US3337671A - Method of making regenerated cellulose filaments - Google Patents

Method of making regenerated cellulose filaments Download PDF

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Publication number
US3337671A
US3337671A US489378A US48937865A US3337671A US 3337671 A US3337671 A US 3337671A US 489378 A US489378 A US 489378A US 48937865 A US48937865 A US 48937865A US 3337671 A US3337671 A US 3337671A
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Prior art keywords
filaments
bath
viscose
spinning
per liter
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Expired - Lifetime
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US489378A
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Inventor
Drisch Nicolas
Herrbach Paul
Rodier Henri
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Chimiotes S A
CHIMIOTES SA
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Chimiotes S A
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Priority claimed from FR825044A external-priority patent/FR1266492A/fr
Priority claimed from FR871411A external-priority patent/FR80314E/fr
Application filed by Chimiotes S A filed Critical Chimiotes S A
Priority claimed from US520032A external-priority patent/US3337673A/en
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Publication of US3337671A publication Critical patent/US3337671A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/22—Corrugating
    • B29C53/30—Corrugating of tubes
    • B29C53/305—Corrugating of tubes using a cording process
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/04—Hollow or tubular parts of organs, e.g. bladders, tracheae, bronchi or bile ducts
    • A61F2/06—Blood vessels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/22—Corrugating
    • B29C53/30—Corrugating of tubes
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • 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
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/02—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of cellulose, cellulose derivatives or proteins
    • 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
    • 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
    • D01F2/08—Composition of the spinning solution or the bath
    • 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
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the present invention relates to a novel method for the production of regenerated cellulose filaments and fibers of high tenacities, having excellent dimensional stability to repeated washings, a substantially circular cross-section, a microfibrillar structure (all core structure) similar to that of cotton as well as a high degree of orientation and good resistance to bending. More particularly, the invention relates to a process for spinning viscose which contains cellulose having a DP of 500 at least, a gamma number of 45-100, and a viscosity of 1504000 poises, in a very dilute sulfuric acid bath containing sodium sulfate and substantially no zinc sulfate.
  • the improvement of the present invention resides in incorporating formaldehyde in the viscose immediately prior to spinning (e.g., injected at the head of the spinning frame) or to the dilute spinning bath, which unexpectedly retards regeneration, whereby filaments with homogenous, stable microfibrillar structure (all core structure) are formed, showing substantially circular cross-section as well as a smooth, regular, uniform surface.
  • Another object of the present invention is to provide a process for the production of regenerated cellulose filaments -and fibers which have high tenacities, and all core microfibrillar structure, substantially circular crosssection, as well as smooth non-crenulated surface.
  • Still another object of the present invention is to provide a process for the production of regenerated cellulose filaments and fibers, which process involves the spinning of viscose which contains cellulose having a DP of at least 500, a gamma number of 45-100 and a viscosity of 1501000 poises, in a dilute bath containing a small amount of sulphuric acid and sodium sulphate with substantially no zinc sulphatee.g., 0.001 gram per liter to .1 gram per liter.
  • both coagulation and regeneration take place in the more concentrated Muller bath.
  • formaldehyde to the more concentrated baths (e.g., Muller baths) to prolong the regeneration period, with the thought that it forms a complex with the cellulose xanthate, and keeps the filaments in a metastable, stretchable state while they are being stretched, permitting uniaxial orientation of the crystalline elements being developed during regeneration.
  • the filaments obtained from a Muller bath are of the all skin or skin-core type and do not have any of the superior qualities of the filaments produced from a dilute bath as in the present invention.
  • the filaments and fibers thus produced are known in the art as polynosic, and they have excellent tenacity values with a high ratio of Wet tenacity to dry tenacity. Furthermore, the polynosic filaments exhibit reduced swelling and are dimensionally stable under repeated washings and dryings. Their elongations are relatively slight and the elasticity modulus in the wet state is relatively high. Therefore, the properties of these filaments are very similar to those of natural cellulose fibers.
  • a viscose which contains at least 3% cellulose, from 1.59% total caustic soda, and whose sulphurization degree is at least 35% relatively to the alpha cellulose.
  • the gamma number of the viscose, when spun must be between 45 and 100.
  • the cellulose contained in the viscose must have a DP of at least 400, preferably greater than 500, and must be free as much as possible from short chains so that a thread having an excellent bending strength may be obtained.
  • the viscose at the time of spinning have a viscosity between 1501000 poises, preferably greater than 400 poises.
  • the viscose is spun into a first bath which contains 8 to 35 grams per liter of sulfuric acid and -65 grams per liter sodium sulfate. Furthermore, it is essential that the sum of the sulfuric acid and sodium sulfate concentrations in the first bath does not exceed the range of 8-75 grams per liter.
  • the formaldehyde is added'to the dilute spinning bath, it must be added in the range of 1-40 grams per liter of the bath.
  • the formaldehyde may be incorporated in the viscose immediately prior to spinning and when added in this manner it should be within the range of 140 grams per kilogram of viscose.
  • the form aldehyde may be added simultaneously to the viscose immediately prior to spinning and to the first dilute spinning bath.
  • the total amount of formaldehyde when added in this manner should not exceed 40 grams per liter of the bath.
  • the invention has substantially eliminated zinc sulfate from the spinning baththat is, the bath may contain zinc sulfate in the amount of 0.001 gram per liter to .1 gram per liter.
  • the bath temperature is preferably within the range of 10-30 C.
  • this invention is primarily based upon the discovery that by the addition of formaldehyde to the viscose immediately prior to spinning or to the first spinning bath, regeneration may be substantially slowed down with consequent increase in stretchability whereby a filament having excellent dimensional stability and tenacity may be obtained.
  • the viscose have a viscosity of 1501000 poises. It was found that when lower viscosities are utilized with baths of low acid and low sulfate concentrations (within ranges of this invention) it is very difiicult, if not impossible, to spin.
  • the filaments obtained from the first bath may be stretched by preferably over 200% and the stretching action may take place in the first bath or in a second very hot acid bath, as well as during travel through the air between the first bath and the second.
  • the tow coming from the second 'bath may be subjected to conventional treatments and degasified (freed from residual CS in a third hot acid bath. Further, the tow may be cut in the acid state and the fibers then fixed in order to obtain curled fibers.
  • the filaments are received on a bobbin but they may be subjected to treatments on thread advancing reels according to the continuous spinning process.
  • the filaments produced in accordance with the present invention have a very high tenacity of at least 5 g./den. in the conditioned state, 4 g./den. in the wet state, as well as a high modulus of elasticity evidenced from an elongation in the wet state of less than 3% under a load of 0.5 g./den.
  • the filaments have an all core structure and have a substantially round cross-section, that is, a smooth, even regular contour and their swelling degree, which is a function of the spinning conditions, is commonly less than 50%.
  • the skin of the filaments is dyed blue, while the core is dyed yellow.
  • filaments produced in accordance with the instant invention and dyed with this technique show an all core structure and differ completely from filaments produced from the more concentrated Muller baths, those filaments showing an all-skin or a skin-core structure.
  • the filaments obtained in accordance with the present invention are nearer to cotton than other filaments of regenerated cellulose. Furthermore, X-ray examination as well as birefringence measurements reveal an extremely orientated structure and it has been found that despite this high degree of orientation the filaments have a good resistance to repeated bending. It has also been found that the fibers are extremely stable to and are not substantially modified by treatment with 6% caustic soda, whereas under the same conditions threads of ordinary rayon are considerably disorganized and even destroyed. Thus, fabrics made from the filaments of the present invention have excellent dimensional stability when subjected to repeated washings.
  • the alkali resistance of the fibers of the present invention is due to the microcrystalline structure of the filaments for it has been found that other rayon filaments having the same high DP are readily attacked by caustic soda whereas the fibers of the present invention are not.
  • the tow was then passed into a second regeneration bath containing 20 g./liter of sulphuric acid and 10 g./ liter of sodium sulphate at a temperature of 93 C., and at the same time was subjected in this bath to a stretch of 200%, which gives a total stretch of 275%. The length of travel through this bath is 150 cm.
  • the tow is finally wound under tension on a bobbin. After the usual treatments of de-acidification, washing, desulphurization and oiling, a thread Was obtained which had the following characteristics:
  • a viscose was prepared in accordance with the procedure set forth in Example I wherein the cellulose concentration was 4.5% and the caustic soda concentration was 5.5%.
  • the viscosity of the viscose was only 70 poises; however, the other characteristics were identical with those of Example I, e.g., DP of 550, gamma number of 75, etc.
  • the viscose was extruded through a spinneret of 2000 6 holes of mm. in the same bath as used in Example I, that is, a bath containing 25 grams of sulphuric acid, 15 grams of sodium sulphate, and 10 grams of formaldehyde per liter at a temperature of 20 C.
  • Example II It was found that it was impossible: to spin at a speed of 10 meters/minute (exit from the first bath) as in Example I. Further, the slightly gelified viscose did not have the necessary cohesion to enable filaments to be drawn and stretched outside of the bath. Moreover, the viscose jets formed at the spinneret exhibited a strong tendency to stick together.
  • the process of the present invention overcomes the disadvantages illustrated herein for it was unexpectedly found that by employing a high viscosity (e.g., at least poises) the gelified filaments formed had sufficient cohesion so that they could be superficially coagulated without rupture. Also, the filaments could be drawn outside the first bath at a speed in order of 10 meters/ minute.
  • a high viscosity e.g., at least poises
  • the viscose and first dilute bath used were exactly the same as used in Example I.
  • the viscose was spun by means of a spinneret having 2000 apertures of of a millimeter in the first bath under exactly the same conditions as Example I.
  • the total stretch was 260% and the filament properties were as follows:
  • Example I was repeated except that a solution of formaldehyde was injected into the viscose immediately prior to spinning so that this viscosecontained 20 g. of formaldehyde per kilogram. No formaldehyde was added to the first bath. In these conditions, the spinning equilibrium was about the same as in Example I. As a result of this experiment, a thread was obtained which had substantially the same characteristics as the thread formed in Example I.
  • EXAMPLE V A viscose having a composition of 5% of cellulose and 2.4% of caustic soda was spun by means of a spinneret having 18,000 holes each of of a millimeter, in a first bath containing 28 g./liter of sulphuric acid and 19 g./liter of sodium sulphate, at a temperature of 19 C. To this bath was added 10 g./liter of formaldehyde and suitable surface-active agents. The tow formed was passed through a second regeneration bath, the stretches, the distance through the bath and the spinning speeds being substantially the same as those indicated in Example I. Finally, the tow passed through a third, hot bath for degasifying and cut in the acid state. After finishing, fibers were obtained which had the following characteristics:
  • Example V Swelling do 49 7 EXAMPLE v1
  • Example V was repeated except that a solution of formaldehyde was injected into the viscose immediately prior to spinning, so that this viscose contained 15 grams of formaldehyde per kilogram of viscose. No formaldehyde was added to the first bath. As aresult of this experiment, a thread was obtained which had substantially the same characteristics as the thread formed in Example V.
  • EXAMPLE VII A viscose containing 5% of cellulose and 2.5% of caustic soda was spun through a tube by means of a spinneret having 40 holes of of a millimetre, into a first bath containing 30 g./ liter of sulphuric acid, 17 g./liter of sodium sulphate and 5 g./liter of formaldehyde, at a temperature of 23 C. The length of travel in the first bath was 450 cm. and the stretch was 35%. The thread issued from the first bath at a speed of 20 m./ minute and was then subjected to a stretch of 190% in a second hot bath similar to that of Example I.
  • the thread which now had a speed of 58 metres per minute was subjected successively, on two-cage bobbins in parallel spirals, to de-acidification, washing and desulphurization treatments. It was finally dried and twisted, all these operations being carried out continuously.
  • Example VII was repeated except that a solution of formaldehyde was injected into the viscose immediately prior to spinning so that this viscose contained 15 grams of formaldehyde per kilogram of viscose. No aldehyde was added to the first batch. As a result of this experiment, a thread was obtained which had substantially the same characteristics as the thread formed in Example VII.
  • Example VIII was repeated except that the formaldehyde was injected to the viscose in the amount of 20 grams per kilogram. As a result of this experiment, the thread obtained had substantially the same characteristics as the thread formed in Example VII.
  • Example VII was repeated except that the first bath contained 10 grams per liter sulphuric acid and 50 grams per liter of sodium sulphate. The other conditions of Example VII were repeated, and, as a result, the thread formed had substantially the same characteristics as the threads formed in Example VII.
  • the threads and fibers described herein are essentially suitable for textile uses, but their features, more particularly high tenacity and high modulus of elasticity, also make them suitable for certain technical applications in particular in the rubber industry.
  • the improvement which comprises adding to a viscose immediately prior to spinning 1 to 40 grams per kilogram of formaldehyde, spinning said viscose which contains a cellulose whose DP is at least 500, and has a viscosity of 150 to 1000 poises, and a gamma number of 45 to 100 into a first dilute bath containing about 8 to about 35 grams per liter of sulphuric acid, about 0 to grams per liter of sodium sulphate, the sum of the sulphuric acid and sodium sulphate concentrations being 8 to grams per liter, and about 0.001 to .1 gram per liter of zinc sulfate, at a temperature between 10 C.
  • the filaments obtained have a very high tenacity both in the conditioned state and in the wet state, excellent dimensional stability, high modulus of elasticity in the wet state, a swelling value less than 55% and a uniform substantially round cross section as well as a smooth, regular surface contour.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Mechanical Engineering (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Gastroenterology & Hepatology (AREA)
  • Pulmonology (AREA)
  • Cardiology (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Artificial Filaments (AREA)
US489378A 1958-07-31 1965-09-22 Method of making regenerated cellulose filaments Expired - Lifetime US3337671A (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US892980XA 1958-07-31 1958-07-31
US1156934XA 1958-07-31 1958-07-31
US1209279XA 1958-07-31 1958-07-31
FR801445A FR1307907A (fr) 1958-07-31 1959-07-29 Procédé pour la fabrication d'artères artificielles et pour le blanchiment des filaments de tétrafluoroéthylène coloré susceptibles de servir à la fabrication desdites artères artificielles
FR825044A FR1266492A (fr) 1960-04-22 1960-04-22 Perfectionnements dans la fabrication des fils, fibres, câblés, pellicules..., en cellulose régénérée
FR871411A FR80314E (fr) 1960-04-22 1961-08-23 Perfectionnements dans la fabrication des fils, fibres, câbles, pellicules, en cellulose régénérée
FR871412A FR80315E (fr) 1960-04-22 1961-08-23 Perfectionnements dans la fabrication des fils, fibres, câbles, pellicules, en cellulose régénérée
FR904601A FR82282E (fr) 1960-04-22 1962-07-20 Perfectionnements dans la fabrication des fils, fibres, câbles, pellicules, en cellulose régénérée
US520032A US3337673A (en) 1958-07-31 1965-12-20 Uniformly corrugated prosthesis and process of making same

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US3337671A true US3337671A (en) 1967-08-22

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US489378A Expired - Lifetime US3337671A (en) 1958-07-31 1965-09-22 Method of making regenerated cellulose filaments

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US (1) US3337671A (xx)
FR (1) FR1307907A (xx)
GB (1) GB8929801A (xx)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3388117A (en) * 1963-03-28 1968-06-11 Courtaulds North America Inc Filaments of regenerated cellulose
US20070224419A1 (en) * 2006-03-21 2007-09-27 Georgia-Pacific Consumer Products Lp Absorbent sheet having regenerated cellulose microfiber network
US20080173419A1 (en) * 2007-01-19 2008-07-24 Georgia-Pacific Consumer Products Lp Method of making regenerated cellulose microfibers and absorbent products incorporating same
US20090020248A1 (en) * 2006-03-21 2009-01-22 Georgia-Pacific Consumer Products Lp Absorbent sheet incorporating regenerated cellulose microfiber
US20090020139A1 (en) * 2006-03-21 2009-01-22 Georgia-Pacific Consumer Products Lp High efficiency disposable cellulosic wiper
WO2012017034A1 (de) * 2010-08-05 2012-02-09 Cordenka Gmbh Korde aus cellulosischen multifilamentgarnen mit erhöhtem einzelfilamenttiter
US8361278B2 (en) 2008-09-16 2013-01-29 Dixie Consumer Products Llc Food wrap base sheet with regenerated cellulose microfiber
US8540846B2 (en) 2009-01-28 2013-09-24 Georgia-Pacific Consumer Products Lp Belt-creped, variable local basis weight multi-ply sheet with cellulose microfiber prepared with perforated polymeric belt

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1543586A (en) * 1978-07-24 1979-04-04 Whitworth B Flexible tube
DE4446473C1 (de) * 1994-12-23 1996-03-07 Maurer Ingo Verfahren zur Herstellung von Papierlampenschirmen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2937070A (en) * 1955-08-02 1960-05-17 Du Pont Viscose process
US3018158A (en) * 1959-05-05 1962-01-23 Rayonier Inc Viscose process
US3107970A (en) * 1960-10-04 1963-10-22 Toho Rayon Kk Process for the manufacture of high tenacity viscose rayon
US3109700A (en) * 1962-05-04 1963-11-05 Courtaulds North America Inc Method for making rayon filaments

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2937070A (en) * 1955-08-02 1960-05-17 Du Pont Viscose process
US3018158A (en) * 1959-05-05 1962-01-23 Rayonier Inc Viscose process
US3107970A (en) * 1960-10-04 1963-10-22 Toho Rayon Kk Process for the manufacture of high tenacity viscose rayon
US3109700A (en) * 1962-05-04 1963-11-05 Courtaulds North America Inc Method for making rayon filaments

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3388117A (en) * 1963-03-28 1968-06-11 Courtaulds North America Inc Filaments of regenerated cellulose
US8980011B2 (en) 2006-03-21 2015-03-17 Georgia-Pacific Consumer Products Lp Method of cleaning residue from a surface using a high efficiency disposable cellulosic wiper
US9345374B2 (en) 2006-03-21 2016-05-24 Georgia-Pacific Consumer Products Lp Method of cleaning residue from a surface using a high efficiency disposable cellulosic wiper
US20090020248A1 (en) * 2006-03-21 2009-01-22 Georgia-Pacific Consumer Products Lp Absorbent sheet incorporating regenerated cellulose microfiber
US9051691B2 (en) 2006-03-21 2015-06-09 Georgia-Pacific Consumer Products Lp Method of making a wiper/towel product with cellulosic microfibers
US7718036B2 (en) * 2006-03-21 2010-05-18 Georgia Pacific Consumer Products Lp Absorbent sheet having regenerated cellulose microfiber network
US20100212850A1 (en) * 2006-03-21 2010-08-26 Georgia-Pacific Consumer Products Lp Absorbent sheet having regenerated cellulose microfiber network
US7985321B2 (en) 2006-03-21 2011-07-26 Georgia-Pacific Consumer Products Lp Absorbent sheet having regenerated cellulose microfiber network
US9057158B2 (en) 2006-03-21 2015-06-16 Georgia-Pacific Consumer Products Lp Method of making a wiper/towel product with cellulosic microfibers
US9655491B2 (en) 2006-03-21 2017-05-23 Georgia-Pacific Consumer Products Lp Method of cleaning residue from a surface using a high efficiency disposable cellulosic wiper
US8187422B2 (en) 2006-03-21 2012-05-29 Georgia-Pacific Consumer Products Lp Disposable cellulosic wiper
US8187421B2 (en) 2006-03-21 2012-05-29 Georgia-Pacific Consumer Products Lp Absorbent sheet incorporating regenerated cellulose microfiber
US8216425B2 (en) 2006-03-21 2012-07-10 Georgia-Pacific Consumer Products Lp Absorbent sheet having regenerated cellulose microfiber network
US9510722B2 (en) 2006-03-21 2016-12-06 Georgia-Pacific Consumer Products Lp Method of cleaning residue from a surface using a high efficiency disposable cellulosic wiper
US9492049B2 (en) 2006-03-21 2016-11-15 Georgia-Pacific Consumer Products Lp Method of cleaning residue from a surface using a high efficiency disposable cellulosic wiper
US9382665B2 (en) 2006-03-21 2016-07-05 Georgia-Pacific Consumer Products Lp Method of making a wiper/towel product with cellulosic microfibers
US9370292B2 (en) 2006-03-21 2016-06-21 Georgia-Pacific Consumer Products Lp Absorbent sheets prepared with cellulosic microfibers
US9345375B2 (en) 2006-03-21 2016-05-24 Georgia-Pacific Consumer Products Lp Method of cleaning residue from a surface using a high efficiency disposable cellulosic wiper
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GB8929801A (xx) 1900-01-01

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