intensity in the case of flax modified according to the invention, an average intensity in the case of bleached flax, whereas it cannot be evaluated in the case of flax. unbleached. this is no doubt due to a superposition of different peaks.
  • 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 with respect to an amorphous cellulose standard 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 flax modified according to the invention with respect to ecru linen, according to the example given later.
  • Patents GB-A-388561, GB-A-476-569 and US-A-4-2633421 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 hulling 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 oars 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.
  • Figures 9 to 12 are the differential enthalpy analysis curves of the four linens: unbleached flax (figur) 9), bleached flax (figure 10), modified flax A (figure 11), modified flax B (figure 12).
  • Unbleached short fiber flax is flax which, after scutching, has undergone a mechanical refining treatment. by different materials such as fine openers.
  • 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 yarns containing flax mixed with synthetic fibers, these yarns being always a minority in flax, with a proportion in 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, 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 treatment of hydrolysis 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.
  • the values obtained for the four flaxes are respectively 23.2 for unbleached flax, 17.2 for bleached flax, 13.8 for modified flax A, and 11.3 for modified flax B, with, in all tests, a coefficient of variation of 2 or 3%.
  • 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 for the total mass of sugars extracted in percentage compared 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 flax modified A and 0.6% for modified flax B.
  • the flax sample is reduced to powder and then pelletized with anhydrous potassium bromide before recording of 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 thiocarbonydrazide 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 skinned in 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 pellets under a pressure of 350 kg / cm2.
  • the recording of the diffracted spectrum is done in an angular domain 20 from 10 to 40 °. Measuring the areas of these diffracted peaks makes it possible to assess the crystallinity of the sample compared to an amorphous cellulose standard.
  • 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 iin, 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 picked up 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 linen treated according to the invention 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)
  • Seasonings (AREA)
  • Preparation Of Fruits And Vegetables (AREA)

Claims (6)

  1. Flachsfasern, dadurch modifiziert, daß sie im wesentlichen aus Grundfasern bestehen und daß sie bei nicht verschlechterter kristalliner Struktur eine äußerst geringe Menge an sich ansetzenden Stoffen aufweisen, wobei diese äußerst geringe Menge daraus ersichtlich ist, daß
    a) die anscheinende Ringstruktur im Elektronenmikroskop im Durchlicht nahezu verschwunden ist, wobei höchstens die beiden dem Lumen am nächsten gelegenen Ringe fortbestehen, wobei diese Beobachtung auf feinen Schnitten des in ein Epoxydharz eingeschlossenen Flachses beruht, nachdem dieser kardiert, nacheinander eine Stunde lang bei 20 °C mit einer Lösung aus 0,1 M Natriumperjodat, eine Stunde lang bei 20 °C mit einer gesättigten Thiokarbohydrazidlösung und 12 Stunden lang bei 20 °C mit einer Osmiumtetroxidlösung behandelt, mit Wasser gespült und gereinigt wurde,
    b) die Gesamtmasse ihrer nach ausgeführter Hydrolyse extrahierbarer und durch Chromatographie mittels Ionenaustausch dosierbarer Zucker unter 4,25 % liegt, und insbesondere die Gesamtmasse an Galaktose unter 1% liegt.
  2. Modifizierte Flachsfasern nach Anspruch 1, dadurch gekennzeichnet, daß ihr Standard-Feinheitswert unter 14,6 liegt.
  3. Modifizierte Flachsfasern nach Anspruch 1, dadurch gekennzeichnet, daß die Größe der in einer zur Kristallebene 002 senkrechten Richtung gemessenen Kristallite über 5,14 nm, d.h. der Größe der Kristallite des rohen Flachses ist.
  4. Herstellungsverfahren für FLachsfasern nach Anspruch 1, das darin besteht, eine Faserpflanze unter hohem Druck einer Dampfbehandlung zu unterziehen, dann den Druck auf den Atmosphärendruck 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 etwa zehn Sekunden bei einem Druck von etwa dreißig bar durchgeführt wird.
  5. Herstellungsverfahren für Flachsfasern nach Anspruch 1, das darin besteht, eine Faserpflanze unter hohem Druck einer Dampfbehandlung zu unterziehen, dann den Druck auf den Atmosphärendruck 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 etwa fünfzehn bar während einer Dauer von etwa neunzig Sekunden stattfindet.
  6. Herstellungsverfahren nach Anspruch 5, dadurch gekennzeichnet, daß die zur Vorbehandlung verwendete Lösung eine Lösung ist, die 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)

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

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

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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
EP0946817A1 (de) * 1996-12-17 1999-10-06 Kimberly-Clark Worldwide, Inc. Verfahren zur behandlung von zellstofffasern
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
FR2592400A1 (fr) 1987-07-03
CN86108934A (zh) 1987-07-15
KR940005920B1 (ko) 1994-06-24
CN1015652B (zh) 1992-02-26
EP0253828B1 (de) 1990-10-24
JPS63502520A (ja) 1988-09-22
EP0253828A1 (de) 1988-01-27
WO1987004194A1 (fr) 1987-07-16
BR8607038A (pt) 1987-12-22
DE3675213D1 (de) 1990-11-29
FR2592400B1 (fr) 1988-08-26
KR870006241A (ko) 1987-07-10

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