US2586796A - Production of viscose rayon - Google Patents

Production of viscose rayon Download PDF

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Publication number
US2586796A
US2586796A US173924A US17392450A US2586796A US 2586796 A US2586796 A US 2586796A US 173924 A US173924 A US 173924A US 17392450 A US17392450 A US 17392450A US 2586796 A US2586796 A US 2586796A
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viscose
bath
degree
filaments
weight
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Drisch Nicolas
Brepson Roland
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TEXTILE and CHEM RES CO Ltd
TEXTILE AND CHEMICAL RESEARCH Co Ltd
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TEXTILE and CHEM RES CO Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose

Definitions

  • the xanthogenation of the alkali cellulose may be eiected with varying quantities of car- 2 bon disulphide e. g. from 30 to 60% or even as high as 150%, calculated on the weight of the alpha-cellulose in the material treated, (d)
  • the preparation of the viscose may be varied so that the produ-ct contains 5 to 8% or even up to 12% of cellulose and from 8 to 5% or even less of caustic alkali.
  • the viscose thus prepared may be ripened to a small extent or to a great extent.
  • the spinning bath may consist of sulphuric acid of a concentration lying between 45 and by Weight and may contain added salts, and the bath may be used at any temperature between 10 C. and +50 C.
  • the length of the path of travel of the ⁇ laments through the spinning bath may vary from 3 to 200 cm.
  • the filaments maybe allowed to travel in air after leaving the spinning bath and before they are washed and the length of the path of this travel through the air may be from 20 to 120 cm. or even as great as 200 cm.
  • the linear speed of travel of the filaments through the bath may vary from l0 to 60 metres per minute.
  • the filaments may be rapidly washed.
  • the filaments may be stretched by passing over xed bearing surfaces or between rollers rotating at successively increasing speeds.
  • pages 113-118 A feature of this product is the possibility of producing very fine denier yarns, for instance as low as 0.3'denier.
  • the present invention is based on the discovery that by a combination of a number of definite conditions it is possible to obtain products of very high quality indeed.
  • a process for the production of high quality viscose rayon filaments having in the Aair-dry condition a tenacity greater than 4.8 gm. per denier and an elongation at the breaking point greater than 8% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose containing less than by weight of molecular chains with a degree of polymerisation below 500 and less than 4% by weight of molecu- Alar chains with a degree of polymerisation below 250, said viscose being prepared via alkali-cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose 4has a degreeof Xanthogenation (y) (as hereinafter defined) between and 50, the concentration of sulphuric acid in the said bath being defined by the formula:
  • a process for the production of ,high quality viscose rayon filaments having in the air-dry condition a tenacity greater than 5.0 gm. per denier and lan elongation at the breaking point greater than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose Acontaining yless than 25% by weight of molecular chains with a degree of polymerisation below 500 and less than 4% by weight of molecular vchains with'a degree of polymerisation below 250, said viscose being prepared via alkali cellulose-of which the mean degree of polymerisation after ripening is greater than 450, which viscose has a degree 'of xanthogenation (y) (as hereinafter defined) between 4.4.and 47, the concentration of sulphuric acid in the said .bath being -defined by the formula:
  • the degree of polymerisation is determined bymeasuring the'viscosity of a carefully prepared cellulose nitrate in'anappropriate organic solvent and multiplying the viscosity thus determined by the'constant defined by Staudinger.
  • the composition of some typical pulps is set out in Table II.
  • the degree of Xanthogenation of the cellulose represented by the symbol y, is the number of hydroxyl groups substituted by -CSS- groupsv per 100 glucose units (i. e. CeHioOs units)l 'y-Values below 40 are impracticable since they yield products of low extensibility and an upper limit is set by the fact that sulphuric acid of strength much greater than 72% has so strong aA dissolving action on the viscose laments that very rapid washing indeed becomes necessary.
  • the viscose In the preparation of the viscose from the cellulose via alkali-cellulose it is preferred to adjust the conditions so as to obtain a viscose containing not more than '7% of cellulose and not less than 6.5% of caustic soda lye (preferably between 6.5 and 8.2% of caustic soda lye).
  • the viscosity of the viscose should be greater than 150 C. G. S. units and preferably greater than 200-250 C. G. S. units.
  • Figure l is a three dimensional diagram showing the optimum tenacities obtained from the best combination of concentrations of acid and y values.
  • Figure 2 is a graph showing the tenacities obtained from combinations of concentrations of acid and specific y values.
  • Figure 3 is a graph comparing the extensibility and tenacity of various type yarns.
  • Figure 4 is a photomicrograph of a cross-section of the Lilienfeld yarn.
  • Figure 5 is a photomicrograph of a cross-section of the yarn of this invention.
  • the highest quality products are obtained using viscose of y-value about 45 and an acid concentration about 65%.
  • the optimum acid concentration for a viscose of particular 'y-value is determined by the formulae set out above and represents the apex of the curve, of somewhat paraboloidal shape, which, for a given 'y-value, connects the tenacity with the sulphuric acid concentration.
  • the variation i3% included in the rst formula above affords a margin on either side of the optimum value at which products having prop*- erties close to the optimum are obtained, and the variation f-2 affords a narrower margin within which the preferred products are obtained.
  • Curves connecting tenacity (wet and dry) with acid concentration for the limiting 'y-values of 40 and 50, and for their intermediate values in accordance with this invention, are illustrated in Figure 2.
  • the filaments should be stretched to the extent of 150-280% and preferably 200-250% continuously with their production and while they are still wet from 'the spinning bath. (The degree of stretch is calculated as the ratio of the increase in length to the original length.)
  • the process described in copending application No. 9,915, led February 19, 1948, now Patent No. 2,538,151 wherein the coagulated filaments are stretched and then led over at least one feed roller before passing to a winding device, the thread being caused to travel 3, 5 or 10 or more metres under tension in air between the feed roller and the winding device for a period of at least three seconds.
  • the tension in the yarn is allowed to even out and a more homogeneous yarn, with less internal strains, is obtained.
  • By allowing the yarn to relax, by removing the stretching tension a product is obtained which has less tendency to shrink than the usual stretched yarn.
  • Example I For the preparation of the viscose, carefully bleached cotton linters having the following properties was selected:
  • the weight average distribution of the chain lengths of the cellulose molecules was determined, by the method described above, using a arefully prepared nitrocellulose dissolved in aceone.
  • the stretched yarn was then passedv into.
  • aqueous washing bath iat 20910. having the -fol lowing composition:
  • the yarn travelled for 100 cm. in this bath and was then passed on to a third roller, similar to the rst and second rollers but rotating at only 195 R. P. M. By this means the yarn was allowed to relax. Finally the yarn was wound up in a conventional spinning pot rotating at '7500 R. P. M. The volume of viscose fed to the spinnerette was controlled by a pump so that a 300 denier yarn was obtained.
  • the yarn was then completely de-acidied with water and then treated with a 1% solution of sulphonated cetyl alcohol. It then had the For the preparation of the viscose, carefullyv bleached cotton linters having the following properties were selected:
  • the weight average distribution of the chain lengths of cellulose molecules was determined, by the method described above, using a carefully prepared nitrocellulose dissolved in acetone.
  • the alkali-cellulose was then placed in a churn of known type and a vacuum of 720 mm.' ofmerfcury was applied. 45 kg. of carbon disulphide was then added and the churn slowly rotated for two vhours at 25 C.
  • the cellulose xanthate thus obtained was dissolved in cold dilute caustic soda'lye to produce a viscose solution containing 5.9% cellulose and '8.0% caustic soda.
  • the temperature at rs't reduced to 6C.' rose-over f5 yhours to 14' C.
  • a scum-preventing material ' e. g. a mixture of the higher branched ali- .zphatic alcohols
  • Y was added.
  • the viscose was :then degassed over a period of 8 hours'at avacuum of r150 mm. of mercury.
  • the ⁇ viscosity of the iproduct wasthen 280C. G..S. units and. the viscose. 'after maturing ,for 36" hours at 14 C was found 'to have a y-value of 46.
  • the viscose thus obtained was spun through .a spinnerette of 600 holes, each 0.06 mm. diameter, into a bath containing 66% by weight of sulphuric acid, at 18 C.
  • the extruded filaments travelled through the bath a distance of 50 cm. and were then passed round two rollers in suc'- cession, each of 10 cm. diameter but rotating at different speeds so as to stretch the filaments to the extent of 240%.
  • the filaments lapped round the second of these rollers 10 turns and the roller was combined with an off-set rod so as to cause automatic displacement of the turns.
  • the stretched yarn was then passed into an aqueous washing bath at 20 C. having the following composition:
  • the yarn travelled for cm. in this bath and was then passed on to a third roller, similar to the first and second rollers but rotating at a slightly lower speed than the second roller. By this means the yarn was allowed to relax. Finally the yarn was wound up in a conventional spinning pot rotating at 7500 R. P. M. The volume of viscose fed to the spinnerette was controlled by a pump so that a 300 denier yarn was obtained.
  • the yarn was then completely de-acidied with water and then treated with a 1% solution of sulphonated cetyl alcohol. It then had the following properties:
  • the yarns of this invention have a higher extensibility (elongation at break) for the same or higher tenacity and have a higher relative value of wet to dry tenacity. They have a higher work-till-rupture value and this is illustrated in Figure 3 of the accompanying drawings in which the curves for the products Tenasco and Dural, calculated from the data given by L. Rose in the paper referred to above, are compared with a product of the foregoing Example II identiiied as curve P.
  • the values for work-till-rupture for Tenasco and Durail are 24.2 and 14.3 respectively, and the value for the yarn P is 23.2 calculated on the same basis.
  • the yarns of this invention have good flexibility and knot strength and the facility with which they may be twisted and woven renders them suitable for ordinary textile uses as well as for cord-twisting for the reinforcement of tyres, for which latter purpose their high degree of elongation at break (greater than 8%) makes them particularly suitable.
  • yarns produced in accordance with the present invention dye readily and evenly, comparing favourably with commercial high tenacity viscose yarns.
  • Percentage concentration by weight of 1 sulphuric acid 1.26'y+8i3 thereafter subjecting the extruded filaments to a stretching operation to increase their length by 150-280% while they are still wet from the spinningbath, washing the filaments in a more dilute acid' bath and allowing them to relax while still in thelacid condition and then winding or winding and y.tv'visting the filaments thus obtained.
  • Percentage concentration by weight of sulphuric acid 1.26fy+8 *3 thereafter subjecting the extruded filaments to a stretching operation to increase their length by -,280% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained
  • Process for the production of high quality viscose rayon filaments having in the air-dry condition a tenacity greater than 4.8 g.
  • Percentage concentration by weight of sulphuric acid 1.26-y+8i3 4a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose containing less than 25% by weight of molecular chains with a degree of polymerisation below 500 and less than 5% by weight of molecular chains with a degree of polymerisation below 250, said viscose being prepared va alkali cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose has a degree of xanthogenation (y) between 40 and 50, the said viscose containing at most '7% of cellulose and at least 6.5% of caustic soda lye and having a viscosity greater than 250 C.
  • G. S. units the concentration of sulphuric acid in the said bath being defined by the formula:
  • Percentage concentration by weight ci sulphuric acid 1.26y+8 f3 thereafter subjecting the extruded filaments to a stretching operation to increase their length by 150-280% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or Winding and twisting the laments thus obtained.
  • Percentage concentration by weight of sulphuric acid 1.26 ⁇ /!8i3 thereafter subjecting the extruded filaments to a stretching operation to increase their length by G-280% while they are still wet from the spinning bath, washing the ilaments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or Winding and twisting the filaments thus obtained.
  • Percentage concentration by weight of sulphuric acid l.26 ⁇ y+8i3 thereafter subjecting the extruded filaments to a stretching operation to increase their length by 15G-280% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained.
  • Percentage concentration by' weight of sulphuric acid 1.26fy
  • Process for the production of high quality viscose rayon filaments having in the air-dry condition a tenacity greater than 4.8 g. per denier and an elongation at the breaking point greater than 8% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cotton linters containing less than 25% by weight of molecular chains with a degree of polymerisation below 500 and less than 4% by weight of molecular chains with a degree of polymerisation below 250, said viscose being prepared via alkali cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose has a degree of xanthogenation ('y) bewteen 40 and 50, the said viscose containing at most 7% of cellulose and atleast 6.5% of caustic soda lye and having a viscosity greater than 250 C.
  • G. S. units the concentration of sulphuric acid in the said bath being
  • Percentage concentration by weight of sulphuric acid 1.26y+8i3 thereafter subjecting the extruded filaments to a stretching operation to increase their length by 15G-280% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and then causing -them to travel in free air under insuflicient tension to cause stretching, for a distance of at least three metres and for a period of at least three seconds, thus allowing the laments to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained.
  • Process for the production of high quality viscose rayon laments having in the air-dry condition a tenacity greater than 5.0 g. per, denier and an elongation at the breaking point greater than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose containing less than 25% by weight of molecular chains with a degree f polymerisation below 500 and less than 4% by weight of molecular ychains with a degree of polymerisation below 250, said viscose being prepared via alkali cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose has a degree of xanthogenation (y) between 44 and 47, the concentration of sulphuric acid in the said bath being defined by the formula:
  • Percentage concentration by weight of sulphuric acid 1.26y
  • Process for the production of high quality viscose rayon filaments having in the air-dry condition a tenacity greater than 5.0 g. per denier and an elongation at the breaking point greater than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cotton linters containing less than 2,5% by weight of molecular chains, with a degree of polymerisation below 500 and less-than.4% by weight of molecular chains with a degree of polymerisation below 250, said viscose being prepared via alkali cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose lhas a Percentage concentration by weight thereafter subjecting the extruded filaments to a stretching operation to increase their length by 20D-250% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or winding and Vtwist
  • Process for .the production of high quality viscose rayon filaments having in the air-dry con- ⁇ dition a tenacity greater than 5.0 g. per denier and an elongation at the breaking point greater than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose containingless.
  • Process for the production of high quality viscose rayon laments having in the air-dry condition a tenacity greater than 5.0 g. per denier and an elongation at the breaking point greater than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose containing less than 25% by weight of molecular chains with a degree of polymerisation below 500 and less than 4% by weight of molecular chains with a degree of polymerisation below 250, said viscose being prepared via alkali cellulose of which the mean degree of polymerisation after ripening-is greaterthan- 450,"which viscose has a degree of xanthogenation (y) between 44 and 47, the-said viscose containing at most 7% of cellulose and at least 6.5% ⁇ of caustic soda lye and having a l viscosity'greater than 150y C. G; S. units,'the concentration of sulphuric acid in the
  • Percentage concentration by weight of sulphuric acid 1.26 ⁇ y ⁇ +8i2 thereafter subjecting the extruded iilamentsr to a stretching operation to increase their length. by 20G-250% while they are still wetl from the spinning bath, washing the filaments in a more dilute acid' bath and allowing them to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained.
  • Process for the production of high quality viscose rayon filaments having in the air-dry condition a tenacity greater than 5.0 g. per denierand anelongation at the breaking point greater than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room temperature a viscose prepared from cellulose containing less than 25% by weight of molecular chains with a degree of polymerisation below 500 and less than 4% by weight oimolecular chains with a degree of polymerisation below 250, said viscose being prepared via alkali cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose has a degree of xanthogenation ('y) between 44 and 47, the said viscose containing at most 7% of cellulosefand at least 6.5% of caustic soda lye and havinga viscosity greater than-250 C.
  • G. S. units. the concentration of sulphuric acid in the said bath being deiine
  • Percentage concentration by weight of sulphuric acid 1.26'y+8i2 thereafter subjecting the extruded filaments to a stretching operation to increase their length by 20G-250% while they are still wet from the spinning bath, washing the laments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or winding and twisting the laments thus obtained.
  • Percentage concentration by weight of sulphuric acid l.26fy+8- I2 thereafter subjecting the extruded iilaments to a stretching operation to increase their length by 20G-250% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and allowing them to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained.
  • Process for the production of high quality viscose rayon iilaments having in the air-dry condition a tenacity greater than 5.0 g. per denier and an elongation at the breaking point greaterI than 8.5% which process comprises extruding into a bath of sulphuric acid at normal room ternperature a viscose prepared from cellulose containing less than 25% by weight of molecular chains with a degree of polymerisation below 500 and less than 4% by weight of molecular chains with a degree of polymerisation below 250, said viscose being prepared via alkali cellulose of which the mean degree of polymerisation after ripening is greater than 450, which viscose has a degree of xanthogenation (y) between 44 and 47 the concentration of sulphuric acid in the said bath being defined by the formula:
  • Percentage concentration by weight of sulphuric acid l.26y ⁇ 8i2 thereafter subjecting the extruded filaments to a stretching operation to increase their length by 20G-250% while they -are still wet from the spinning bath, washing the filaments in a more dilute acid bath and then causing them to travel in free air under insufficient tension to cause stretching, for a distance of at least three metres and for a period of at least three seconds, thus allowing the laments to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained.
  • Percentage concentration by Weight of sulphuric acid 1.26y+8i2 thereafter subjecting the extruded laments to a Stretching operation to increase their length by 20G-250% while they are still wet from the spinning bath, washing the filaments in a more dilute acid bath and then causing them to travel in free air under insufficient tension to cause stretching, for a distance of at least three metres and for a period of at least three seconds, thus allowing the laments to relax while still in the acid condition and then winding or winding and twisting the laments thus obtained.
  • Percentage concentration by weight of sulphuric acid 1.26y 8 i 2 thereafter subjecting the extruded laments to a stretching operation to increase their length by 20G-250% while they are still wet from the spinning bath, washing the laments in a more dilute acid bath and then causing them to travel in free air under insufficient tension to cause stretching, for a distance of at least three metres and for a period of at least three seconds, thus allowing the laments to relax while still in the acid condition and then winding or winding and twisting the filaments thus obtained.
  • Viscose rayon filaments having in the airdry condition a tenacity greater than 4.8 g. per denier and an elongation at breaking point greater than 8% and having a work-till-rupture value greater than 20 g. cm./metre/denier, and made by the process defined in claim 1.
  • Viscose rayon iilaments having in the airdry condition a tenacity greater than 5.0 g. per denier and an elongation at breaking point greater than 8.5% and having a work-till-rupture value greater than 20 g. cm./metre/denier, and made by the process dened in claim 12.
  • NICOLAS DRISCH. ROLAND BREPSON NICOLAS DRISCH. ROLAND BREPSON.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
US173924A 1948-05-11 1950-07-14 Production of viscose rayon Expired - Lifetime US2586796A (en)

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GB12944/48A GB650896A (en) 1948-05-11 1948-05-11 Improvements in or relating to the production of viscose rayon

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US (1) US2586796A (en, 2012)
CH (1) CH283711A (en, 2012)
DE (1) DE971618C (en, 2012)
FR (1) FR985847A (en, 2012)
GB (1) GB650896A (en, 2012)
NL (1) NL88549C (en, 2012)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699983A (en) * 1951-08-03 1955-01-18 Textile & Chem Res Co Ltd Production of viscose rayon
US2937922A (en) * 1954-03-24 1960-05-24 Rayonier Inc Viscose process
US2952508A (en) * 1953-09-16 1960-09-13 Rayonier Inc Viscose process and products produced thereby
WO2009086571A3 (de) * 2008-01-11 2009-09-11 Lenzing Ag Mikrofaser
CN102409461A (zh) * 2011-09-26 2012-04-11 宜宾海丝特纤维有限责任公司 利用潮丝饼制备绣花线的工艺方法
CN103643313A (zh) * 2013-12-04 2014-03-19 宜宾丝丽雅集团有限公司 适用于卷绕装置外置的新型纺丝机的纺丝工艺

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL299635A (en, 2012) * 1962-11-06
CN100395385C (zh) * 2005-11-16 2008-06-18 东华大学 用于帘子线的莱赛尔纤维的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE838936C (de) * 1944-07-25 1952-05-15 Glanzstoff Ag Verfahren zur Herstellung von Viscosekunstfaeden

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699983A (en) * 1951-08-03 1955-01-18 Textile & Chem Res Co Ltd Production of viscose rayon
US2952508A (en) * 1953-09-16 1960-09-13 Rayonier Inc Viscose process and products produced thereby
US2937922A (en) * 1954-03-24 1960-05-24 Rayonier Inc Viscose process
WO2009086571A3 (de) * 2008-01-11 2009-09-11 Lenzing Ag Mikrofaser
US20100291823A1 (en) * 2008-01-11 2010-11-18 Lenzing Ag Microfiber
US11932969B2 (en) 2008-01-11 2024-03-19 Lenzing Aktiengesellschaft Microfiber
CN102409461A (zh) * 2011-09-26 2012-04-11 宜宾海丝特纤维有限责任公司 利用潮丝饼制备绣花线的工艺方法
CN102409461B (zh) * 2011-09-26 2014-02-26 宜宾海丝特纤维有限责任公司 利用粘胶长丝的潮丝饼制备绣花线的工艺方法
CN103643313A (zh) * 2013-12-04 2014-03-19 宜宾丝丽雅集团有限公司 适用于卷绕装置外置的新型纺丝机的纺丝工艺
CN103643313B (zh) * 2013-12-04 2016-06-22 宜宾丝丽雅集团有限公司 适用于卷绕装置外置的纺丝机的纺丝工艺

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NL88549C (en, 2012)
CH283711A (fr) 1952-06-30
GB650896A (en) 1951-03-07
FR985847A (fr) 1951-07-24

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