WO2000004787A9 - Packaging biological materials - Google Patents
Packaging biological materialsInfo
- Publication number
- WO2000004787A9 WO2000004787A9 PCT/US1999/016576 US9916576W WO0004787A9 WO 2000004787 A9 WO2000004787 A9 WO 2000004787A9 US 9916576 W US9916576 W US 9916576W WO 0004787 A9 WO0004787 A9 WO 0004787A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane according
- permeable
- polysiloxane
- block copolymer
- blocks
- Prior art date
Links
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 17
- 239000012620 biological material Substances 0.000 title claims abstract description 14
- -1 polysiloxane Polymers 0.000 claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 37
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 29
- 229920001400 block copolymer Polymers 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 10
- 230000004927 fusion Effects 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 40
- 230000035699 permeability Effects 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000037361 pathway Effects 0.000 claims 1
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 229920001688 coating polymer Polymers 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003490 calendering Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007756 gravure coating Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 3
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 2
- 235000017647 Brassica oleracea var italica Nutrition 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000019693 cherries Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical group CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009470 controlled atmosphere packaging Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical class CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000009448 modified atmosphere packaging Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23B7/148—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/18—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient
- B65D81/20—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient under vacuum or superatmospheric pressure, or in a special atmosphere, e.g. of inert gas
- B65D81/2069—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient under vacuum or superatmospheric pressure, or in a special atmosphere, e.g. of inert gas in a special atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D2565/38—Packaging materials of special type or form
- B65D2565/381—Details of packaging materials of special type or form
- B65D2565/388—Materials used for their gas-permeability
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1317—Multilayer [continuous layer]
- Y10T428/1321—Polymer or resin containing [i.e., natural or synthetic]
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/24998—Composite has more than two layers
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- This invention relates to gas-permeable membranes which are useful in particular for the packaging of biological materials, especially fresh produce.
- a respiring material should be stored in a container having a total permeability to O 2 and a total permeability to C0 2 which are correlated with (i) the atmosphere outside the package (usually air), (ii) the rates at which the material consumes O 2 and produces CO 2 , and (iii) the temperature, in order to produce an atmosphere within the container (the "packaging atmosphere") having the desired O 2 and CO 2 concentrations for preservation of the material.
- the total permeability to water vapor may also be significant.
- CAP controlled atmosphere packaging
- MAP modified atmosphere packaging
- OTR O 2 transmission rate
- COTR CO 2 transmission rate
- the O 2 transmission rate (referred to herein as OTR) and CO 2 transmission rate (referred to herein as COTR), of a body composed of a particular material, are the amounts of O 2 and CO 2 , respectively, which will pass through a defined area of that body under defined conditions.
- the total permeabilities of a container to O 2 and CO 2 depend, therefore, upon the areas, OTRs and COTRs of the various parts of the container.
- the preferred packaging atmosphere depends on the stored material. For many materials, the preferred concentration of O 2 is less than the preferred concentration of CO 2 .
- broccoli is generally best stored in an atmosphere containing 1-2% O 2 and 5-10% C0 2 ; berries are generally best stored in an atmosphere containing 5- 10% O 2 and 10-20% CO ; and cherries are generally best stored in an atmosphere containing 5-8% O 2 and 10-20% CO 2 .
- the container In order to produce a packaging atmosphere having a high ratio of CO 2 to O 2 , the container should have a low ratio of total CO 2 permeability to total 0 2 permeability.
- the term R ratio is used herein to denote the ratio of COTR to OTR for a particular material or the ratio of total C0 2 permeability to total 0 2 permeability of a container or part of a container.
- Respiring biological materials are often stored at temperatures substantially below normal room temperature, but exposed to room temperatures before being used. At room temperatures, the respiration rate increases. Therefore, in order to maintain the desired packaging atmosphere, the permeability of the container preferably increases sharply between storage temperatures and room temperatures.
- containers should comprise (i) one or more barrier sections which are relatively large in area and are composed of materials having relatively low OTR and COTR values (e.g.
- atmosphere-control members composed of a membrane prepared by coating a thin layer of a polymer onto a microporous film.
- the permeability of these membranes is lower, and as a result such atmosphere-control members are of practical size.
- the coating polymer in particular the use of a low-melting side chain crystalline (SCC) polymer as described in International Publication No. WO 96/38495, the membranes can have OTRs which increase sharply with temperature.
- SCC side chain crystalline
- the SCC polymers tend to be somewhat tacky, and, therefore, to be partially removed from the microporous base film during handling.
- their inherent permeability to gases is such that, in order to produce a coated membrane of desired size and O 2 permeability, the coating must be rather thin (e.g. 2-3 microns thick). Such thin coatings are difficult to apply uniformly and are liable to be damaged during use.
- the known coated membranes generally have R ratios which are too high when the desired packaging atmosphere contains a relatively large proportion of C0 2 .
- This invention provides improved gas-permeable membranes which can be used to overcome these problems and which comprise (a) a gas-permeable substrate, particularly a microporous polymeric film, and
- a polymeric coating on the microporous film comprising a block copolymer which has a heat of fusion ⁇ H of at least 5 J/g, and which comprises (i) polysiloxane polymeric blocks, and
- gas permeable membranes are particularly useful as atmosphere control members in packages for respiring biological materials, and will be chiefly described by reference to such use. It is to be understood, however, that the invention includes gas-permeable membranes which are useful for other purposes.
- this invention makes it possible to prepare gas-permeable membranes which are resistant to damage through abrasion, have uniform properties, and which combine (a) a P 10 value of at least 1.8, e.g.
- OTR O 2 permeability
- COTR CO 2 permeability
- OTR and COTR values are measured at about 22 °C. unless otherwise noted, and are given in ml/m 2 .atm.24hrs, with the equivalent in cc/100 inch 2 - atm 24 hrs in parentheses.
- OTR and COTR values were measured using a permeability cell (supplied by Millipore) in which a mixture of O 2 , C0 and helium is applied to the sample, using a pressure of 0.035 kg/cm 2 (0 .5 psi), and the gases passing through the sample were analyzed for 0 2 and C0 2 by a gas chromatograph.
- the cell could be placed in a water bath to control the temperature.
- the abbreviation P 10 is used to denote the ratio of OTR at a first temperature T ⁇ °C (OTR 2 ) to OTR at a second temperature T 2 °C (OTR 2 ), where T 2 is (T- ⁇ o C-10 °C), T-i being a temperature in the range 10-25 °C, or, when T 2 is a temperature which is not (T- ⁇ .10) °C, but is a temperature lower than T-i , to denote the ratio T!-T 2 OTR 2
- the abbreviation R is used to denote the ratio of COTR to OTR. Pore sizes are measured by mercury porosimetry or an equivalent procedure.
- T 0 denotes the onset of melting
- T p denotes the crystalline melting point
- ⁇ H denotes the heat of fusion.
- T 0 , T p and ⁇ H are measured by means of a differential scanning calorimeter (DSC) at a rate of 10 °C./minute and on the second heating cycle.
- DSC differential scanning calorimeter
- the microporous base film preferably used as the porous substrate in this invention comprises a polymeric matrix which provides a network of interconnected pores such that gases can pass through the film.
- the average pore size of the base film can be 0.02 to 5 micron, but is preferably greater than 0.05 micron and less than 0.24, particularly less than 0.20, especially less than 0. 15, micron.
- Preferably at least 70%, particularly at least 90%, of the pores have a pore size of less than 0.24micron.
- at least 60%, particularly at least 80%, of the pores have a pore size of less than about 0. 15 micron.
- Particularly at least 60%, especially at least 70%, of the pores have a pore size of less than about 0.11 micron.
- the pores preferably constitute 35 to 80%, particularly 60 to 75%, by volume of the film.
- a narrow range of pore sizes is preferred. For example, it is preferred that less than 20% of the pores have a size less than 0.014 micron, and that less than 20% of the pores have a pore size greater than 0.13 micron.
- the base film should have sufficient strength (and other physical properties) to ensure that it is not damaged in processing or in use.
- the base film preferably has a tear strength of at least 30g, particularly at least 70g, when measured by the following test.
- a sample of the film, 10 by 1.27 cm, is used.
- a slit 5 mm long is made in one of the short sides. The two flaps on either side of the slit are placed in opposing jaws of an Instron tensile tester, and the tear strength measured at a jaw separation rate of 12.7cm(5 inch)/minute.
- the base film has too low a tear strength, it is possible to prepare a satisfactory membrane by laminating the base film, before or after it has been coated, to a support film which has a satisfactory tear strength and sufficient porosity that its presence does not adversely affect the permeability of the coated membrane. It is also preferred that the microporous base film should have a Sheffield smoothness of at least 30. It is also preferred that the base film is composed of a material that can be heat-sealed.
- Preferred polymers for polymeric matrix of the base film are (1 ) essentially: linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 18, preferably 18 to 39, deciliters/gram, (2) essentially linear ultrahigh molecular weight polypropylene having an intrinsic viscosity of at least 6 deciliters/gram, and (3) mixtures of (1 ) and (2).
- the preferred base film includes a finely divided, particulate, substantial ⁇ water insoluble, inorganic filler, for example a siliceous filler, which is distributed throughout the matrix and which is present in amount 50 to 90%. particularly 50 to 85%, by weight of the base film.
- the filler is preferably silica, particularly precipitated silica, especially silica having an average ultimate particle size of less than 0.1 micrometer.
- the filler occupies 35 to 80% of the total volume of microporous film.
- Particularly preferred, because they have a relatively narrow range of pore sizes, are films made by extruding a polymeric composition which contains an inorganic filler and a processing oil, e.g.
- a paraffinic oil, naphthenic oil or aromatic oil uniformly distributed therein; followed by extraction of the processing oil, e.g. with trichioroethylene.
- Suitable films are disclosed, for example, in US Patent Nos. 4,937,115 and 3,351 ,495; such films are sold by PPG Industries under the tradename "Teslin".
- the thickness of the base film is preferably 0.03 to 0.65 mm.
- the microporous base film can be modified by calendering at a nip pressure of 17.8 to 266.6 kg per linear cm (100 to 1500 pli). Calendering the base film often, results in coated films which have reduced OTR values and increased R values,
- the base film can be uniaxiaily or biaxially calendered.
- the base film can also be stretched, uniaxiaily or biaxially.
- block copolymer is used in this specification in a broad sense to include random block copolymers, ordered block copolymers (including thermoplastic elastomers), and graft block copolymers in which one of the blocks is the polymer backbone and the other blocks are pendant from the backbone.
- the block copolymer used as a coating polymer in this invention comprises, and may consist essentially of,
- the crystalline polymeric blocks must have sufficient crystallinity, and be present in a large enough proportion, that the block copolymer has a heat of fusion ⁇ H of at least 5J/g, preferably at least 10 J/g, with higher values resulting in higher P10 values.
- the polysiloxane polymeric block is present in amount sufficient to reduce the tackiness of the crystalline polymer to a level such that the layer of coating polymer is not easily damaged during routine handling. A small proportion, e.g. 5 to 15%) by weight of the block copolymer, can be effective for this purpose.
- the copolymer should contain the polysiloxane blocks in amount such that the oxygen permeability of the copolymer is substantially greater than the oxygen permeability of the crystalline polymer alone, for example at least 1.2 times, preferably at least 1.5 times, the oxygen permeability of the crystalline polymer alone.
- the copolymer may contain, for example, up to 80% of the polysiloxane blocks, and preferably contains 15 to 60%, particularly 20 to 40%, of polysiloxane blocks. It is preferred that the oxygen permeability of the block copolymer is such that the coating weights at which it can be conveniently and consistently applied result in a coated membrane having the desired OTR.
- the crystalline polymeric blocks have a melting point T p of -5 °C. to 40 °C, with T p being selected with a view to the temperature range over which an increase in OTR is desired. Generally T p is from -5 °C. to 15 °C.
- the crystalline polymeric blocks can all be the same, or there can be two or more different kinds of crystalline polymer block. Suitable polymers from which the crystalline polymeric blocks can be derived include the polymers described in US Patent No. 5,254,354. Particularly preferred are side chain crystalline (SCC) polymers.
- SCC polymers can be prepared for example by copolymerizing (i) at least one n-alkyl or -fluoroalkyl acrylate or methacrylate in which the alkyl group contains at least 12 carbon atoms, preferably one or more of docosanyl, octadecyl, hexadecyl, tetradecyl, and dodecyl acrylates, and (ii) one or more comonomers selected from acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid in which the esterifying group contains less than 10 carbon atoms, e.g.
- SCC polymers generally have a high R ratio, e.g. greater than 5, except for those polymers which contain substantial amounts of fluoroalkyl and/or cycloalkyl groups.
- Particularly preferred SCC polymers are those prepared by copolymerizing (i) at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon atoms and (ii) one or more comonomers selected from acrylic acid , methacrylic acid, and esters of acrylic or methacrylic acid in which the esterifying group contains less than 10 carbon atoms.
- the polysiloxane blocks in the block copolymer can be derived from conventional polysiloxanes, e.g. polyalkyl siloxanes, for example polydimethylsiioxanes and polymethyl n-alkyl siloxanes wherein the n-alkyl group contains a dodecyl, tetradecyl or hexadecyl group or other group which confers crystalline character on the polysiloxane.
- the polysiloxane blocks can all be of the same kind or there can be two or more different kinds of polysiloxane block.
- the block copolymers can be prepared using conventional synthetic techniques.
- One method of making the block copolymer comprises copolymerizing a mixture of reactants which comp ⁇ ses (i) one or more monomers which will react to, form a crystalline polymer, e.g. monomers which comprise at least one n-alkyl: acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon, atoms, and (ii) a polysiloxane having a copolymerizable group, e.g. a methacryioxypropylgroup, at one end of the polymer chain.
- the block copolymers prepared by this method have a backbone which provides the crystalline block, and polysiloxane blocks which are pendant from that backbone. These copolymers are believed to be novel, and as such form part of the present invention.
- Another method comprises reacting (i) a crystalline polymer having a melting point of -5 to 40 °C. and containing at least one reactive group, and (ii) a polysiloxane containing at least one group which will react with said reactive group on the crystalline polymer.
- Suitable reactive groups in the polysiloxane include amino groups.
- Suitable reactive groups in the crystalline polymer include carboxylic acid groups which will react with amino groups on a polysiloxane.
- the block copolymer can contain other blocks which are not polysiloxane blocks or crystalline blocks as defined above. Two or more block copolymers as defined above can be blended together, or the block copolymer(s) as defined above can be blended with another polymer.
- the coating polymer can be applied to the porous substrate as a coating composition which comprises the coating polymer dissolved in a suitable solvent, e.g. toluene, tetrahydrofuran, heptane or methyl ethyl ketone. After the composition has been applied, the solvent is removed by heating, leaving the polymer adherent to the substrate.
- a suitable solvent e.g. toluene, tetrahydrofuran, heptane or methyl ethyl ketone.
- the concentration of the coating polymer in the coating composition is preferably 2 to 12%, e.g. 5 to 10%, based on the weight of the composition.
- the coating composition can contain other ingredients in addition to the polymer and the solvent.
- the coating can be carried out in any convenient way, for example by hand using a Meyer rod, or using commercially available coating equipment, e.g. gravure- coating equipment, which is preferred, or knife-over-roll equipment.
- a single coating is normally adequate, but a second coating of the same or a different coating composition can be applied after drying the first.
- the coating is carried out using a gravure coating roll having a theoretical cell volume of 31 x 10 6 to 232.5 x10 6 cubic microns per mm 2 (20 x 10 9 to 150 x 10 9 cubic microns per inch 2 ), preferably 62 x 10 6 to 124 x 10 6 cubic microns per mm 2 (40 x 10 9 to 80 x 10 9 cubic microns per inch 2 ), or using equipment which provides a similar coating weight.
- the coating weight is preferably 1.5 to 5, particularly 2 to 4, e.g. 2.9 to 3.6, g/m 2 .
- the membrane preferably has a P- ratio, over at least one 10°C. range between -5 and 15 °C, preferably over at least one 10 °C. range between O °C. and 15 °C, of at least 1.3, preferably at least 2, particularly at least 2.5, especially at least 2.6.
- the membrane preferably has an OTR of 775,000 to 7,750,000 (50,000 to 500,000), preferably 1 ,550,000 to 3,875,000 (100,000 to 250,000), particularly at least 2,325,000,(150,000).
- the R ratio of the membrane is preferably at least 2, particularly at least 2.5, especially at least 3; and when the OTR is 775,000 to 3,100,000 (50,000 to 200,000), the R ratio is preferably more than 3.8 -0.00000045 P' (3.8 - 0.000007P), particularly up to 7.4-0.00000116
- the membrane preferably also has these values for OTR and R when the OTR and COTR are measured at any temperature between 20 and 25 °C.
- the membrane preferably has these values for OTR, P 10 and R both when the O 2 and CO 2 permeabilities are measured at 0.7 kg/cm 2 (10 psi) and when they are measured at 0.035 kg/cm 2 (0.5 psi).
- the membrane can be covered by a covering layer, so that the polymeric coating is sandwiched between the microporous film and the covering layer, providing that the covering layer is sufficiently porous not to have an adverse effect on permeability.
- the covering layer is generally different from, but can be the same as, the base film.
- the cover layer can be melt-bonded to the coated film.
- the use of a covering layer adds to the cost of the product.
- the properties of the membrane can be modified by calendering, uniaxiaily or biaxially, preferably at a nip pressure of 17.8 to 266.6 kg per linear cm. (100 to 1500 pli). Calendering generally reduces the OTR and increases the R ratio of the membrane.
- the novel gas-permeable membrane of this invention provides at least part of an atmosphere-control member in a container which is sealed (or is suitable for sealing) around a respiring biological material.
- the container can contain a single novel control member, or two or more novel control members (which will usually be the same, but can be different).
- the container in order to ensure that the internal pressure within the container can equilibrate with ambient pressure, the container can contain a pinhole.
- the invention includes the possibility that the container also contains one or more atmosphere-control members which are not in accordance with the present invention.
- the remainder of the container i.e. the barrier section or sections, which is of much larger area than the control member(s), is composed of one or more materials which are relatively impermeable to O and CO 2 , e.g. a suitable polymeric film or other shaped article.
- the barrier sections are composed of a material whose OTR and COTR are so low that the packaging atmosphere is substantially determined only by the control member(s).
- the barrier sections have OTR and COTR values which (although low) are high enough that, having regard to the relative large area of the barrier section(s), a substantial proportion of the 0 2 entering the packaging atmosphere passes through the barrier: sections. At 22 °C this proportion can be, for example, as high as 50%, but is generally less than 25%.
- the barrier section is provided by a bag of flexible polymeric film or by two preformed, relatively rigid, polymeric members which have been heat-sealed to each other, and the atmosphere-control member covers an aperture cut into the bag or one of the preformed members.
- the control member(s) can be secured to the barrier section(s) in any way, for example through heat sealing or with an adhesive.
- the size of the containers can vary considerably. In one category, the container contains up to 2.26 kg (5 lb) of produce. In another category, the containers are much larger, e.g. containing up to 1500 lb. (680 kg) of produce.
- a wide range of respiring biological materials can be packaged in containers of the invention, including cherries, broccoli, cut lettuce, cauliflower, mushrooms, asparagus, and strawberries.
- the size and nature of the atmosphere-control members control the absolute and relative amounts of 0 2 and CO 2 which can enter and leave the container, and, therefore, the packaging atmosphere within the container.
- the desired packaging atmosphere will depend upon the biological material within the container, and the temperature, and the atmosphere-control member(s) should be selected accordingly.
- Those skilled in the art of packaging biological materials will have no difficulty, having regard to the disclosure in this specification and their own knowledge, in designing containers which will give substantially improved results under practical conditions of use and which can be economically manufactured.
- ADMS is a polydimethyl siloxane terminated at each end by an amino group and having an M w of about 27,000, which is available from
- VDMS is a polydimethyl siloxane terminated at each end by a vinyl group and having an M w of about 28,000, which is available from
- MACDMS is a polydimethylsiloxane terminated at one end only by a methacryloxypropyl group, which is available from Gelest under the trade name MCR M-17.
- DMS is a room temperature vulcanizable (RTV) polydimethyl siloxane available from General Electric under the tradename Sylgard
- AIBN is 2,2'-azobis (2-methylpropionitrile).
- Esperox is t-amylperoxy-2-ethylhexanoate, which is available from Witco
- TMI dimethyl meta-isopropenyl benzyl isocyanate, which is available from American Cyanamid under the tradename TMI.
- Tesiin SP7 is a microporous polyethylene film containing about 50% silica, which is available from PPG Industries under the tradename Tesiin SP7. It has a thickness of about 0.18 mm (0.007 inch), a tear strength of about 90g, a porosity of about 65%, an average pore size of about 0.1 micron and a largest pore size of 4-10 microns.
- BuAc is butyl acetate.
- MEK is methyl ethyl ketone.
- Examples AI-A7 show the preparation of SCC polymers.
- Examples AI-A5 show the preparation of SCC polymers which are subsequently reacted with a polysiloxane to form a block copolymer.
- Examples A6 and A7 show the direct preparation of SCC/siloxane block copolymers through the use of a polysiloxane which is terminated at one end with an unsaturated group which will copolymerize with the acrylate monomers.
- SCC polymers having the Mw, Mn, T and AH values shown in Table I were prepared using the monomers, solvents and initiators, and amounts thereof (in parts by weight) shown in Table 1. In a first step, the monomers, and the solvents and initiators shown for the first step, were maintained at the temperature and for the time shown in Table 1 for the first step.
- Examples AI-A7 show the preparation of SCC polymers.
- Examples AI-A5 show the preparation of SCC polymers which are subsequently reacted with a polys
- Example Bl, B2, B4, B5 and B6 SCC/siioxane block copolymers were prepared using one of the SCC polymers prepared in Examples A2 to A5 and 3: polysiloxane, in the amounts (in parts by weight) shown in Table 2.
- Example B 1 the reaction was carried out in butyl acetate (260 parts by weight), and the reaction, mixture was heated under reflux at 11 °C for 6 hours. Similar reaction conditions were employed in Examples B2-B5
- Example B6 the SCC polymer (A5) was, diluted to 4% solids, and the polysiloxane (ADMS) was then added.
- ADMS polysiloxane
- Example B3 the SCC polymer and the polysiloxane were merely blended together, and no reaction took place between them.
- the DMS was diluted to 90% solids with toluene and hand-coated onto Tesiin SP7 using a #30 Meyer rod.
- the other polymers were diluted in a suitable solvent (usually heptane) to a desired concentration, as shown in Table 3.
- the diluted solution was coated onto a Tesiin SP7 substrate using a gravure coating cylinder having a theoretical cell volume of 5 9 x 10' cubic microns per inch 2 and then allowed to dry.
- the coating weight of the dry polymer varies, for example, with the molecular weight of the polymer; when the concentration of the polymer is 5-8%, the use of this gravure coating cylinder results in a dry coating weight of about 1.5-4 g/m 2 .
- the OTR and COTR of the coated substrate were measured and the value of R was calculated. The values obtained changed somewhat during the first four days after coating, but did not change substantially thereafter.
- the OTR and COTR of a number of different samples were measured, and Table 3 reports the average of four samples, and, in the column headed "OTR RSD %", the standard deviation of the measured samples, expressed as a percentage. For some samples, the OTR was measured at 0 and 10 °C or at 7 and 22°C and the P 10 value was calculated, and is reported in Table 3. The P10 value of the 5% B4 sample between 5 and 15°C was also measured and found to be 3.4.
Abstract
Description
Claims
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JP2000560790A JP4447167B2 (en) | 1998-07-23 | 1999-07-22 | Packaging of biological products |
DE69907199T DE69907199D1 (en) | 1998-07-23 | 1999-07-22 | BIOLOGICAL PACKAGING MATERIAL |
EP99935832A EP1098569B1 (en) | 1998-07-23 | 1999-07-22 | Packaging biological materials |
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US09/121,082 | 1998-07-23 | ||
US09/121,082 US6548132B1 (en) | 1998-07-23 | 1998-07-23 | Packaging biological materials |
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-
1998
- 1998-07-23 US US09/121,082 patent/US6548132B1/en not_active Expired - Lifetime
-
1999
- 1999-07-22 WO PCT/US1999/016576 patent/WO2000004787A1/en active IP Right Grant
- 1999-07-22 JP JP2000560790A patent/JP4447167B2/en not_active Expired - Lifetime
- 1999-07-22 DE DE69907199T patent/DE69907199D1/en not_active Expired - Lifetime
- 1999-07-22 EP EP99935832A patent/EP1098569B1/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9233063B2 (en) | 2009-12-17 | 2016-01-12 | Air Products And Chemicals, Inc. | Polymeric compositions for personal care products |
Also Published As
Publication number | Publication date |
---|---|
JP4447167B2 (en) | 2010-04-07 |
US6548132B1 (en) | 2003-04-15 |
JP2002521014A (en) | 2002-07-16 |
EP1098569B1 (en) | 2003-04-23 |
DE69907199D1 (en) | 2003-05-28 |
EP1098569A1 (en) | 2001-05-16 |
WO2000004787A1 (en) | 2000-02-03 |
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