US20120202398A1 - Biodegradable fibre and its process of manufacture - Google Patents
Biodegradable fibre and its process of manufacture Download PDFInfo
- Publication number
- US20120202398A1 US20120202398A1 US13/497,209 US201013497209A US2012202398A1 US 20120202398 A1 US20120202398 A1 US 20120202398A1 US 201013497209 A US201013497209 A US 201013497209A US 2012202398 A1 US2012202398 A1 US 2012202398A1
- Authority
- US
- United States
- Prior art keywords
- cellulose
- fibre
- cellulose acetate
- fibres
- fibre according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
- A24D3/068—Biodegradable or disintegrable
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/02—Manufacture of tobacco smoke filters
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- 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
-
- 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
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
-
- 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
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
Definitions
- the present invention concerns biodegradable composite fibres.
- biodegradable polymers such as PHB/PVB and starches as the filter tow or fibre raw material.
- the present invention seeks to address these problems.
- FIG. 1 shows three slides showing fibres of i) cellulose acetate; ii) cellulose; and iii) a blend of cellulose and cellulose acetate in accordance with the invention.
- FIG. 2 shows the slides of FIG. 1 after 2 weeks biodegradation under anaerobic conditions.
- FIG. 3 shows the slides of FIG. 1 after 4 weeks biodegradation under anaerobic conditions.
- FIG. 4 shows the slides of FIG. 1 after 6 weeks biodegradation under anaerobic conditions.
- a biodegradable fibre comprising composite filaments of cellulose and cellulose acetate.
- Cellulose and cellulose acetate are typically cast in the form of fibres or films.
- this invention concerns fibres.
- Preferred fibres in accordance with the invention comprise fibres spun from a coagulated solution of cellulose and cellulose acetate.
- composite filaments of cellulose/cellulose acetate shall be understood to mean filaments spun from a dope comprising cellulose and cellulose acetate.
- composite filaments of cellulose/cellulose acetate have significantly greater biodegradability than equivalent filaments comprising only cellulose or cellulose acetate. Without wishing to be bound by any such theory, we believe that the presence of acetate in the composite may disrupt the crystallinity of the cellulose, causing it to biodegrade more rapidly than cellulose itself.
- cellulose is cast or spun from viscose, and it is difficult or impossible to cast or spin cellulose acetate from the same blend because of the likelihood of hydrolysis of the cellulose acetate under such conditions.
- cellulose acetate is conventionally cast or spun from acetone and it is difficult or impossible to cast or spin cellulose from the same blend because of the limited solubility of cellulose in acetone.
- the fibre of the invention is preferably formed from fibres of cellulose and cellulose acetate spun or cast as a blend from an ionic liquid (IL) or from N-methylmorphilone-N-oxide (NMMO).
- IL ionic liquid
- NMMO N-methylmorphilone-N-oxide
- ILs and NMMO for dissolving cellulose and other polymers has been well documented, for example in US20050288484 and US 20070006774 of the University of Alabama, US20080188636 of the North Carolina State University and WO2005098546 of Holbrey et al.
- a wide range of ionic liquids including those disclosed in the aforesaid publications, are suitable for dissolving cellulose and cellulose acetate and for casting as blends fibres or films therefrom.
- suitable IL include those based on imidazole, pyrrole, thiazole or pyrazole cations in combination with halogen, phosphate, carboxylate or metal chloride anions.
- ILs include 1-butyl-3-methylimidazolium chloride (BMIM-Cl) 1-butyl-3-methylimidazolium acetate (BMIM-Ac) and 1-ethyl-3-methylimidazolium acetate (EMIM-Ac).
- BMIM-Cl 1-butyl-3-methylimidazolium chloride
- BMIM-Ac 1-butyl-3-methylimidazolium acetate
- EMIM-Ac 1-ethyl-3-methylimidazolium acetate
- the solution of cellulose and cellulose acetate from which fibres are spun or cast is referred to herein as a dope.
- the dope may also comprise an aprotic solvent such as DMSO, DMF, THF or dioxane to aid dissolution of the cellulose and/or cellulose acetate.
- aprotic solvent such as DMSO, DMF, THF or dioxane.
- DMSO dimethyl methoxysulfate
- the blend of cellulose acetate and cellulose in the dope may also comprise one or more further thermoplastic materials, such as polyhydroxyalkanoates such as PHB and/or PHVB which may add further functionality, such as water barrier functionality, to the fibres of the invention.
- Other functional additives may include triacetin, polyacrylonitrile (PAN), poly-2-hydroxyethylmethylacrylate (PHEMA), polyvinylalcohol (PVA), polyaniline and polyethylene glycol for functional purposes such as modification of absorption profile, degradation enhancement (by, for example, water-soluble materials), and processability improvement, in connection for example with wet strength.
- the weight ratio of cellulose to cellulose acetate in the dope, and consequently in the fibre of the invention is from 10:90 to 90:10, for example from 20:80 to 80:20, or from 30:70 to 70:30.
- the dope comprises a solids content of up to about 50% w/w, preferably up to about 40% w/w, more preferably up to about 30% w/w and most preferably up to about 20% w/w.
- the fibres of the invention may additionally comprise one or more plasticisers, such as triacetin.
- the plasticiser may be included in the dope, or may added subsequent to spinning or casting, for example by spraying onto the surface of the formed fibre.
- the fibres of the invention may additionally comprise a catalyst promoting oxidative degradation of the fibre.
- Suitable catalysts include iron and copper oxides and chlorides, which may be introduced into the fibre by immersing the composite filaments in an aqueous solution of a water-soluble iron or copper salt, such as sulphate or chloride, and precipitating the oxide (preferably in nano-form) onto or into the filament by treatment with sodium hydroxide or other suitable precipitating agent.
- the fibres may also comprise one or more lubricants to reduce electrostatic charge.
- Preferred lubricants include mineral oils. For example, 1% w/w of mineral oil with an emulsifier may be applied to the composite filaments during spinning of the fibres.
- the fibres of the invention comprise composite filaments of cellulose/cellulose acetate manufactured at 1, 5 or 9 denier per filament (filament thickness (denier per filament) being defined as the mass (grams) of 9000 m of a single filament).
- total denier (defined as the total mass of 9000 m of fibre, typically comprising many thousands, for example 11,000, individual fibres) will vary considerably depending on the methods employed in fibre spinning and the number of individual filaments in the fibre.
- One typical fibre mass would 35,000 g.
- the fibres of the invention comprise fibres having a trilobal filament cross-section (optionally formed using triangular spinneret holes) to optimise surface area.
- the moisture content of the fibres according to the invention is preferably at least about 2% w/w, more preferably at least about 5% w/w, even more preferably at least about 10% w/w.
- Moisture content has been found to be important for preventing electrical charges, but should preferably not be too high (e.g. not higher than 50% w/w) because with a very high moisture content it may be difficult for the fibre to retain a crease.
- the fibres of the invention preferably comprise entangled filaments.
- Also provided in accordance with the invention is a material woven or otherwise made from the fibre as hereinbefore described.
- a garment or soft furnishing made at least partly from a material as hereinbefore described.
- Also provided in accordance with the invention is a process for manufacturing fibres comprising providing a solution comprising a blend of cellulose and cellulose acetate in an ionic liquid or in NMMO, and spinning or casting the blend into a protic solvent to generate fibres.
- Water is the preferred protic solvent for the regenerative casting of the blend.
- composite cellulose/cellulose acetate materials can be produced at any ratio by regenerating solutions in water and/or other protic solvents.
- the rate of coagulation in water has been found to be dependant on the cellulose acetate content of the dope, where increased levels of cellulose acetate reduce the rate of coagulation.
- this invention provides a biodegradable film cast from a coagulated dope comprising cellulose and cellulose acetate, the resulting film being a cellulose/cellulose acetate composite material.
- FIG. 1 shows three slides showing fibres of i) cellulose acetate; ii) cellulose; and iii) a blend of cellulose and cellulose acetate in accordance with the invention.
- FIG. 2 shows the slides of FIG. 1 after 2 weeks biodegradation under anaerobic conditions.
- FIG. 3 shows the slides of FIG. 1 after 4 weeks biodegradation under anaerobic conditions.
- FIG. 4 shows the slides of FIG. 1 after 6 weeks biodegradation under anaerobic conditions.
- fibres were spun from solutions of i) cellulose (DP ⁇ 800) and ii) 1:1 cellulose: cellulose acetate (Eastman, CA-398-30), at 10% solids in EMIM-Ac: DMSO (20:80).
- EMIM-Ac DMSO (20:80).
- a 40-orifice spinneret with an orifice diameter of 70 ⁇ m was used, which was submerged in a room temperature coagulation bath containing clean water.
- the fibres were reeled-up wet, extensively washed on the reel then dried at 50° C.
- a surprising property of these composite materials is that the rate of biodegradation under anaerobic environments exceeds that of cellulose and greatly exceeds that of cellulose acetate under the same conditions (see appendix 1). It is thought (although this theory is in no way to be considered binding) that the two components form an intimately mixed composite and that the enhanced rate of degradation arises from a reduction in the crystallinity of the cellulose. Degradation of the cellulose component of the composite is thought to lead to the cellulose acetate component being deposited on a molecular scale. We have also found that the rate of biodegradation under aerobic conditions of the fibres in accordance with the invention is similarly improved.
- Fibre according to the invention is manufactured using a dry-spinning process.
- a dope is first prepared by dissolving cellulose diacetate and cellulose (1:1 blend) at 10% solids in EMIM-Ac: DMSO (20:80). TiO2 is added to give a whitened appearance.
- the dope is then filtered and spun into chambers, causing the filaments to solidify and become thinner. More than 10,000 filaments are spun from a series of spinning cabinets, which are combined to form a single band.
- a material is woven from the fibre, and a garment is made from the material.
- the resulting garment is found to retain to advantageous biodegradability properties as shown in Example 1 and to have an acceptable comfort signature.
Abstract
The present invention concerns a biodegradable fibre comprising composite filaments of cellulose and cellulose acetate, and a process for making such a fibre comprising providing a solution dope comprising a blend of cellulose and cellulose acetate in an ionic liquid or in N-methylmorphilone-N-oxide (NMMO), and spinning casting the blend into a protic solvent to generate fibres. The invention also concerns materials made from such a fibre, and garments or soft furnishings made from such a material.
Description
- This application claims priority to International Patent Application No. PCT/GB2010/051771, filed Oct. 21, 2010, which claims priority to Great Britain Patent Application No. 0918633.9, filed Oct. 23, 2009. The entirety of all of the aforementioned applications is incorporated herein by reference.
- The present invention concerns biodegradable composite fibres.
- One of the most pressing issues for manufacturers of fibres is the rate at which the fibres biodegrade. Cellulose acetate fibres can take between one month and three years to biodegrade, dependant on environmental conditions.
- A range of approaches to the preparation of biodegradable fibres, particularly for use in the manufacture of cigarette filter tows, have been suggested and include the use of composites of cellulose acetate with other biodegradable polymers, additives for increasing the rate of degradation of cellulose acetate, cellulose acetate with a low degree of substitution (DS) for increased biodegradability, and biodegradable polymers such as PHB/PVB and starches as the filter tow or fibre raw material.
- However, to date no satisfactory commercial solution has been found for producing consumer-acceptable fibres that degrade sufficiently quickly
- The present invention seeks to address these problems.
- The invention will now be more particularly described in the following drawings:
-
FIG. 1 shows three slides showing fibres of i) cellulose acetate; ii) cellulose; and iii) a blend of cellulose and cellulose acetate in accordance with the invention. -
FIG. 2 shows the slides ofFIG. 1 after 2 weeks biodegradation under anaerobic conditions. -
FIG. 3 shows the slides ofFIG. 1 after 4 weeks biodegradation under anaerobic conditions. -
FIG. 4 shows the slides ofFIG. 1 after 6 weeks biodegradation under anaerobic conditions. - According to the present invention there is provided a biodegradable fibre comprising composite filaments of cellulose and cellulose acetate.
- Cellulose and cellulose acetate are typically cast in the form of fibres or films. In one of its aspects, this invention concerns fibres. Preferred fibres in accordance with the invention comprise fibres spun from a coagulated solution of cellulose and cellulose acetate.
- Reference herein to composite filaments of cellulose/cellulose acetate shall be understood to mean filaments spun from a dope comprising cellulose and cellulose acetate.
- We have found that composite filaments of cellulose/cellulose acetate have significantly greater biodegradability than equivalent filaments comprising only cellulose or cellulose acetate. Without wishing to be bound by any such theory, we believe that the presence of acetate in the composite may disrupt the crystallinity of the cellulose, causing it to biodegrade more rapidly than cellulose itself.
- Conventionally, cellulose is cast or spun from viscose, and it is difficult or impossible to cast or spin cellulose acetate from the same blend because of the likelihood of hydrolysis of the cellulose acetate under such conditions. Conversely, cellulose acetate is conventionally cast or spun from acetone and it is difficult or impossible to cast or spin cellulose from the same blend because of the limited solubility of cellulose in acetone.
- However, we have found that by casting or spinning cellulose and cellulose acetate from an ionic liquid (IL) or from N-methylmorphilone-N-oxide (NMMO), it is possible to form spun fibres and cast films comprising a composite blend of these materials. The enhanced biodegradability of such composites and their suitability for use in fibre manufacture has not previously been recognised.
- Consequently, the fibre of the invention is preferably formed from fibres of cellulose and cellulose acetate spun or cast as a blend from an ionic liquid (IL) or from N-methylmorphilone-N-oxide (NMMO).
- The use of ILs and NMMO for dissolving cellulose and other polymers has been well documented, for example in US20050288484 and US 20070006774 of the University of Alabama, US20080188636 of the North Carolina State University and WO2005098546 of Holbrey et al. A wide range of ionic liquids, including those disclosed in the aforesaid publications, are suitable for dissolving cellulose and cellulose acetate and for casting as blends fibres or films therefrom. General types of suitable IL include those based on imidazole, pyrrole, thiazole or pyrazole cations in combination with halogen, phosphate, carboxylate or metal chloride anions. Particularly preferred ILs include 1-butyl-3-methylimidazolium chloride (BMIM-Cl) 1-butyl-3-methylimidazolium acetate (BMIM-Ac) and 1-ethyl-3-methylimidazolium acetate (EMIM-Ac).
- The solution of cellulose and cellulose acetate from which fibres are spun or cast is referred to herein as a dope. The dope may also comprise an aprotic solvent such as DMSO, DMF, THF or dioxane to aid dissolution of the cellulose and/or cellulose acetate. One particularly preferred aprotic solvent is DMSO.
- The blend of cellulose acetate and cellulose in the dope may also comprise one or more further thermoplastic materials, such as polyhydroxyalkanoates such as PHB and/or PHVB which may add further functionality, such as water barrier functionality, to the fibres of the invention. Other functional additives may include triacetin, polyacrylonitrile (PAN), poly-2-hydroxyethylmethylacrylate (PHEMA), polyvinylalcohol (PVA), polyaniline and polyethylene glycol for functional purposes such as modification of absorption profile, degradation enhancement (by, for example, water-soluble materials), and processability improvement, in connection for example with wet strength.
- The weight ratio of cellulose to cellulose acetate in the dope, and consequently in the fibre of the invention is from 10:90 to 90:10, for example from 20:80 to 80:20, or from 30:70 to 70:30.
- Typically, the dope comprises a solids content of up to about 50% w/w, preferably up to about 40% w/w, more preferably up to about 30% w/w and most preferably up to about 20% w/w.
- The fibres of the invention may additionally comprise one or more plasticisers, such as triacetin. The plasticiser may be included in the dope, or may added subsequent to spinning or casting, for example by spraying onto the surface of the formed fibre.
- The fibres of the invention may additionally comprise a catalyst promoting oxidative degradation of the fibre. Suitable catalysts include iron and copper oxides and chlorides, which may be introduced into the fibre by immersing the composite filaments in an aqueous solution of a water-soluble iron or copper salt, such as sulphate or chloride, and precipitating the oxide (preferably in nano-form) onto or into the filament by treatment with sodium hydroxide or other suitable precipitating agent.
- The fibres may also comprise one or more lubricants to reduce electrostatic charge. Preferred lubricants include mineral oils. For example, 1% w/w of mineral oil with an emulsifier may be applied to the composite filaments during spinning of the fibres.
- Preferably the fibres of the invention comprise composite filaments of cellulose/cellulose acetate manufactured at 1, 5 or 9 denier per filament (filament thickness (denier per filament) being defined as the mass (grams) of 9000 m of a single filament).
- The total fibre mass (total denier) (defined as the total mass of 9000 m of fibre, typically comprising many thousands, for example 11,000, individual fibres) will vary considerably depending on the methods employed in fibre spinning and the number of individual filaments in the fibre. One typical fibre mass would 35,000 g.
- Preferably the fibres of the invention comprise fibres having a trilobal filament cross-section (optionally formed using triangular spinneret holes) to optimise surface area.
- The moisture content of the fibres according to the invention is preferably at least about 2% w/w, more preferably at least about 5% w/w, even more preferably at least about 10% w/w. Moisture content has been found to be important for preventing electrical charges, but should preferably not be too high (e.g. not higher than 50% w/w) because with a very high moisture content it may be difficult for the fibre to retain a crease.
- The fibres of the invention preferably comprise entangled filaments.
- Also provided in accordance with the invention is a material woven or otherwise made from the fibre as hereinbefore described.
- Also provided in accordance with the invention is a garment or soft furnishing made at least partly from a material as hereinbefore described.
- Also provided in accordance with the invention is a process for manufacturing fibres comprising providing a solution comprising a blend of cellulose and cellulose acetate in an ionic liquid or in NMMO, and spinning or casting the blend into a protic solvent to generate fibres.
- Water is the preferred protic solvent for the regenerative casting of the blend.
- In the process of the invention, composite cellulose/cellulose acetate materials can be produced at any ratio by regenerating solutions in water and/or other protic solvents. The rate of coagulation in water has been found to be dependant on the cellulose acetate content of the dope, where increased levels of cellulose acetate reduce the rate of coagulation.
- In another aspect, this invention provides a biodegradable film cast from a coagulated dope comprising cellulose and cellulose acetate, the resulting film being a cellulose/cellulose acetate composite material.
- The invention will now be more particularly described in the Examples which follow and which make reference to the following drawings:
-
FIG. 1 shows three slides showing fibres of i) cellulose acetate; ii) cellulose; and iii) a blend of cellulose and cellulose acetate in accordance with the invention. -
FIG. 2 shows the slides ofFIG. 1 after 2 weeks biodegradation under anaerobic conditions. -
FIG. 3 shows the slides ofFIG. 1 after 4 weeks biodegradation under anaerobic conditions. -
FIG. 4 shows the slides ofFIG. 1 after 6 weeks biodegradation under anaerobic conditions. - The invention will now be more particularly described in the Examples:
- The biodegradability of wet-spun fibres of blended cellulose/cellulose acetate was assessed in comparison with equivalent wet-spun fibres of cellulose, and equivalent wet-spun fibres of cellulose acetate.
- Using standard wet-spinning equipment fibres were spun from solutions of i) cellulose (DP ˜800) and ii) 1:1 cellulose: cellulose acetate (Eastman, CA-398-30), at 10% solids in EMIM-Ac: DMSO (20:80). A 40-orifice spinneret with an orifice diameter of 70 μm was used, which was submerged in a room temperature coagulation bath containing clean water. The fibres were reeled-up wet, extensively washed on the reel then dried at 50° C.
- With reference to
FIGS. 1 to 4 , a surprising property of these composite materials is that the rate of biodegradation under anaerobic environments exceeds that of cellulose and greatly exceeds that of cellulose acetate under the same conditions (see appendix 1). It is thought (although this theory is in no way to be considered binding) that the two components form an intimately mixed composite and that the enhanced rate of degradation arises from a reduction in the crystallinity of the cellulose. Degradation of the cellulose component of the composite is thought to lead to the cellulose acetate component being deposited on a molecular scale. We have also found that the rate of biodegradation under aerobic conditions of the fibres in accordance with the invention is similarly improved. - The application of these composite materials in the manufacture of fibres offers a route to achieving a fibrous product with both the desired versatility and comfort achieved by using cellulose acetate alone, but with greatly increased rates of biodegradation.
- Fibre according to the invention is manufactured using a dry-spinning process. A dope is first prepared by dissolving cellulose diacetate and cellulose (1:1 blend) at 10% solids in EMIM-Ac: DMSO (20:80). TiO2 is added to give a whitened appearance. The dope is then filtered and spun into chambers, causing the filaments to solidify and become thinner. More than 10,000 filaments are spun from a series of spinning cabinets, which are combined to form a single band. A material is woven from the fibre, and a garment is made from the material.
- The resulting garment is found to retain to advantageous biodegradability properties as shown in Example 1 and to have an acceptable comfort signature.
Claims (14)
1. A biodegradable fibre comprising composite filaments of cellulose and cellulose acetate.
2. The fibre according to claim 1 , further comprising one or more further thermoplastic materials.
3. The fibre according to claim 2 , wherein the further thermoplastic material is selected from one or more of PHB, PHVB, polyacrylonitrile (PAN), poly-2-hydroxyethylmethylacrylate (PHEMA), polyvinylalcohol (PVA), polyaniline and polyethylene glycol.
4. The fibre according to claim 1 , wherein the weight ratio of cellulose to cellulose acetate is from 10:90 to 90:10.
5. The fibre according to claim 4 , wherein the ratio of cellulose to cellulose acetate is from 20:80 to 80:20.
6. The fibre according to claim 5 , wherein the ratio of cellulose to cellulose acetate is from 30:70 to 70:30.
7. The fibre according to claim 1 , further comprising one or more plasticisers.
8. The fibre according to claim 1 , further comprising a catalyst promoting oxidative degradation of the fibre.
9. The fibre according to claim 1 , further comprising one or more lubricants to reduce electrostatic charge on the fibre.
10. A material woven produced from the fibre according to claim 1 .
11. A garment or soft furnishing at least partly made from the material according to claim 10 .
12. A process for manufacturing the fibre according to claim 1 , comprising:
providing a solution dope comprising a blend of cellulose and cellulose acetate in an ionic liquid or in N-methylmorphilone-N-oxide (NMMO); and
spinning or casting the blend into a protic solvent to generate fibres.
13. The process according to claim 12 , wherein the dope further comprises an aprotic solvent to aid dissolution of the cellulose and/or cellulose acetate.
14. The process according to claim 13 , wherein the aprotic solvent comprises one or more of DMSO, DMF, THF or dioxane.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0918633.9 | 2009-10-23 | ||
GB0918633A GB2474694B (en) | 2009-10-23 | 2009-10-23 | Biodegradable composites |
PCT/GB2010/051771 WO2011048420A1 (en) | 2009-10-23 | 2010-10-21 | Biodegradable fibre and its process of manufacture |
Publications (1)
Publication Number | Publication Date |
---|---|
US20120202398A1 true US20120202398A1 (en) | 2012-08-09 |
Family
ID=41426623
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/497,220 Expired - Fee Related US8833376B2 (en) | 2009-10-23 | 2010-09-17 | Biodegradable composites |
US12/893,572 Expired - Fee Related US8464728B2 (en) | 2009-10-23 | 2010-09-29 | Biodegradable composites |
US13/497,209 Abandoned US20120202398A1 (en) | 2009-10-23 | 2010-10-21 | Biodegradable fibre and its process of manufacture |
US13/896,716 Abandoned US20130247926A1 (en) | 2009-10-23 | 2013-05-17 | Biodegradable composites |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/497,220 Expired - Fee Related US8833376B2 (en) | 2009-10-23 | 2010-09-17 | Biodegradable composites |
US12/893,572 Expired - Fee Related US8464728B2 (en) | 2009-10-23 | 2010-09-29 | Biodegradable composites |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/896,716 Abandoned US20130247926A1 (en) | 2009-10-23 | 2013-05-17 | Biodegradable composites |
Country Status (20)
Country | Link |
---|---|
US (4) | US8833376B2 (en) |
EP (2) | EP2490557B1 (en) |
JP (3) | JP5944317B2 (en) |
KR (1) | KR101818559B1 (en) |
CN (4) | CN102595942A (en) |
BR (2) | BR112012009307A2 (en) |
CY (1) | CY1117628T1 (en) |
ES (2) | ES2532147T3 (en) |
GB (1) | GB2474694B (en) |
HK (1) | HK1217157A1 (en) |
HR (1) | HRP20160504T1 (en) |
HU (2) | HUE025084T2 (en) |
MX (1) | MX2012004043A (en) |
MY (1) | MY182730A (en) |
PL (2) | PL2490557T3 (en) |
PT (2) | PT2490557E (en) |
RS (1) | RS54787B1 (en) |
SG (1) | SG181064A1 (en) |
SI (1) | SI2491172T1 (en) |
WO (2) | WO2011048397A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150354096A1 (en) * | 2012-12-20 | 2015-12-10 | Convatec Technologies Inc. | Processing of chemically modified cellulosic fibres |
US10493101B2 (en) | 2005-12-14 | 2019-12-03 | Convatec Technologies Inc. | Antimicrobial composition |
US11135315B2 (en) | 2010-11-30 | 2021-10-05 | Convatec Technologies Inc. | Composition for detecting biofilms on viable tissues |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA3007805C (en) | 2010-04-29 | 2019-11-26 | The Regents Of The University Of California | Pathway recognition algorithm using data integration on genomic models (paradigm) |
US10192641B2 (en) * | 2010-04-29 | 2019-01-29 | The Regents Of The University Of California | Method of generating a dynamic pathway map |
MX2014004435A (en) * | 2011-10-17 | 2014-05-28 | Sulzer Mixpac Ag | Cartridge, method for producing said cartridge, and multi-component cartridge. |
CN102493021B (en) * | 2011-12-06 | 2014-01-08 | 东华大学 | Method for preparing cellulose nanocrystal reinforced polyhydroxybutyrate-hydroxyvalerate (PHBV) nanofiber |
US9854833B2 (en) * | 2012-02-16 | 2018-01-02 | R. J. Reynolds Tobacco Company | Apparatus and associated method for forming a filter component of a smoking article |
KR101362494B1 (en) * | 2012-03-07 | 2014-02-14 | 주식회사 케이티앤지 | Cigarette filter with technology reducing cigarette smell on hands, and cigarette having the same |
US9670596B2 (en) * | 2012-05-21 | 2017-06-06 | Bridgestone Corporation | Production method for purified polysaccharide fibers, purified polysaccharide fibers, fiber-rubber complex, and tire |
JP5948146B2 (en) * | 2012-05-21 | 2016-07-06 | 株式会社ブリヂストン | Process for producing purified polysaccharide fiber, purified polysaccharide fiber, fiber-rubber composite, and tire |
JP5993614B2 (en) * | 2012-05-21 | 2016-09-14 | 株式会社ブリヂストン | Purified polysaccharide fiber, fiber-rubber composite and tire manufacturing method |
JP5948147B2 (en) * | 2012-05-21 | 2016-07-06 | 株式会社ブリヂストン | Process for producing purified polysaccharide fiber, purified polysaccharide fiber, fiber-rubber composite, and tire |
US20150189913A1 (en) * | 2012-07-13 | 2015-07-09 | Philip Morris Products S.A. | Degradable filter for smoking articles |
US9179709B2 (en) * | 2012-07-25 | 2015-11-10 | R. J. Reynolds Tobacco Company | Mixed fiber sliver for use in the manufacture of cigarette filter elements |
US9119419B2 (en) * | 2012-10-10 | 2015-09-01 | R.J. Reynolds Tobacco Company | Filter material for a filter element of a smoking article, and associated system and method |
JP2014227619A (en) | 2013-05-21 | 2014-12-08 | 株式会社ブリヂストン | Method of producing refined polysaccharide fiber, refined polysaccharide fiber and tire |
KR101455002B1 (en) | 2013-06-28 | 2014-11-03 | 코오롱인더스트리 주식회사 | Lyocell Material Cigarette Filter and Method for the Same |
KR102125049B1 (en) * | 2013-12-26 | 2020-07-08 | 코오롱인더스트리 주식회사 | Lyocell Material Cigarette Filter and Method for the Same |
EP3051011B1 (en) | 2013-09-26 | 2023-01-11 | Kolon Industries, Inc. | Lyocell material for cigarette filter and method for preparing same |
US20170006912A1 (en) * | 2014-03-13 | 2017-01-12 | Daicel Corporation | Cellulose acetate tow band for use in cigarette filter, cigarette filter, apparatus for manufacturing tow band, and method of manufacturing tow band |
WO2016003145A1 (en) * | 2014-06-30 | 2016-01-07 | 코오롱인더스트리 주식회사 | Modified cross-section lyocell material for tobacco filter, and preparation method therefor |
KR102211219B1 (en) * | 2014-06-30 | 2021-02-03 | 코오롱인더스트리 주식회사 | Lyocell Material with Noncircle Cross Section for Cigarette Filter And Manufacturing Method of the same |
US10011931B2 (en) | 2014-10-06 | 2018-07-03 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing dyed and welded substrates |
KR102211186B1 (en) | 2014-12-31 | 2021-02-03 | 코오롱인더스트리 주식회사 | Lyocell Material Cigarette Filter and Method for the Same |
JP2018535822A (en) * | 2015-10-07 | 2018-12-06 | ロディア・アツェトウ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングRhodia Acetow GmbH | Nonwoven fabrics containing cellulose acetate fibers and uses thereof |
KR20170079531A (en) * | 2015-12-30 | 2017-07-10 | 코오롱인더스트리 주식회사 | Lyocell Fiber and the method for making it |
CN108495958B (en) * | 2016-01-26 | 2021-06-11 | 富士胶片株式会社 | Nanofiber and nonwoven fabric |
CN109072542B (en) | 2016-03-25 | 2022-03-08 | 天然纤维焊接股份有限公司 | Method, process and apparatus for producing a weld matrix |
KR102304833B1 (en) | 2016-05-03 | 2021-09-24 | 네추럴 파이버 웰딩 인코포레이티드 | Methods, processes, and apparatus for making dyed and welded substrates |
US10524500B2 (en) | 2016-06-10 | 2020-01-07 | R.J. Reynolds Tobacco Company | Staple fiber blend for use in the manufacture of cigarette filter elements |
GB201705186D0 (en) * | 2017-03-31 | 2017-05-17 | Innovia Films Ltd | Fibre |
CN106807348B (en) * | 2017-04-07 | 2019-04-12 | 武夷学院 | Activated carbon fiber-loaded TiO2The preparation method of photochemical catalyst |
EP3643185A4 (en) | 2017-06-19 | 2021-05-26 | Japan Tobacco, Inc. | Smoking article filter and production method therefor |
JP2021515540A (en) * | 2018-02-01 | 2021-06-24 | ジェイティー インターナショナル エス.エイ.JT International S.A. | Biodegradable filter with improved taste |
US11395507B2 (en) | 2018-09-07 | 2022-07-26 | Altria Client Services Llc | Filter for an e-vaping device, e-vaping device with the filter, and method of forming the filter |
CN109619674B (en) * | 2018-11-22 | 2021-12-03 | 湖北中烟工业有限责任公司 | Preparation method of lotus fiber for cigarettes and moisturizing filter tip containing lotus fiber |
CN110250568A (en) * | 2019-06-13 | 2019-09-20 | 上海洁晟环保科技有限公司 | A kind of purposes of cellulose diacetate pulp as cigarette filter stick |
KR102182459B1 (en) * | 2019-06-17 | 2020-11-24 | 김대식 | Manufacturing process of tow for electronic cigarette firter |
KR102386075B1 (en) * | 2020-03-13 | 2022-04-12 | 주식회사 케이티앤지 | Plasticizer for improved bio-degradability, filter, and smoking article including the same |
CN111548772A (en) * | 2020-05-29 | 2020-08-18 | 南通大学 | Multi-walled carbon nanotube composite shape-stabilized phase change material and preparation method and application thereof |
JP7037833B2 (en) * | 2020-06-23 | 2022-03-17 | 日本特装株式会社 | Masks and mask manufacturing methods |
CN112704263A (en) * | 2020-11-29 | 2021-04-27 | 湖北中烟工业有限责任公司 | Cigarette filter tip capable of promoting degradation by using biological enzyme |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3082178A (en) * | 1955-08-31 | 1963-03-19 | Eastman Kodak Co | Composition consisting of cellulose acetate and copolymer of n, n-dimethyl-acrylamide |
US3943079A (en) * | 1974-03-15 | 1976-03-09 | Monsanto Company | Discontinuous cellulose fiber treated with plastic polymer and lubricant |
US4533507A (en) * | 1981-06-18 | 1985-08-06 | James River-Dixie/Northern, Inc. | Fiber moisture control in the formation of dry-laid webs |
US4731093A (en) * | 1984-10-22 | 1988-03-15 | Hoechst Aktiengesellschaft | Process for fixing pigments on fiber materials and sheetlike structures |
US5540874A (en) * | 1993-02-16 | 1996-07-30 | Mitsubishi Rayon Company Ltd. | Cellulose solution for shaping and method of shaping the same |
US5731083A (en) * | 1991-12-09 | 1998-03-24 | Courtaulds Plc | Cellulosic fibres |
US5779736A (en) * | 1995-01-19 | 1998-07-14 | Eastman Chemical Company | Process for making fibrillated cellulose acetate staple fibers |
US6075177A (en) * | 1993-01-22 | 2000-06-13 | Acordis Fibres (Holdings) Limited | Wound dressing |
US20050288163A1 (en) * | 2004-06-25 | 2005-12-29 | Celanese Acetate Llc | Cellulose acetate tow and method of making same |
US20070207315A1 (en) * | 2004-03-26 | 2007-09-06 | Toray Industries, Inc., | Fabric for Clothing and a Production Method Thereof |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1244609A (en) * | 1967-10-18 | 1971-09-02 | Courtaulds Ltd | Tobacco smoke filters |
US3756253A (en) * | 1970-12-18 | 1973-09-04 | Mitsubishi Acetate Co Ltd | Cellulose acetate fiber tobacco smoke filter and process of manufacturing the same |
FR2412272A1 (en) * | 1977-12-23 | 1979-07-20 | Job Ets Bardou Job Pauilhac | PROCESS FOR THE REALIZATION OF CIGARETTE FILTERS AND FILTERS THUS OBTAINED |
GB2012552B (en) | 1978-01-14 | 1982-11-24 | Amf Inc | Instantaneous slurry preparation on a continuous basis |
US5105834A (en) * | 1989-12-18 | 1992-04-21 | R.J. Reynolds Tobacco Company | Cigarette and cigarette filter element therefor |
TW256845B (en) * | 1992-11-13 | 1995-09-11 | Taisyal Kagaku Kogyo Kk | |
JPH06298999A (en) * | 1993-02-16 | 1994-10-25 | Mitsubishi Rayon Co Ltd | Solution for casting cellulose and method for casting using the same |
TW241198B (en) * | 1993-09-06 | 1995-02-21 | Daicel Chem | A tobacco filter material and a method of producing the same |
JP3515119B2 (en) | 1993-11-29 | 2004-04-05 | テンセル リミティド | Cigarette filter |
JP3454584B2 (en) * | 1994-10-18 | 2003-10-06 | ダイセル化学工業株式会社 | Filter for tobacco smoke and method for producing the same |
US5856006A (en) * | 1994-09-19 | 1999-01-05 | Daicel Chemical Industries, Ltd. | Tobacco filter material and a method for producing the same |
JP3696951B2 (en) * | 1994-09-22 | 2005-09-21 | ダイセル化学工業株式会社 | Cigarette smoke filter material and method for producing the same |
DE19536505A1 (en) * | 1995-09-29 | 1997-04-10 | Biotec Biolog Naturverpack | Biodegradable filter material and process for its manufacture |
JP3677332B2 (en) * | 1995-10-20 | 2005-07-27 | ダイセル化学工業株式会社 | Tobacco filter material and tobacco filter using the same |
JPH09291414A (en) * | 1996-04-22 | 1997-11-11 | Oji Paper Co Ltd | Biodegradable cellulose acetate-based fiber and its production |
JPH09302520A (en) * | 1996-05-14 | 1997-11-25 | Kuraray Co Ltd | Production of readily fibrillating fiber |
EP0977912B1 (en) * | 1997-05-02 | 2004-09-22 | Cargill, Incorporated | Degradable polymer fibers; preparation; product; and methods of use |
US5891375A (en) * | 1997-07-24 | 1999-04-06 | Alfacel S.A. | Processes for precipitating tertiary amine oxide cellulose solutions containing esters and products made therefrom |
JP2931810B1 (en) * | 1998-03-31 | 1999-08-09 | 日本たばこ産業株式会社 | Biodegradable cellulose acetate molded product and filter plug for tobacco |
TWI274556B (en) * | 1999-03-11 | 2007-03-01 | Japan Tobacco Inc | Biodegradable cellulose acetate structures and tobacco filters |
DE19951062C2 (en) * | 1999-10-22 | 2002-04-04 | Rhodia Acetow Gmbh | A high performance cigarette filter |
DE10352152A1 (en) * | 2003-11-04 | 2005-06-23 | Hauni Maschinenbau Ag | Process and assembly to manufacture cigarette filter fibers that area combination of cellulose ester and cellulose |
US7888412B2 (en) | 2004-03-26 | 2011-02-15 | Board Of Trustees Of The University Of Alabama | Polymer dissolution and blend formation in ionic liquids |
US6924029B1 (en) * | 2004-06-25 | 2005-08-02 | Celanese Acetate, Llc | Cellulose acetate tow and method of making same |
CN1261625C (en) * | 2004-09-30 | 2006-06-28 | 长沙卷烟厂 | Method for using poly ethylene glycol as spinning additive |
US7856989B2 (en) * | 2004-12-30 | 2010-12-28 | Philip Morris Usa Inc. | Electrostatically produced fast dissolving fibers |
EP1907470B1 (en) | 2005-06-29 | 2013-04-10 | The University of Alabama | Ionic liquid reconstituted cellulose composites as solid support matrices |
DE102006022009B3 (en) * | 2006-05-10 | 2007-12-06 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Process for producing cellulosic multicomponent fibers |
CN100574657C (en) * | 2006-09-14 | 2009-12-30 | 郑州大学 | Short viscose cigarette filter |
WO2008098037A2 (en) | 2007-02-06 | 2008-08-14 | North Carolina State University | Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids |
JP2010535024A (en) * | 2007-08-01 | 2010-11-18 | フィリップ・モーリス・プロダクツ・ソシエテ・アノニム | Decomposable cigarette filter |
JP2009203467A (en) * | 2008-01-31 | 2009-09-10 | Kri Inc | Solvent for dissolving cellulose and molded article from cellulose solution |
US8375958B2 (en) * | 2008-05-21 | 2013-02-19 | R.J. Reynolds Tobacco Company | Cigarette filter comprising a carbonaceous fiber |
CN102912474B (en) * | 2012-10-10 | 2014-09-03 | 广东省均安牛仔服装研究院 | Composite fiber and preparation method thereof |
-
2009
- 2009-10-23 GB GB0918633A patent/GB2474694B/en not_active Expired - Fee Related
-
2010
- 2010-09-17 CN CN2010800467767A patent/CN102595942A/en active Pending
- 2010-09-17 PT PT10760393T patent/PT2490557E/en unknown
- 2010-09-17 SG SG2012038576A patent/SG181064A1/en unknown
- 2010-09-17 KR KR1020127012035A patent/KR101818559B1/en active IP Right Grant
- 2010-09-17 BR BR112012009307A patent/BR112012009307A2/en active Search and Examination
- 2010-09-17 MX MX2012004043A patent/MX2012004043A/en active IP Right Grant
- 2010-09-17 US US13/497,220 patent/US8833376B2/en not_active Expired - Fee Related
- 2010-09-17 MY MYPI2012001760A patent/MY182730A/en unknown
- 2010-09-17 CN CN201510929978.0A patent/CN105342004A/en active Pending
- 2010-09-17 ES ES10760393.8T patent/ES2532147T3/en active Active
- 2010-09-17 JP JP2012534772A patent/JP5944317B2/en not_active Expired - Fee Related
- 2010-09-17 EP EP10760393.8A patent/EP2490557B1/en not_active Not-in-force
- 2010-09-17 WO PCT/GB2010/051562 patent/WO2011048397A1/en active Application Filing
- 2010-09-17 HU HUE10760393A patent/HUE025084T2/en unknown
- 2010-09-17 PL PL10760393T patent/PL2490557T3/en unknown
- 2010-09-29 US US12/893,572 patent/US8464728B2/en not_active Expired - Fee Related
- 2010-10-21 PT PT107690505T patent/PT2491172E/en unknown
- 2010-10-21 JP JP2012534777A patent/JP6084462B2/en not_active Expired - Fee Related
- 2010-10-21 ES ES10769050T patent/ES2571224T3/en active Active
- 2010-10-21 HU HUE10769050A patent/HUE029230T2/en unknown
- 2010-10-21 CN CN201610404310.9A patent/CN106012088A/en active Pending
- 2010-10-21 CN CN2010800467771A patent/CN102597343A/en active Pending
- 2010-10-21 RS RS20160336A patent/RS54787B1/en unknown
- 2010-10-21 WO PCT/GB2010/051771 patent/WO2011048420A1/en active Application Filing
- 2010-10-21 SI SI201031177A patent/SI2491172T1/en unknown
- 2010-10-21 BR BR112012009308A patent/BR112012009308A2/en not_active Application Discontinuation
- 2010-10-21 EP EP10769050.5A patent/EP2491172B1/en active Active
- 2010-10-21 US US13/497,209 patent/US20120202398A1/en not_active Abandoned
- 2010-10-21 PL PL10769050T patent/PL2491172T3/en unknown
-
2013
- 2013-05-17 US US13/896,716 patent/US20130247926A1/en not_active Abandoned
-
2015
- 2015-10-19 JP JP2015205279A patent/JP2016053236A/en active Pending
-
2016
- 2016-05-06 HK HK16105179.4A patent/HK1217157A1/en unknown
- 2016-05-11 HR HRP20160504TT patent/HRP20160504T1/en unknown
- 2016-05-20 CY CY20161100437T patent/CY1117628T1/en unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3082178A (en) * | 1955-08-31 | 1963-03-19 | Eastman Kodak Co | Composition consisting of cellulose acetate and copolymer of n, n-dimethyl-acrylamide |
US3943079A (en) * | 1974-03-15 | 1976-03-09 | Monsanto Company | Discontinuous cellulose fiber treated with plastic polymer and lubricant |
US4533507A (en) * | 1981-06-18 | 1985-08-06 | James River-Dixie/Northern, Inc. | Fiber moisture control in the formation of dry-laid webs |
US4731093A (en) * | 1984-10-22 | 1988-03-15 | Hoechst Aktiengesellschaft | Process for fixing pigments on fiber materials and sheetlike structures |
US5731083A (en) * | 1991-12-09 | 1998-03-24 | Courtaulds Plc | Cellulosic fibres |
US6075177A (en) * | 1993-01-22 | 2000-06-13 | Acordis Fibres (Holdings) Limited | Wound dressing |
US5540874A (en) * | 1993-02-16 | 1996-07-30 | Mitsubishi Rayon Company Ltd. | Cellulose solution for shaping and method of shaping the same |
US5779736A (en) * | 1995-01-19 | 1998-07-14 | Eastman Chemical Company | Process for making fibrillated cellulose acetate staple fibers |
US20070207315A1 (en) * | 2004-03-26 | 2007-09-06 | Toray Industries, Inc., | Fabric for Clothing and a Production Method Thereof |
US20050288163A1 (en) * | 2004-06-25 | 2005-12-29 | Celanese Acetate Llc | Cellulose acetate tow and method of making same |
Non-Patent Citations (1)
Title |
---|
Barani, H et. al., "Preparation of Polyacrylonitrile and Cellulose Acetate Blend Fibers through We-Spinning," November 8, 2006, Journal of Applied Polymer Science, Vol. 103, pp. 2000-2005. * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10493101B2 (en) | 2005-12-14 | 2019-12-03 | Convatec Technologies Inc. | Antimicrobial composition |
US11135315B2 (en) | 2010-11-30 | 2021-10-05 | Convatec Technologies Inc. | Composition for detecting biofilms on viable tissues |
US20150354096A1 (en) * | 2012-12-20 | 2015-12-10 | Convatec Technologies Inc. | Processing of chemically modified cellulosic fibres |
US11286601B2 (en) | 2012-12-20 | 2022-03-29 | Convatec Technologies, Inc. | Processing of chemically modified cellulosic fibres |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2491172B1 (en) | Use of composite filaments of cellulose and cellulose acetate for enhancing biodegradability | |
CN105705523B (en) | Polysaccharide fiber and preparation method thereof | |
US11330836B2 (en) | Lyocell material for tobacco filter | |
US10806174B2 (en) | Lyocell material for cigarette filter and method for preparing same | |
WO2016140307A1 (en) | Cellulose acetate fiber, production method therefor, and filter tow for cigarettes | |
CN113166406A (en) | Method for preparing functional fiber | |
US20170156394A1 (en) | Modified cross-section lyocell material for tobacco filter, and preparation method therefor | |
DK2491172T3 (en) | USE OF THE KOMPOSITFILAMENTER and cellulose acetate TO INCREASE IN BIODEGRADABILITY | |
KR101472097B1 (en) | Manufacturing method of cellulose fiber using ionic liquid | |
TWI827733B (en) | Method for preparing a functional fiber | |
KR101306233B1 (en) | Cellulose filament fiber, preparation method thereof, and tire cord comprising the same | |
JP2008179926A (en) | Cellulose fatty acid-mixed ester ultrafine fiber precursor and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: INNOVIA FILMS LIMITED, UNITED KINGDOM Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MARSHALL, COLIN;MOFFAT, JAMIE;REEL/FRAME:028113/0882 Effective date: 20120405 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |