WO2000076322A1 - Compositions de materiaux destinees a la production de composites cellulosiques reduisant l'adherence - Google Patents

Compositions de materiaux destinees a la production de composites cellulosiques reduisant l'adherence Download PDF

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Publication number
WO2000076322A1
WO2000076322A1 PCT/GB2000/001812 GB0001812W WO0076322A1 WO 2000076322 A1 WO2000076322 A1 WO 2000076322A1 GB 0001812 W GB0001812 W GB 0001812W WO 0076322 A1 WO0076322 A1 WO 0076322A1
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WO
WIPO (PCT)
Prior art keywords
cellulose
composition
emulsion
anionic polymer
wax
Prior art date
Application number
PCT/GB2000/001812
Other languages
English (en)
Inventor
Lei Jong
Original Assignee
Devro Plc
Teepak Investments, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Devro Plc, Teepak Investments, Inc. filed Critical Devro Plc
Priority to EP00929699A priority Critical patent/EP1189516A1/fr
Priority to AU47702/00A priority patent/AU4770200A/en
Publication of WO2000076322A1 publication Critical patent/WO2000076322A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/06—Cellulose hydrate
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C13/0013—Chemical composition of synthetic sausage casings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/22—Cellulose xanthate
    • C08L1/24—Viscose

Definitions

  • This invention is related to a material composition based on regenerated cellulose for adhesion-reducing applications, especially adhesion towards hydrophilic substances such as polyamides, meat emulsions, proteins, polyacrylic acids, polyvinyl alcohols, and so on. It is well known that cellulose comprises many hydrophilic hydroxy groups and that cellulose readily adheres to hydrophilic materials as above described. It is also known that hydrophilic substances do not wet and adhere to a hydrophobic substrate.
  • U.S. Patent 3,224,885 describes the incorporation of alkyl ketene dimers into cellulose.
  • a ketene dimer content between 0.1 and 10 percent by the weight of cellulose in the viscose is effective in imparting improved peelability from the sausage meat surface.
  • Solid alkyl ketene dimers can be added to the viscose in the form of aqueous emulsion containing emulsifying agents. The ketene dimer containing viscose compositions were all extruded onto a paper web within about 10 minutes after viscose and the ketene dimer had been mixed.
  • Cellulose fiber reinforced polyethylene composite has been used as a means to improve the stiffness of polyethylene.
  • interfacial bonding appears to be unfavored.
  • the cellulose fiber surface is modified by maleated polypropylene grafts, the fiber is converted to a predominantly dispersion-force solid.
  • Such surface modified fibers improve the elastic and storage moduli when used in polypropylene, polystyrene or chlorinated polyethylene composite.
  • a cellulose composite composition that includes paraffin wax, carboxy containing anionic polymer, and cellulose.
  • the composite composition is formed by the coagulation, regeneration and drying of a mixture consisting of paraffin wax emulsion, carboxy containing anionic polymer emulsion, and viscose.
  • the composite has a hydrophobic surface with reduced adhesion to hydrophilic surfaces when compared with regenerated cellulose alone or when compared with cellulose including paraffin wax alone or cellulose including carboxy containing anionic polymer alone.
  • the composition is thus a synergistic cellulose containing composition having a lower adhesion to a hydrophilic surface than cellulose with or without the other individual components of the composition.
  • the composition is prepared by coagulation and regeneration of a mixture comprising a hydrophobic wax, e.g. paraffin wax, emulsion; anionic polymer emulsion; and viscose.
  • the regenerated product is then dried to obtain a cellulose product having a hydrophobic surface.
  • neither carboxylic acid containing polymer nor wax alone, when mixed with cellulose can produce the same degree of hydrophobic surface as the combination of both at the same total weight fraction in the cellulose composite.
  • a cellulose composite containing 30% of 2:1 mixture of poly (ethylene-acrylic acid) and wax has a more hydrophobic surface towards the polypeptide than a cellulose composite containing 30% of wax or 30% of poly (ethylene-acrylic acid) .
  • the current process is a one-step process instead of a two-step coating process first requiring regeneration of a cellulose surface followed by a coating process.
  • the cellulose composite contains carboxylic acid containing polymer (a) , wax (b) , and cellulose (c) .
  • Polymer (a) is introduced as an emulsion in the form of an aqueous dispersion of carboxylic acid containing polymer neutralized with an alkaline material such as potassium hydroxide, sodium hydroxide, or ammonium hydroxide.
  • the wax (b) is the aqueous dispersion of wax through the action of surfactants which can be anionic, cationic, or nonionic.
  • surfactants which can be anionic, cationic, or nonionic.
  • (c) is in the form of viscose that is the aqueous solution of cellulose in CS 2 , in the presence of an aqueous alkali metal hydroxide such as sodium hydroxide.
  • Aqueous solution of components (a) , (b) , and (c) results in a material that can be coagulated by the well known acid/salt regeneration solution process.
  • Carboxy group as used herein means a carboxylic acid group or a carboxylic acid salt group.
  • Viscose as used herein means traditional xanthate viscose formed by dissolution of alkali cellulose in carbon disulfide as well as other solutions of cellulose that can be precipitated or regenerated, such as cupraammonium cellulose, cellulose aminomethanate, and cellulose-tertiary amine oxide solutions .
  • the composite compositions of the invention may be prepared by mixing together effective amounts of anionic polymer emulsion, wax emulsion, and viscose, e.g. xanthate solution in an aqueous environment to obtain a solution from which cellulose may be precipitated.
  • Precipitated as used herein means either precipitation of non- derivatized cellulose from a solution, e.g. cellulose in a cupraammonium solution or an amine oxide solution, or by coagulation of a derivatized cellulose, e.g. xanthate cellulose or cellulose aminomethanate; followed by regeneration to remove derivatizing groups.
  • the precipitated cellulose encloses the anionic polymer and wax to form a solid cellulose composite. Upon the removal of water from the swollen cellulose composite, the surface of the composite becomes hydrophobic, substantially reducing wetting and adhesion by hydrophilic substances.
  • the weight percentages of the components of the composition are based on the total dry weight of the compositions.
  • Anionic polymers suitable for practicing this invention typically are hydrocarbon polymers containing a few percent of carboxylic acid functional groups or their salts (carboxy groups) . These hydrocarbon polymers are synthesized by free radical, anionic, cationic, or emulsion polymerization of unsaturated monomers with a few percent of carboxy containing unsaturated monomers .
  • the carboxy functional groups may or may not be protected during the polymerization process, depending on the reaction used in polymer formation.
  • the desired percentage of carboxy containing monomer units in terms of total monomer units in the polymer is ⁇ 30%, preferably ⁇ 20%.
  • the amount of carboxy groups in the polymer is effective, upon the neutralization with alkali, to impart a certain degree of dispersability and stability to the polymer in the aqueous solution.
  • Carboxylic acid containing polymers can be neutralized by alkaline solutions containing lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, amine, etc. While neutralized carboxylic acid groups are required to impart substantial water solubility to the polymer, a minimum amount of such groups is preferred to retain the hydrophobicity of polymers for their intended application. Hydrocarbon monomer units in these anionic polymers can be partially unsaturated but preferably contain no unsaturation in the final polymer structure.
  • Suitable hydrocarbon monomers for the construction of anionic polymers for use in the present invention are ethylene, propylene, butadiene, hexadiene, isobutene, isoprene, 4-methyl-pentene, styrene, xylylene, methyl styrene, etc.
  • the amount of carboxy containing polymer used in practicing the invention should be greater than 1%, preferably >5%, more preferably >10%.
  • the emulsions used in preparing the compositions of the invention usually contain from about 10 to about 40 weight percent anionic polymer and sufficient emulsion is used to obtain from about 10 to about 75 and preferably from about 20 to about 50 weight percent of polymer in the dry composite composition of the invention.
  • Wax used in practicing the invention is hydrophobic wax that should be a solid at room temperature (70OF) .
  • These waxes may be paraffin wax, e.g. in the form of mixed hydrocarbon waxes containing a high proportion of C 16 - C 40 alkanes, macrocyrstalline, microcrystalline paraffin wax produced by a solvent dewaxing process, or slack wax produced by a sweating process.
  • the wax is usually a saturated hydrocarbon wax but may be a partially or completely halogenated C 16 - C 42 , e.g. with fluorine, Paraffin wax suitable to be used in the present invention may be represented, for example, by Paracol wax emulsion from Hercules.
  • the waxes are emulsified with the aid of cationic, anionic, or nonionic surfactants to form stable emulsions.
  • anionic or nonionic surfactant is used in the emulsification.
  • the wax emulsions used to prepare the composite composition may contain from about 10 to about 40 weight percent wax. Sufficient wax emulsion is used to obtain a wax concentration in the finished dried cellulose composite greater than 1%, preferably greater than 5%, and more preferably greater than 10%, based on the total dry weight of the composition.
  • a fluoroalkyl acrylate polymer may optionally be included in the mixture.
  • "Fluoroalkyl acrylate polymer” as used herein means a fluorinated acrylate polymer preferably containing from about 25 to about 40 weight percent flurine.
  • Such acrylate polymers can be formed by means known to those skilled in the art, e.g. heating of a fluorinated ester of acrylic acid in the presence of an initiator such as a peroxide. Copolymers can also be formed by heating the fluorinated acrylic acid ester with other compounds reactive with acrylic unsaturation, e.g. other acrylic acid esters.
  • a particularly suitable fluorinated acrylic acid ester is 2-propenoic acid, 2 ⁇ ⁇ (heptadecafluoro-octyl) sulfonyl ⁇ methyl amino ⁇ ethyl ester.
  • Suitable comonomers to make fluoroalkyl acrylate copolymers are 2-propenoic acid, 2 -methyl-oxiranyl methyl ester; and 2-propenoic acid, 2-ethoxyethyl ester.
  • a preferred fluoroalkyl acrylate copolymer contains 35 to 40 weight percent fluorine and is made by the copolymerization of ethanaminium, N,N,N-trimethyl-2- ⁇ (2- methyl-l-oxo-2-propenyl) -oxy ⁇ - , chloride; 2-propenoic acid, 2-methyl-, oxiranylmethyl ester; 2-propenoic acid, 2- ethoxyethyl ester; and 2-propenoic acid, 2 ⁇ (heptadecafluoro-octyl) sulfonyl ⁇ methyl amino ⁇ ethyl ester.
  • This preferred fluoroalkyl acrylate copolymer has been assigned CAS Reg. No. 92265-81-1.
  • the quantity of fluropolymer e.g. fluoroalkyl- acrylate polymer, when included, may be any suitable amount, but usually from 0.1 to 15 percent and preferably 0.1 to 5 percent by weight of mixture.
  • surface tension can be considered to have reference to a single factor consisting of such variables as intermolecular, or secondary bonding forces, such as permanent dipole forces, induced dipole forces, dispersion or non-polar Van der Waals forces, hydrogen bonding forces, and ionic bonding forces.
  • Surface tension is theorized and experimentally confirmed to influence surface wetting and non-wetting effects and thus has an effect upon adhesive characteristics. It is an experimental fact that wetting is the first requirement for an adhesion to occur between two surfaces.
  • polarity Surface tension is theorized to consist of two types of interactions, one is polar interaction and another one is non-polar interaction.
  • the fraction of polar interaction within the total interaction is defined as "polarity" .
  • Many polymer solids have been experimentally found to have a good correlation between the polarity determined by contact angle measurement and their chemical structures.
  • polyethylene has a polarity of 0-3% because the majority of the polymer structure comprises alkyl chains and does not contain any significant amount of polar functional groups such as ether, hydroxyl, sulfone, imine, halogen, carbonate, amide, or carboxylic acid.
  • polyamide contains amide functional groups and has a polarity of 20-40%, depending on the fraction of other non-polar structure in the polymers . Due to the good correlation between the polarity of a material surface and the chemical structure of the material, polarity is considered a characteristic parameter of a particular surface and has influence on the wetting and non-wetting behaviour of the surface.
  • Interfacial tension between two surfaces is another characteristic parameter which measures the compatability between two surfaces .
  • a zero interfacial tension indicates a complete wetting between two surfaces, whereas a positive interfacial tension indicates partial wetting.
  • Another characteristic parameter is the spreading coefficient which measures how easy a surface can be wetted by a substance, a positive spreading coefficient indicates good wetting and a negative value indicates poor wetting.
  • the composition of the current invention can also be used to produce hydrophobic fibers which can then be used to increase the compatability between the cellulose fiber and polyethylene in the application of increasing the stiffness of polyethylene composite.
  • hydrophobic fibres can also be used in the manu acturing of papers and textiles to produce articles possessing at least some moisture-barrier characteristics.
  • the composite materials of the present invention may be used for the formation of cellulose containing hydrophobic products such as films, coatings, laminates, fibres, sheets, fiber-reinforced cellulose casing, cellulose casings, etc.
  • a 10% aqueous dispersion of sodium salt of poly (ethylene-acrylic acid), ⁇ PEA ⁇ , 80/20 ethylene/acrylic acid was mixed with 10% of paraffin wax emulsion at 4:1 ratio.
  • 23.8 gm of 10% emulsion mixture prepared as described were then mixed with 29.5 grams of xanthate viscose containing about 8% of cellulose.
  • the viscose containing the emulsion mixture was spread on a cellulose fiber paper web with a Vz" diameter #90 wire-wound rod and subsequently coagulated and regenerated in a conventional sulfuric acid/sodium sulfate bath as previously described.
  • sample A The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 15 minutes at 103°C The surface tension was measured to be 35 dyne/cm with a polypeptide spreading coefficient of -31 dyne/cm, a polarity of 0%, and a polypeptide-composite interfacial tension of 21 dyne/cm. This sample was designated as sample A.
  • the surface tension was measured to be 34 dyne/cm with a polypeptide spreading coefficient of -33 dyne/cm, a polarity of 1%, and a polypeptide-composite interfacial tension of 20 dyne/cm. This sample is designated as sample B.
  • sample C The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 20 minutes at 102°C The surface tension was measured to be 35 dyne/cm with a polypeptide spreading coefficient of -30 dyne/cm, a polarity of 3%, and a polypeptide-composite interfacial tension of 18 dyne/cm. This sample is designated as sample C.
  • sample D The surface tension was measured to be 31 dyne/cm with a polypeptide spreading coefficient of -28 dyne/cm, a polarity of 9%, and a polypeptide-composite interfacial tension of 13 dyne/cm. This sample is designated as sample D.
  • This example is for a blend of cellulose and wax only without poly (ethylene-acrylic acid).
  • the surface properties were measured and compared with that of the foregoing examples illustrating the present invention.
  • 14.6 grams 9.9% wax emulsion were mixed with 27.1 grams of viscose containing about 8% of cellulose.
  • the viscose containing the emulsion mixture was cast on a fibrous cellulose paper web with a V-.” diameter #90 wire-wound rod and subsequently coagulated and regenerated in a conventional sulfuric acid/sodium sulfate bath as previously described.
  • the resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 15 minutes at 100°C. This sample is designated as sample E.
  • This example is for a blend of cellulose and wax without poly (ethylene-acrylic acid) .
  • the surface properties were measured and compared with that of the current invention. 10.1 grams 9.6% wax emulsion were mixed with 28.3 grams of viscose containing about 8% of cellulose. After homogenization, the viscose containing the emulsion mixture was cast on a cellulose paper web with a Vfe" diameter #90 wire-wound rod and subsequently coagulated and regenerated in a conventional acid/salt bath as previously described. The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 15 minutes at 100°C. This sample is designated as sample F.
  • This example is for a blend of cellulose and wax only without poly (ethylene-acrylic acid).
  • the surface properties were measured and compared with that of the current invention. 6.5 grams of 10% wax emulsion were mixed with 30.9 grams of viscose containing about 8% of cellulose. After homogenization, the viscose containing the emulsion mixture was cast on a cellulose paper web with a Vz" diameter #90 wire-wound rod and subsequently coagulated and regenerated in the conventional acid/salt bath previously described. The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 20 minutes at 102°C. This sample is designated as sample G.
  • This example is for a blend of cellulose and poly (ethylene-acrylic acid) without wax.
  • the surface properties were measured and compared with that of the current invention. 17.8 grams of 10% aqueous emulsion of poly (ethylene-acrylic acid) were mixed with 33.4 grams of viscose containing about 8% of cellulose. After homogenization, the viscose containing the emulsion mixture was cast on a cellulose paper web with a V2 1 ' diameter #90 wire-wound rod and subsequently coagulated and regenerated in the conventional acid/salt bath as previously described.
  • sample H The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 35 minutes at 100°C. This sample is designated as sample H.
  • the surface properties are measured and compared with that of the current invention. 12.7 grams of 10% aqueous emulsion of poly (ethylene-acrylic acid) are mixed with 36.9 grams of viscose containing of 8% of cellulose. After homogenization, the viscose containing the emulsion mixture was cast on a cellulose paper web with a V2" diameter #90 wire-wound rod and subsequently coagulated and regenerated in the conventional acid/salt bath previously described. The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 20 minutes at 100°c. This sample is designated as sample I.
  • the surface properties are measured and compared with that of the current invention. 10.4 grams of 10% aqueous emulsion of poly (ethylene-acrylic acid) are mixed with 52.1 grams of viscose containing about 8% of cellulose. After homogenization, the viscose containing the emulsion mixture is cast on the cellulose paper web with a V2" diameter #90 wire-wound rod and subsequently coagulated and regenerated in the previously described conventional acid/salt bath. The resultant regenerated cellulose fiber reinforced composite was then dried in an oven for 30 minutes at 100°c. This sample is designated as sample J.
  • the surface properties including surface tension, polarity, interfacial tension, work of adhesion, and protein spreading coefficient of the foregoing samples were measured and calculated from the contact angle data obtained by using a series of solvents with varying surface tension and polarity.
  • the contact angle measurements were carried out by using a Contact Angle Viewer manufactured by Kayeness, Inc. in Honey Brook, PA.
  • the work of adhesion, interfacial tension, and spreading coefficient are calculated from the surface tension and polarity of composite surface and polypeptide (mixed poly ( -methyl-L- glutamate) ⁇ sheet) surface.
  • the polypeptide surface had a surface tension of 42 dyne/cm and a polarity of 36%.
  • the polypeptide was used as a standard to evaluate the adhesion on different surfaces.
  • the physical characterization method used here is not intended as an absolute measurement of surface properties, but instead it is used consistently for all surfaces to demonstrate the difference between different surfaces for the purpose of comparison.
  • the surface properties of Examples 1 through 10 are tabulated in Table 1 for easy comparison.
  • the method of measuring the surface properties is the same in this example as that described in Example 11.
  • the current example gives the surface properties of an alkyl ketene dimer coated cellulose surface, which has been known to give minimum adhesion to the hydrophilic surface such as sausage meat surface (for example, U.S. Patent 3,158,492 and U.S. Patent 3,106,471).
  • the surface properties including surface tension, polarity, interfacial tension, work of adhesion, and polypeptide spreading coefficient are listed in Table II.
  • the tube was then stuffed with brine injected, salted, de-boned and de-fatted pork lion.
  • the stuffed product was dried, smoked, cooked, cooled, and frozen. After freezing, the tube was peeled. The casing could be easily peeled without adhesion spots. The surface properties were measured, indicating a polarity equal to 0.4% and surface tension equal to 39 dyne/cm.
  • the tube was then stuffed with de-fatted pork loin, as described in Example 13.
  • the stuffed product was dried, smoked, cooked, cooled, and frozen. After freezing, the tube was peeled.
  • the casing could be easily peeled without adhesion spots.
  • the surface properties were measured, indicating a polarity equal to 0.4% and surface tension equal to 34 dyne/cm.
  • the same casing was also stuffed with salted, lean pork back meat, smoked, cooked, and cooled to ⁇ 2°C.
  • the casing was peeled the next day.
  • the casing could be peeled easily without any adhesion spots.
  • the same casing was also stuffed with lean skinned pork bellies, which had been salted and rolled through spices and gelatin. The product was cooked, and then cooled to ⁇ 2°C . The casing was peeled the next day. The casing could again be peeled easily without any adhesion spots .
  • compositions of the present invention also can contain fillers, colorants, stabilizers, and the like.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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  • Food Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention porte sur une composition de matériaux composites cellulosiques comprenant une cire hydrophobe, un polymère anionique contenant carboxy et une cellulose. Cette composition composite est obtenue par coagulation, régénération et séchage d'un mélange comprenant une émulsion de cire hydrophobe, une émulsion polymère anionique contenant carboxy et une viscose. Le composite a une surface hydrophobe dont l'adhérence aux surfaces hydrophiles est réduite comparé à la cellulose régénérée seule, ou comparé à la cellulose comprenant une cire de paraffine seule ou une cellulose comprenant un polymère anionique seul contenant carboxy. Cette composition est donc une composition synergique contenant une cellulose et ayant une adhérence à une surface hydrophile inférieure à celle de la cellulose avec ou sans les autres composants individuels de la composition. Cette composition est préparée par précipitation (coagulation et/ou régénération) à partir d'un mélange comprenant une émulsion de cire hydrophobe, une émulsion polymère anionique et une viscose. Le produit régénéré est ensuite séché de façon à obtenir un matériau composite ayant une surface hydrophobe.
PCT/GB2000/001812 1999-06-15 2000-05-11 Compositions de materiaux destinees a la production de composites cellulosiques reduisant l'adherence WO2000076322A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00929699A EP1189516A1 (fr) 1999-06-15 2000-05-11 Compositions de materiaux destinees a la production de composites cellulosiques reduisant l'adherence
AU47702/00A AU4770200A (en) 1999-06-15 2000-05-11 Material compositions for the production of adhesion-reducing cellulose composites

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33310499A 1999-06-15 1999-06-15
US09/333,104 1999-06-15

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WO2000076322A1 true WO2000076322A1 (fr) 2000-12-21

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EP (1) EP1189516A1 (fr)
AU (1) AU4770200A (fr)
CZ (1) CZ20014506A3 (fr)
WO (1) WO2000076322A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9210943B2 (en) 2010-08-31 2015-12-15 Viskoteepak Belgium Nv Food casings with modified adhesion and release properties and methods of manufacture
EP2978798A4 (fr) * 2013-03-25 2016-11-16 Fpinnovations Inc Films de cellulose avec au moins une surface hydrophobe ou moins hydrophile

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2144383A (en) * 1937-06-23 1939-01-17 Du Pont Method of moistureproofing
GB859804A (en) * 1959-06-12 1961-01-25 Union Carbide Corp Improvements in and relating to drying regenerated cellulose tubing
US3753740A (en) * 1969-12-23 1973-08-21 Tee Pak Inc Easily peelable sausage casing
EP0055056A1 (fr) * 1980-12-22 1982-06-30 Rohm And Haas Company Fibres de rayonne alliée, à haute capacité de rétention de liquides, procédé pour leur fabrication et articles contenant ces fibres
FR2667867A1 (fr) * 1990-10-11 1992-04-17 Wolff Walsrode Ag Procede pour la fabrication d'une enveloppe tubulaire de pelabilite amelioree.
US5198492A (en) * 1989-02-13 1993-03-30 Rohn And Haas Company Low viscosity, fast curing binder for cellulose
WO1997049293A1 (fr) * 1996-06-26 1997-12-31 Cryovac, Inc. Emballage contenant un produit alimentaire cuit emballe dans une pellicule qui comprend une couche adhesive pour aliments contenant un copolymere d'olefine/acide acrylique a haute temperature de ramollissement vicat
WO1998058015A1 (fr) * 1997-06-16 1998-12-23 Lenzing Aktiengesellschaft Composition contenant de fines particules solides

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2144383A (en) * 1937-06-23 1939-01-17 Du Pont Method of moistureproofing
GB859804A (en) * 1959-06-12 1961-01-25 Union Carbide Corp Improvements in and relating to drying regenerated cellulose tubing
US3753740A (en) * 1969-12-23 1973-08-21 Tee Pak Inc Easily peelable sausage casing
EP0055056A1 (fr) * 1980-12-22 1982-06-30 Rohm And Haas Company Fibres de rayonne alliée, à haute capacité de rétention de liquides, procédé pour leur fabrication et articles contenant ces fibres
US5198492A (en) * 1989-02-13 1993-03-30 Rohn And Haas Company Low viscosity, fast curing binder for cellulose
FR2667867A1 (fr) * 1990-10-11 1992-04-17 Wolff Walsrode Ag Procede pour la fabrication d'une enveloppe tubulaire de pelabilite amelioree.
WO1997049293A1 (fr) * 1996-06-26 1997-12-31 Cryovac, Inc. Emballage contenant un produit alimentaire cuit emballe dans une pellicule qui comprend une couche adhesive pour aliments contenant un copolymere d'olefine/acide acrylique a haute temperature de ramollissement vicat
WO1998058015A1 (fr) * 1997-06-16 1998-12-23 Lenzing Aktiengesellschaft Composition contenant de fines particules solides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9210943B2 (en) 2010-08-31 2015-12-15 Viskoteepak Belgium Nv Food casings with modified adhesion and release properties and methods of manufacture
US9694385B2 (en) 2010-08-31 2017-07-04 Viskoteepak Belgium Nv Method of manufacturing food casings with modified adhesion and release properties
EP2978798A4 (fr) * 2013-03-25 2016-11-16 Fpinnovations Inc Films de cellulose avec au moins une surface hydrophobe ou moins hydrophile

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EP1189516A1 (fr) 2002-03-27
CZ20014506A3 (cs) 2002-05-15
AU4770200A (en) 2001-01-02

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