NZ756502B2 - Degradable sheet material - Google Patents
Degradable sheet material Download PDFInfo
- Publication number
- NZ756502B2 NZ756502B2 NZ756502A NZ75650218A NZ756502B2 NZ 756502 B2 NZ756502 B2 NZ 756502B2 NZ 756502 A NZ756502 A NZ 756502A NZ 75650218 A NZ75650218 A NZ 75650218A NZ 756502 B2 NZ756502 B2 NZ 756502B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- amount
- sheet material
- composition
- additive
- transition metal
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 claims abstract description 126
- 239000000654 additive Substances 0.000 claims abstract description 75
- 230000000996 additive Effects 0.000 claims abstract description 73
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 68
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 35
- 229960003563 Calcium Carbonate Drugs 0.000 claims abstract description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 34
- 229920002472 Starch Polymers 0.000 claims abstract description 30
- 239000008107 starch Substances 0.000 claims abstract description 30
- 235000019698 starch Nutrition 0.000 claims abstract description 30
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 239000000292 calcium oxide Substances 0.000 claims abstract description 21
- -1 polyethylene Polymers 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 14
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 14
- 150000001408 amides Chemical class 0.000 claims abstract description 13
- 239000004743 Polypropylene Substances 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 239000004698 Polyethylene (PE) Substances 0.000 claims abstract description 10
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- 150000001785 cerium compounds Chemical class 0.000 claims abstract description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 7
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 7
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 7
- 229920001155 polypropylene Polymers 0.000 claims abstract description 7
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 7
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 7
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims description 37
- 238000006731 degradation reaction Methods 0.000 claims description 36
- 230000004059 degradation Effects 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 19
- 235000012171 hot beverage Nutrition 0.000 claims description 12
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-M stearate Chemical compound CCCCCCCCCCCCCCCCCC([O-])=O QIQXTHQIDYTFRH-UHFFFAOYSA-M 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N Calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000029087 digestion Effects 0.000 claims description 4
- 230000000813 microbial Effects 0.000 claims description 4
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 238000002144 chemical decomposition reaction Methods 0.000 claims description 3
- 230000000977 initiatory Effects 0.000 claims description 3
- 238000011068 load Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003856 thermoforming Methods 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-Triazacyclononane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000010102 injection blow moulding Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 238000009472 formulation Methods 0.000 description 16
- 230000027455 binding Effects 0.000 description 14
- 239000003446 ligand Substances 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 235000013305 food Nutrition 0.000 description 8
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- PEVZEFCZINKUCG-UHFFFAOYSA-L copper;octadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O PEVZEFCZINKUCG-UHFFFAOYSA-L 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000013361 beverage Nutrition 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000020965 cold beverage Nutrition 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000015220 hamburgers Nutrition 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 150000003511 tertiary amides Chemical class 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 210000003278 Egg Shell Anatomy 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N Iron(III) oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N Phosphite Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 210000001138 Tears Anatomy 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000001010 compromised Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 230000000593 degrading Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000003203 everyday Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010807 litter Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 150000002823 nitrates Chemical group 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000003244 pro-oxidative Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003156 secondary amide group Chemical group 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 239000004460 silage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001929 titanium oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000002087 whitening Effects 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/22—Boxes or like containers with side walls of substantial depth for enclosing contents
- B65D1/26—Thin-walled containers, e.g. formed by deep-drawing operations
- B65D1/265—Drinking cups
-
- 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
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/105—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with enzymes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention provides a sheet material formed of a degradeable composition, the composition comprising: 30 to 80 wt% calcium carbonate by weight of the composition; an additive; and the balance a polymer selected from polyethylene, polypropylene and copolymers and blends thereof, wherein the additive comprises, by combined weight of the additive and the polymer: (a) two or more transition metal compounds in a total amount of from 0.15 to 0.6 wt%; (b) a mono-or poly-unsaturated C14-C24 carboxylic acid, or an ester, anhydride or amide thereof, in an amount of from 0.04 to 0.08 wt%; (c) a synthetic rubber in an amount of from 0.04 to 0.2 wt%; and, optionally: (d) dry starch in an amount of from 0 to 20 wt%; and/or (e) calcium oxide in an amount of from 0 to 1 wt%; and/or (f) a phenolic antioxidant stabilizer in an amount of from 0 to 0.2 wt%; wherein the two or more transition metal compounds are selected from iron, manganese, copper, zinc, titanium, cobalt and cerium compounds and wherein the transition metals in the two or more transition metal compounds are different. e additive comprises, by combined weight of the additive and the polymer: (a) two or more transition metal compounds in a total amount of from 0.15 to 0.6 wt%; (b) a mono-or poly-unsaturated C14-C24 carboxylic acid, or an ester, anhydride or amide thereof, in an amount of from 0.04 to 0.08 wt%; (c) a synthetic rubber in an amount of from 0.04 to 0.2 wt%; and, optionally: (d) dry starch in an amount of from 0 to 20 wt%; and/or (e) calcium oxide in an amount of from 0 to 1 wt%; and/or (f) a phenolic antioxidant stabilizer in an amount of from 0 to 0.2 wt%; wherein the two or more transition metal compounds are selected from iron, manganese, copper, zinc, titanium, cobalt and cerium compounds and wherein the transition metals in the two or more transition metal compounds are different.
Description
Degradable Sheet Material
The present invention relates to a disposable sheet material suitable for use as
packaging or for forming a container. The sheet material is especially suitable for use
where a waterproof material is required for a single- or temporary-use. A preferred
application is a disposable beverage container for holding hot or cold beverages,
commonly referred to as a “coffee cup”. The material described herein is particularly
advantageous since it readily degrades and addresses concerns with the slow
degradation of standard packaging materials.
Every day tons of paper packaging materials are thrown away. Since the product
appears to be made of paper, the end consumer wrongly assumes that the material
will quickly degrade which may encourage them to litter, or may even expect the
material to be recyclable and place the material in a recycling bin. However, where a
paper material has been made waterproof this is commonly by fusing paper with
polyethylene, a material that cannot be separated out again in a standard recycling
process, and which prevents the material quickly degrading when littered.
This is a particular problem for coffee cups, which are used to sell take-away
beverages such as coffee and tea from high-street shops such as coffee shops.
These cups are typically made from card which has been treated to be waterproofed
and may be provided with a separate or integrated sleeve to insulate the contents
and protect the consumers’ hands from hot or cold beverage liquids.
It is also known to provide plastic packaging materials and containers, including
plastic coffee cups. The use of such polymer materials have many benefits and can
provide strong, chemically and biologically inert materials at relatively low cost.
Unfortunately many of these characteristics make them difficult to dispose of without
causing lasting damage to the environment. The very short functional life of plastic
containers leads to rapid build-up of waste material which is inert to most physical
and chemical action to which they are subjected during conventional disposal.
17556843_1 (GHMatters) P111754.NZ
As the global population becomes more aware of the human effect on our climate,
our ecosystems and the planet as a whole, there is growing demand to increase the
amount of waste which is recycled. Accordingly, there is a growing demand for
alternatives to conventional polymer materials.
Several degradable polymer compositions have been developed. However, there are
significant disadvantages associated with these conventional degradable polymers.
Conventional degradable polymers (such as aliphatic polyesters) are generally more
difficult and complicated to process, resulting in lower output. These materials have
significantly higher densities and lower strength than conventional non-degradable
commodity polymers.
US 4,016,117 discloses the use of biodegradable filler materials, such as starch, and
an autoxidising substance such as a fat which, when exposed to transition metals in
soil, yield peroxides which attack carbon-carbon linkages in the resin.
US 4,931,488 discloses the addition of a biologically degradable substance (starch),
an iron compound (FeOH(stearate)2), and a fatty acid or fatty acid ester (such as
soya oil which is a mix of fatty acid esters) to a thermoplastic polymer. The resultant
plastic composition degrades under the action of heat and/or ultraviolet light and/or
insolation. These compositions have disadvantageous abiotic degradation and
biodegradation rates.
The modern consumer is becoming increasingly aware of their social responsibilities
and their carbon footprint. Accordingly there is increased adverse publicity
associated with this waste issue and an environmentally friendly alternative is
urgently being sought. Accordingly, it is desirable to provide a degradable sheet
material suitable for use in forming packaging or containers, especially coffee cups
and/or tackle at least some of the problems associated with the prior art or, at least,
to provide a commercially useful alternative thereto. In particular, there is a desire to
provide a packaging material or wrapping which is recyclable and in addition,
especially if littered, is readily degradable.
17556843_1 (GHMatters) P111754.NZ
According to a first aspect, the present invention provides a sheet material formed of
a degradable composition, the composition comprising:
to 80wt% calcium carbonate by weight of the composition;
an additive; and
the balance a polymer selected from polyethylene, polypropylene and
copolymers and blends thereof,
wherein the additive comprises, by combined weight of the additive and the
polymer:
(a) two or more transition metal compounds in a total amount of from
0.15 to 0.6wt%;
(b) a mono- or poly-unsaturated C14-C24 carboxylic acid, or an ester,
anhydride or amide thereof, in an amount of from 0.04 to 0.08wt%;
(c) a synthetic rubber in an amount of from 0.04 to 0.2wt%;
and, optionally:
(d) dry starch in an amount of from 0 to 20wt%; and/or
(e) calcium oxide in an amount of from 0 to 1 wt%; and/or
(f) a phenolic antioxidant stabilizer in an amount of from 0 to 0.2 wt%;
wherein the two or more transition metal compounds are selected from iron,
manganese, copper, zinc, titanium, cobalt and cerium compounds and wherein the
transition metals in the two or more transition metal compounds are different.
Preferably the sheet material is a disposable coffee cup. Although the following
disclosure focuses on sheet materials, the disclosure applies equally to an
embodiment where the sheet material is in the form of a disposable coffee cup.
Preferably the additive substantially consists of the listed components (a) to (f).
Preferably the composition substantially consists of the additive, calcium carbonate
and the polymer. That is, preferably the composition comprises less than 5wt% of
other ingredients, more preferably less than 1wt% and most preferably comprises no
other ingredients.
The present invention will now be further described. In the following passages
different aspects of the invention are defined in more detail. Each aspect so defined
17556843_1 (GHMatters) P111754.NZ
may be combined with any other aspect or aspects unless clearly indicated to the
contrary. In particular, any feature indicated as being preferred or advantageous may
be combined with any other feature or features indicated as being preferred or
advantageous.
The present invention provides a sheet material which can be used for packaging or
to form a container. One example of the sheet is a conventional burger wrapping.
This is a thin waterproof wrapping which is often discarded by a consumer falsely
believing it to be readily degradable. Another example is a moulded container, or
folded and glued container such as food carton for use in conveying take-away
foods. Other examples include product packaging for general retail use.
Advantageously the compositions disclosed herein may be heat-sealed to form
closed containers or sealed packaging.
A disposable coffee cup is a container suitable for holding a single serving of a
beverage and from which a consumer can imbibe the beverage. Typically such a
container has a volume of from 30ml to 1l, and more typically from 200 to 350ml. The
container is suitable for holding a hot beverage at a temperature of up to 100°C,
although typically the peak temperature in use is only 80 to 95°C. The container is,
therefore, waterproof within the time period expected for use, i.e. at least 1 day. The
coffee cup is disposable meaning that it is intended to be disposed of after use,
rather than reused for another beverage. The container has an opening through
which the container may be filled and emptied.
Typical coffee cups are a hollow frustroconical body with a base and with a narrower
diameter at the base such as from 3 to 8cm and a wider diameter at the top/mouth
such as from 5 to 10cm, with a height such as from 5 to 15cm. Typical weights for
the coffee cup are from 5 to 20g, and usually about 10-12g.
The sheet material is formed of a degradable composition. The following description
uses the term degradable to refer to the synthetic polymer components which
breakdown into CO H O, biomass and inorganic salts under normal composting
2, 2
conditions and in other environments. As will be appreciated, the calcium carbonate
17556843_1 (GHMatters) P111754.NZ
does not breakdown, but is left as an inert powder component once the polymer has
degraded. Thus, the following discussion refers interchangeably to the degradation
of the composition and the degradation of the polymer which forms the structure of
the sheet. Advantageously, the sheets described herein are even recyclable since
calcium carbonate/polyethylene masterbatch is often added to recyclate to improve
processing. That is, the high calcium carbonate content does not prevent recycling.
Due to the low levels of polymer, the sheets may even be compostable under certain
conditions.
The composition comprises 30 to 80wt% calcium carbonate, by weight of the
composition. Calcium carbonate is cheap, naturally abundant and renewable. It is
widely used in personal care applications, paper whitening, indigestion tablets and
the like. If oxidised it forms lime (Calcium Oxide) which is commonly added to
drinking water. Calcium carbonate can be sourced from chalk mines, seashells or
eggshells. Preferably the composition comprises from 50 to 75wt% and most
preferably from 60 to 70wt% calcium carbonate.
The addition of calcium carbonate provides a robust final material which fragments
easily once degradation has begun and has a low cost and impact on the
environment. Preferably the calcium carbonate has a mean longest diameter of from
1 to 30 microns, preferably 1 to 20 microns. This is desired for good distribution
within the polymer and permits ready processing of the composition, including
extrusion.
The calcium carbonate is held within a polymer selected from polyethylene,
polypropylene and copolymers and blends thereof. These polymers preferably
provide from 19 to 69wt% of the composition, with the balance additive and calcium
carbonate. Preferably the polymer is HDPE. Preferably the polymer has a melt-flow
index of from 10 to 20, since this allows good processing of the composition
comprising the calcium carbonate as described herein.
The inclusion of calcium carbonate in a polymer is known. For example, Natural
Mineral Paper (NMP) is a composite material consisting of mostly calcium carbonate
17556843_1 (GHMatters) P111754.NZ
(rock mineral) up to 80% and an organic binder HDPE (high density polyethylene).
This material was invented in the 1970’s and has only found a use in niche markets
such as luxury gift bags, labels, baggage tags, and stationery.
Furthermore, adding calcium carbonate to polyolefins is popular at the moment as it
can be used to improve processing times and reduce costs by adding weight/volume
to materials, reducing costs. These materials can also have improved tensile
properties and light barrier properties. Masterbatches have now been developed that
can improve processing for recycled products, by improving miscibility between
different polymers, especially in the case of 3 or 5-layer films containing a gas barrier
layer.
The “paper” forming the Natural Mineral Paper maintains many of the properties of
paper such as a clean dead-fold and good retention of inks, but it is also waterproof,
tear resistant and much cheaper and cleaner to produce as it uses less energy,
water and does not require bleaching agents. Many of the current manufacturers
claim that it is photodegradable, perhaps as a result of Ferric Oxide impurities in the
chalk, but do not give a timeline for degradation – and given this property have not
considered a wider potential for use. The current generation of Stone Paper (NMP)
typically contains calcium carbonate to HDPE at ratios of 80:20 for sheet thicknesses
of less than 300 µm (for use as printing paper, labels etc., paper-like bags), and
60:40 for sheet thicknesses of more than 300 µm (for use as card, glossy boxes and
the like).
The composition of the sheet material discussed herein may contain other
particulates in addition to the calcium carbonate and other ingredients described
herein, such as other particulates of metal carbonates and metal oxides. However,
the presence of such additional particulates is preferably less than 20wt%, more
preferably less than 5wt% and most preferably less than 1wt% by weight of the
composition. In a preferred embodiment the composition consists of the ingredients
described herein without any further particulates.
17556843_1 (GHMatters) P111754.NZ
The polymer further comprises an additive which is responsible for achieving the
degradable properties of the composition. The additive is described herein with
respect to the combined weight of the additive and the polymer. In practice when
making a composition for a sheet material, the additive may be pre-formed as a
masterbatch with an amount of polyethylene, polypropylene and copolymers and
blends thereof, before being mixed with the bulk polymer and calcium carbonate.
The additive comprises, by combined weight of the additive and polymer, two or
more transition metal compounds in a total amount of from 0.15 to 0.6wt%,
preferably 0.2 to 0.3 wt%. The following description uses the term transition metal to
refer to any of the metallic elements of groups IVB–VIII, IB, and IIB, or 4–12 in the
periodic table. Preferred transition metals are iron, manganese, copper, cobalt and
cerium, preferably where the iron is used it is in the +3 oxidation state and where
copper is used it is in the +2 oxidation state. These compounds catalyse the
degradation. Including large amounts of transition metal increases the cost of the
degradable composition and may lead to transition metal build-up in waste disposal
sites. Additionally, since the transition metal plays a catalytic role in the degradation
process, increasing the transition metal content above these amounts has a
decreasing impact on the degradation rate.
The two or more transition metal compounds are selected from iron (preferably
ferric), manganese, copper, zinc, titanium, cobalt and cerium compounds and the
transition metals in the two or more transition metal compounds are different.
Preferably the transition metal in the two or more transition metal compounds
comprise:
(i) iron, manganese and copper; or
(ii) manganese and copper; or
(iii) iron and manganese.
The temperature of the polymer composition as well as its exposure to light may also
affect its degradation rate. The present inventors have surprisingly found that the
choice of transition metal can be used to further tune these effects. In particular the
17556843_1 (GHMatters) P111754.NZ
present inventors have found that iron is a more efficient photo catalyst whilst
manganese is a more efficient thermal catalyst of the degradation process. The
transition metal component may, therefore, be used to tune the degradation rate
depending on the expected exposure to heat and light of a particular product.
Specific transition metals may have effects on the properties of the polymer
composition. For example, iron compounds may colour the polymer composition.
Additionally, other metals such as copper advantageously increase the degradation
rate but may make the polymer composition unsuitable for certain applications due to
its toxicity. In colour sensitive compositions iron may be avoided. For use in the food
industry copper may be avoided.
Preferably the transition metal compounds comprise moieties selected from stearate,
carboxylate, acetylacetonate, triazacyclononane or combinations of two or more
thereof. Preferably, the transition metal compounds may be present with a weight
ratio of iron stearate and manganese stearate to copper stearate is from 4:1 to 8:1.
Preferably, the transition metal compounds may be present with a weight ratio of
ferric stearate and manganese stearate to copper stearate is from 4:1 to 8:1.
Alternatively or in addition, certain non-ionic ligands that play an active role in the
degradation may also be included. Where present, the non-ionic ligands are
preferably selected from amines, imines, amides, phosphites, phosphines, and
carbenes. The present inventors have found that such non-ionic ligands can have an
advantageous effect on the degradation rate of the composition whilst maintaining
the essential material properties. Non-ionic ligands preferably constitute at least 5%
of the ligands and preferably up to 50% of the ligands, preferably 10 to 40% of the
ligands.
Preferably the transition metal ligands are chosen in order to make the transition
metal physically and chemically compatible with the polymer. Advantageously, ligand
selection may affect the transition metal’s catalytic activity. The ligands may be
17556843_1 (GHMatters) P111754.NZ
chosen to make the metal compatible with the particular polyolefin used and to
control the degradation rate of the polymer composition.
Preferably, the ligands of the metal compounds are inorganic ligands and/or
saturated organic ligands. Preferably the ligands of the metal compounds do not
comprise mono- or poly-unsaturated C14-C24 carboxylic acid, or an ester, anhydride
or amide thereof.
The additive comprises a mono- or poly-unsaturated C -C carboxylic acid in an
14 24
amount of from 0.04 to 0.08wt%, preferably 0.04 to 0.06 wt% by combined weight of
the additive and polymer. The following description uses the term carboxylic acid to
refer to the range of molecules containing a carboxylic acid –(COOH) moiety. The
carboxylic acid of the present invention is mono- or poly-unsaturated and has a
carbon backbone containing between 14 and 24 carbon atoms, meaning it has at
least one double bond in the carbon backbone. The carbon backbone of the
carboxylic acid may be linear, branched or aromatic. Preferably the mono- or poly-
unsaturated carboxylic acid is a C16-C20 carboxylic acid. Preferred carboxylic acids
are oleic, linoleic and cinnamic, most preferably the carboxylic acid is oleic acid.
Alternatively, the additive comprises an ester, anhydride or amide of a mono- or
poly-unsaturated C14-C24 carboxylic acid in an amount of from 0.04 to 0.08wt%,
preferably 0.04 to 0.06 wt% by combined weight of the additive and polymer.
The carboxylic acid or an ester, anhydride or amide components are preferably “free”
or “non-coordinated”, in the sense that they do not form a part of a transition metal
compound.
Where the additive comprises an ester of a mono- or poly-unsaturated C14-C24
carboxylic acid the alcohol component preferably comprises a C -C alcohol, more
1 30
preferably a saturated straight chain C1-C30 alcohol.
Where the additive comprises an anhydride of a mono- or poly-unsaturated C -C
14 24
carboxylic acid, the anhydride may or may not be symmetrical. The second
17556843_1 (GHMatters) P111754.NZ
carboxylic acid component preferably comprises a C1-C30 carboxylic acid, more
preferably a saturated straight chain C -C carboxylic acid.
1 30
Where the additive comprises an amide of a mono- or poly-unsaturated C14-C24
carboxylic acid the amide may be a primary, secondary or tertiary amide. Where a
secondary or tertiary amide is present, each of the carbon chains preferably
comprises from 1 to 30 carbon atoms, more preferably each carbon chain is a C1-C30
alkyl group.
Unless otherwise specified, where features of the carboxylic acid are discussed in
this description it is intended to also encompass the ester, anhydride or amide
thereof.
Without wishing to be bound by theory, it is believed that the mono- or poly-
unsaturated C -C carboxylic acid in the polymer composition autoxidises to yield
14 24
peroxides which can attack the carbon-carbon linkages of the polymer chain, making
the polymer susceptible to normal degradation processes. The presence of transition
metals catalyse the autoxidation increasing the degradation rate of the composition.
Including more than 0.08 wt% mono- or poly-unsaturated C14-C24 carboxylic acid
may cause the polymer to be excessively air sensitive. Excessive autoxidation of the
carboxylic acid may cause relatively high peroxide concentrations and rapid
breakdown of the polymer structure. This may cause shelf life issues. Conversely,
including less than 0.04 wt.% mono- or poly-unsaturated C14-C24 carboxylic acid may
lead to a negligible degradation rate. The inventors have found that including the
between 0.04 and 0.08 wt.% mono- or poly-unsaturated C -C carboxylic acid
14 24
allows tuning of the degradation rate to desirable values for many applications.
Surprisingly, the present inventors have found that linear mono-unsaturated acids,
and in particular oleic acid, show the greatest effect on degradation rate. This would
not be expected by the chemical stability of these compounds in isolation since, in
general, the more double bonds in a carboxylic acid the more susceptible to
oxidation it is.
17556843_1 (GHMatters) P111754.NZ
The additive comprises a synthetic rubber in an amount of from 0.04 to 0.2wt%,
preferably 0.08 to 0.12 wt%, most preferably about 0.1 wt% by combined weight of
the additive and polymer. The following description uses the term rubber to refer to
viscous, elastic polymers. Rubbers are amorphous polymers which exist at
temperatures above their glass transition temperature. Preferably the rubber of the
present invention is an unsaturated rubber, more preferably the rubber of the present
invention comprises polyisoprene, styrene-isoprene, styrene-isoprene-styrene, or a
blend of two or more thereof.
The rubber content may advantageously improve the mechanical properties of the
polymer composition. Additionally, rubbers are generally less chemically stable than
the bulk polyolefin. Accordingly, the rubber content may improve the degradation
rate without adversely affecting the physical properties of the polymer. In this way it
seems to act as a co-catalyst.
Advantageously, the presence of the synthetic rubber in the polymer composition
improves the elasticity. This helps to counteract the embrittlement of the polymer
composition caused by the other additives. Including less than 0.04 % synthetic
rubber may lead to the polymer being excessively brittle and unsuitable. Including
more than 0.12% synthetic rubber may lead to rapid degradation rates and may
adversely affect the material properties of the polymer. Additionally, it is believed that
the synthetic rubber content increases the degradation rate without the need to
increase the transition metal, starch, or carboxylic acid content.
The additive optionally comprises dry starch in an amount of from 0 to 20wt%,
preferably 0 to 10 wt%, more preferably 0.1 to 1 wt% and most preferably 0.1 to 0.4
wt% by combined weight of the additive and polymer. The following description uses
the term starch to refer to a polysaccharide comprising a large number (general 500-
2,000,000 monomer units) of glucose units joined by glycosidic bonds. The starch of
the present invention is dry starch. That is, the starch contains less that 5wt% water
by weight of the starch, preferably less than 1 wt% water, most preferably the starch
contains essentially no water.
17556843_1 (GHMatters) P111754.NZ
Including large quantities of starch may increase the density and reduce the tensile
strength of the polymer. Additionally, high starch contents may lead to shelf life
problems due to rapid degradation. High starch contents make the polymer content
susceptible to cosmetic and physical damage due to exposure to water and
microorganisms. If insufficient starch is included the additive may have an
insignificant effect on the biodegradation rate.
The additive optionally comprises calcium oxide in an amount of from 0 to 1wt%,
preferably from 0 to 0.4wt%, more preferably from 0.1 to 0.3 wt% by combined
weight of the additive and polymer. The following description uses the term calcium
oxide to refer to the crystalline solid with the chemical formula CaO. Advantageously
calcium oxide reacts with and immobilises water in the composition. This stabilises
the composition during processing and may reduce the occurrence of blemishes and
discoloration of the final product. Surprisingly and unexpectedly the present
inventors have also found that increasing the calcium oxide content of the polymer
composition may increase the degradation rate. Advantageously, the CaO content
may be used to improve degradability without the need of increasing the transition
metal of starch content. Including more than 0.4 wt% CaO leads to embrittlement of
the polymer.
The additive optionally comprises an oxygen generating additive. Oxygen
generating additives may be organic or inorganic. Preferably, the oxygen generating
additive is selected from nitrates, peroxides, sulphates and phosphates or
combinations of two or more thereof. Preferably the oxygen generating additive is
calcium nitrate. Preferably the oxygen generating additive is present in an amount of
from 0.1 to 1.0 wt% by combined weight of the additive and polymer. The oxygen-
generating additive was found to further accelerate the rate of the oxidation of the
polymer.
The additive optionally comprises a phenolic antioxidant stabilizer in an amount of
from 0 to 0.2 wt%, preferably from 0.02 to 0.15wt%. Phenolic antioxidant stabilisers
are well known in the art and include, for example, Irganox 1076 and Irganox 1010.
17556843_1 (GHMatters) P111754.NZ
The phenolic antioxidant stabiliser was found to allow increased control over the
timing of the degradation of the polymer. Specifically, the inclusion of a phenolic
antioxidant stabiliser may delay the onset of degradation, increasing the shelf life of
a product and the period in which the product may be recycled in existing polyolefin
recycling streams.
Preferably the additive further comprises a colour additive, such as, but not
exclusively carbon black or titanium oxide.
Accordingly, the present disclosure provides a sheet material made from a
composition based on a specific combination of ingredients which permits the
provision of an ideal degradable composition.
Preferably the sheet material has a mean thickness of from 100 to 500 microns,
preferably 200 to 400 microns.
According to one embodiment the sheet material has an expanded gas-containing
structure. That is, the sheet material can be provided with trapped internal voids
which provide an insulating benefit to the user. For an expanded material the
thickness may be preferably 1000 microns to 10cm.
According to a further aspect there is provided packaging or a container formed of
the sheet material as described herein.
In the preferred embodiment of a coffee cup, the cup preferably further comprises a
component selected from the group consisting of a lid, a handle and a sleeve,
wherein said component is also formed of the degradable composition.
The present disclosure provides a coffee cup made from a composition based on a
specific combination of ingredients which permits the provision of an ideal
degradable composition.
17556843_1 (GHMatters) P111754.NZ
Preferably the cup has a wall thickness of from 100 to 500 microns, preferably 200 to
400 microns.
According to one embodiment the composition has an expanded gas-containing
structure. That is, the cup wall can be provided with trapped internal voids which
provide an insulating benefit to the walls of the cup to avoid the user burning their
hands on a hot beverage. For an expanded cup the wall thickness may be from 400
to 3000 microns, preferably 1000 to 2000 microns.
According to a further aspect there is provided a method of forming a container, the
method comprising:
forming a composition comprising 30 to 80wt% calcium carbonate, an additive
and a polymer,
shaping the composition to form a container,
wherein the polymer and additive are as described herein.
According to a further aspect there is provided a method of forming a disposable
coffee cup, the method comprising:
forming a composition comprising 30 to 80wt% calcium carbonate, an additive
and a polymer,
shaping the composition to form a coffee cup,
wherein the polymer and additive are as described herein.
In the foregoing embodiments, the step of forming typically comprises mixing the
components, optionally with the additive provided in a masterbatch concentrated
composition, to form a composition.
Preferably the step of shaping the composition to form a container or coffee cup
comprises moulding the composition into a container configuration, or forming and
shaping one or more sheets of the composition into a container configuration and,
optionally, fixing the configuration with heat-sealing or gluing, or 3D printing.
17556843_1 (GHMatters) P111754.NZ
Preferably the shaping is by moulding such as by thermoforming, injection moulding,
injection blow-moulding, or compression moulding. Shaping could alternatively
include folding techniques. This could include pressure heat sealing.
Advantageously, due to the polymer content, this can be achieved without the use of
adhesive.
Preferably the method is for making the container or coffee cup described in detail
above.
According to a further aspect there is provided a method of initiating the chemical
degradation of the packaging or container as described herein, wherein the method
comprises exposing the sheet material to temperatures in excess of 50°C, preferably
by loading the container with a hot beverage or foodstuff, or by exposing the
container to microwave heating. That is, the composition described herein is heat
sensitive such that the use with, for example, a hot beverage starts the degradation.
The degradation is slow, such that the container or packaging still serves its intended
purpose, but degrades within the next few weeks after use. Preferably primary
disintegration occurs substantially within 6 weeks, preferably within 4 weeks and
secondary microbial digestion occurs substantially within 1 year, preferably within 6
months.
Primary degradation/disintegration described herein would preferably be 2-6 weeks
and this can be demonstrated in fugitive (roadside, wasteland), soil and aerobic
compost environments. Typically the primary degradation leaves the container with a
compromised structural integrity such that it is no longer suitable for its original
purpose. Microbial digestion of materials will be up from 6 months to 1 year provided
that the sheet material is in an environment with suitable microorganisms. The
degraded materials would become white chalk powder.
According to a further aspect there is provided a method of initiating the chemical
degradation of a disposable coffee cup as described herein, wherein the method
comprises exposing the coffee cup to temperatures in excess of 50°C, preferably by
loading the coffee cup with a hot beverage. That is, the composition described herein
17556843_1 (GHMatters) P111754.NZ
is heat sensitive such that the use with a hot beverage starts the degradation. The
degradation is slow, such that the cup still serves its intended purpose, but degrades
within the next few weeks after use. Preferably primary disintegration occurs
substantially within 6 weeks, preferably within 4 weeks and secondary microbial
digestion occurs substantially within 1 year, preferably within 6 months.
According to another aspect there is provided the use of an additive to initiate
degradation of a sheet material (or coffee cup) comprising said additive following
exposure to temperatures in excess of 50°C, wherein the additive and sheet material
composition are as described herein. Preferably the exposure to temperatures in
excess of 50°C comprises contacting the sheet material with a hot beverage or
foodstuff, or exposing the sheet material (or coffee cup) to microwave heating.
The sheet material of the present invention seeks to solve the problem of incorrectly
handled disposal of packaging and containers, such as coffee cups. Where
consumers believe their container is recyclable, it is advantageous that the present
invention provides a recyclable material which can be included in standard recycling
processes since the ingredients are compatible with other recycled materials. Where
consumers believe that their container is simply made of paper and will naturally
degrade if discarded in a ditch, it is advantageous that the present invention provides
a degradable material which will quickly degrade under such conditions.
Examples of specific applications for the sheet material discussed herein include
paper plates, cartons for food/drink, packaging paper, food labels,
horticulture/agriculture tags, drink straws, business cards, gift boxes and paper-like
bags. These are particularly suitable for cast films. Other applications include
disposable cutlery, disposable containers such as flower pots, yoghurt pots,
takeaway food containers and hot/cold beverage cup lids, which can be made with
thermoforming techniques. Other applications include degradable carrier bags,
garbage bags, seed/grain bags, cement bags, and silage wrap, as well as food
wraps such as burger sheets, all of which can be made with blown films. Expanded
compositions could be employed as include single use insulating drinks/food
17556843_1 (GHMatters) P111754.NZ
containers, packaging materials, insulation, temporary plastic seating, bicycle seats,
or bicycle helmets. Advantageously the material can be readily printed on.
All percentages used in this disclosure are by weight unless otherwise specified.
For the avoidance of doubt, an example is provided of the relative amounts. In a
composition comprising 50wt% calcium carbonate, 1wt% additive and the balance
(49wt%) is polymer, a component of the additive which is 0.5wt% of the combined
weight of the polymer and additive, is 0.25wt% of the whole composition.
The invention will now be described in relation to the following non-limiting figures.
Figure 1 shows an exemplary container.
Figure 2 shows an exemplary coffee cup and lid.
The invention will now be described in relation to the following non-limiting examples.
Examples
An exemplary sheet formulation is described below.
Example Formulation for Thermoformed NMP Products
A sheet for forming a container (a coffee cup) was prepared from a composition of a
polyolefin comprising of HDPE or PP, a copolymer or a blend PE/PP of Melt Flow
Index of 10-30 g/10 mins, containing Calcium Carbonate of particle size 1-30 micron.
To this was added a masterbatch additive formulation (0.2-5%) comprising a mixture
of metal stearates, carboxylates, pro-oxidant such as metal nitrates, phosphates,
calcium oxide, metal carbonate, dry starch and an unsaturated rubber. Carbon Black
or other pigments can be added in 0.1-10% loadings for coloration
Example Formulation for Film Blown Products
17556843_1 (GHMatters) P111754.NZ
A sheet for forming a container was prepared from a Polyolefin comprising of HDPE,
LLDPE or PP, a copolymer or blend of Melt Flow Index 0.2-2 g/10 mins, containing
Calcium Carbonate of particle size of particle size 1-30 micron, and an additive
formulation (0.1-5%) comprising a mixture for metal stearates as above, with addition
of Carbon Black as a colorant.
Example Formulation for Expanded PP Products
An expanded PP grade resin was prepared containing Calcium carbonate from 30-
50% with average diameter from 0.1 to 5 micron, would contain a 0.1-5% of the
additive describe herein, containing dry starch, unsaturated rubber and a mixture of
metal catalysts. This was shaped into the form of a coffee cup.
Specific Formulations
The following formulations were used to form a plastic suitable for forming a coffee
cup by the addition of further HDPE and calcium carbonate. The calcium carbonate
represented 50wt% of the mixture, and the HDPE represented 48w% of the mixture.
The cups were tested under extreme weathering conditions and demonstrated fast
decomposition. In addition, the cups had a good paper-like feel and suitable strength
for the intended application.
Formulation 1
An additive formulation was prepared consisting of:
i) Dried starch - 10.00 wt.%
ii) Manganese stearate - 4.00 wt.%
iii) Ferric stearate - 8.00 wt.%
iv) Copper stearate - 1.30 wt.%
v) Oleic acid - 2.00 wt.%
vi) SIS /SI copolymer - 4.00 wt.%
vii) Calcium oxide - 10 wt.%
17556843_1 (GHMatters) P111754.NZ
viii) LLDPE - 60.70 wt.%
Formulation 2
An additive formulation was prepared consisting of:
i) Dried starch - 10.00 wt.%
ii) Manganese stearate - 2.00 wt.%
iii) Ferric stearate - 10.00 wt.%
iv) Irganox 1076 - 13.0 wt.%
v) Oleic acid - 1.00 wt.%
vi) SIS /SI copolymer - 2.00 wt.%
vii) Calcium oxide - 10.00 wt.%
viii) LLDPE - 52.0 wt.%
Formulation 3
An additive formulation was prepared consisting of:
i) Dried starch - 10.00 wt.%
ii) Manganese stearate - 4.00 wt.%
iii) Copper stearate - 8.00 wt.%
iv) Oleic acid - 6.00 wt.%
v) SIS /SI copolymer - 2.00 wt.%
vi) LLDPE - 70.00 wt.%
Example formulations 1,2 and 3 were formed by hot extruding components ii-viii then
separately adding the starch. By adding the starch separately it may be added after
the heating steps, avoiding damaging the structure.
Formulation 4
An additive formulation was prepared consisting of:
i) Manganese stearate - 4.00 wt.%
ii) Ferric stearate - 8.00 wt.%
17556843_1 (GHMatters) P111754.NZ
iii) Copper stearate - 1.30 wt.%
iv) Oleic acid - 6.00 wt.%
v) SIS /SI copolymer - 1.00 wt.%
vi) Calcium oxide - 10.00 wt.%
vii) LLDPE - 69.70 wt.%
Formulation 5
An additive formulation was prepared consisting of:
i) Manganese stearate - 4.00 wt.%
ii) Ferric stearate - 8.00 wt.%
iii) Copper stearate - 1.30 wt.%
iv) Oleic acid - 2.00 wt.%
v) SIS /SI copolymer - 1.00 wt.%
vi) Calcium oxide - 10.00 wt.%
vii) Irganox 1076 - 10.00 wt.%
viii) LLDPE - 63.70 wt.%
Example formulations 4 and 5 were formed by hot extruding the components.
The compositions are summarised below:
1 2 3 4 5
i) Dried starch 10.0 10.0 10.0
ii) Manganese stearate 4.0 2.0 4.0 4.0 4.0
iii) Ferric stearate 8.0 10.0 8.0 8.0
iv) Copper stearate 1.3 8.0 1.3 1.3
v) Oleic acid 2.0 1.0 6.0 6.0 2.0
vi) SIS /SI copolymer 4.0 2.0 2.0 1.0 1.0
vii) Calcium oxide 10.0 10.0 10.0 10.0
viii) LLDPE 60.7 52.0 70.0 69.7 63.7
ix) Irganox 1076 13.0 10.0
Although preferred embodiments of the invention have been described herein in
detail, it will be understood by those skilled in the art that variations may be made
thereto without departing from the scope of the invention or of the appended claims.
17556843_1 (GHMatters) P111754.NZ
Claims (29)
1. A sheet material formed of a degradable composition, the composition comprising: 5 30 to 80wt% calcium carbonate by weight of the composition; an additive; and the balance a polymer selected from polyethylene, polypropylene and copolymers and blends thereof, wherein the additive comprises, by combined weight of the additive and the 10 polymer: (a) two or more transition metal compounds in a total amount of from 0.15 to 0.6wt%; (b) a mono- or poly-unsaturated C -C carboxylic acid, or an ester, 14 24 anhydride or amide thereof, in an amount of from 0.04 to 0.08wt%; 15 (c) a synthetic rubber in an amount of from 0.04 to 0.2wt%; and, optionally: (d) dry starch in an amount of from 0 to 20wt%; and/or (e) calcium oxide in an amount of from 0 to 1 wt%; and/or (f) a phenolic antioxidant stabilizer in an amount of from 0 to 0.2 wt%; 20 wherein the two or more transition metal compounds are selected from iron, manganese, copper, zinc, titanium, cobalt and cerium compounds and wherein the transition metals in the two or more transition metal compounds are different.
2. The sheet material according to claim 1, wherein the composition comprises 25 from 60 to 70wt% calcium carbonate.
3. The sheet material according to claim 2, wherein the calcium carbonate has a mean longest diameter of from 1 to 30 microns. 30
4. The sheet material according to any one of the preceding claims having a mean thickness of from 100 to 500 microns. 17556843_1 (GHMatters) P111754.NZ
5. The sheet material according to claim 4, wherein the mean thickness is from 200 to 400 microns.
6. The sheet material according to any one of claims 1 to 3, wherein the 5 composition has an expanded gas-containing structure.
7. The sheet material according to any one of the preceding claims, wherein the transition metal compounds comprise moieties selected from stearate, carboxylate, carbonate, acetylacetonate, triazacyclononane or combinations of two or more 10 thereof.
8. The sheet material according to any one of the preceding claims, wherein the transition metal in the two or more transition metal compounds comprise: (i) iron, manganese and copper; or 15 (ii) manganese and copper; or (iii) iron and manganese.
9. The sheet material according to any one of the preceding claims, wherein the composition comprises an oxidising additive.
10. The sheet material according to claim 9, wherein the oxidising additive is calcium nitrate.
11. The sheet material according to any one of the preceding claims, wherein the 25 mono- or poly-unsaturated C -C carboxylic acid is a C -C linear carboxylic acid; 14 24 16 20 and/or wherein the synthetic rubber comprises an unsaturated polymer; and/or wherein the polymer is HDPE. 30
12. The sheet material according to claim 11, wherein the mono- or poly- unsaturated C14-C24 carboxylic acid is oleic acid. 17556843_1 (GHMatters) P111754.NZ
13. The sheet material according to claim 11 wherein the synthetic rubber comprises styrene-isoprene-styrene.
14. The sheet material according to claim 13 wherein the styrene-isoprene- 5 styrene comprises a blend of a styrene-isoprene-styrene and a styrene-isoprene copolymer.
15. The sheet material according to claim 11 wherein the polymer is HDPE having a melt-flow index of from 10 to 20.
16. The sheet material according to any one of the preceding claims, wherein the composition comprises, by combined weight of the additive and the polymer: (b) two or more transition metal stearates in a total amount of from 0.2 to 0.3wt%; and/or 15 (c) a mono-unsaturated C -C linear carboxylic acid in an amount of from 16 20 0.04 to 0.06wt%; and/or (d) a synthetic rubber in an amount of from 0.08 to 0.12wt%; and/or (e) dry starch in an amount of from 0.1 to 0.4wt%; and/or (f) calcium oxide in an amount of from 0.1 to 0.3wt%; and/or 20 (g) calcium nitrate in an amount from 0.1 to 1.0wt%.
17. Packaging or a container formed of the sheet material according to any of the preceding claims. 25
18. A disposable coffee cup formed of the sheet material according to any of the preceding claims, optionally further comprising a component selected from the group consisting of a lid, a handle and a sleeve, wherein said component is also formed of the degradable composition. 30
19. A method of forming a container, the method comprising: forming a composition comprising 30 to 80wt% calcium carbonate by weight of the composition, an additive and the balance a polymer, shaping the composition to form a container, 17556843_1 (GHMatters) P111754.NZ wherein the polymer is selected from polyethylene, polypropylene and copolymers and blends thereof, and wherein the additive comprises, by combined weight of the additive and the polymer: 5 (a) two or more transition metal compounds in a total amount of from 0.15 to 0.6wt%; (b) a mono- or poly-unsaturated C14-C24 carboxylic acid, or an ester, anhydride or amide thereof, in an amount of from 0.04 to 0.08wt%; (c) a synthetic rubber in an amount of from 0.04 to 0.2wt%; 10 and, optionally: (d) dry starch in an amount of from 0 to 20wt%; and/or (e) calcium oxide in an amount of from 0 to 1 wt%; and/or (f) a phenolic antioxidant stabilizer in an amount of from 0 to 0.2 wt%; wherein the two or more transition metal compounds are selected from ferric, 15 manganese, copper, zinc, titanium, cobalt and cerium compounds and wherein the transition metals in the two or more transition metal compounds are different.
20. The method according to claim 19, wherein the container is a coffee cup, and the step of shaping the composition to form a container comprises shaping the 20 composition to form a coffee cup.
21. The method according to claim 19 or claim 20, wherein the step of shaping the composition to form a container comprises: (a) moulding the composition into a container configuration; or 25 (b) forming and shaping one or more sheets of the composition into a container configuration and, optionally, fixing the configuration with heat-sealing or gluing; or (c) 3D printing. 30
22. The method according to claim 21, wherein the step of shaping the composition to form a container comprises thermoforming, injection moulding, injection blow-moulding, or compression moulding the composition into a container configuration. 17556843_1 (GHMatters) P111754.NZ
23. The method according to any one of claims 19 to 22, wherein the method is for making the container according to claim 17 or the disposable coffee cup according to claim 18.
24. A method of initiating the chemical degradation of the packaging or container according to claim 17 or the disposable coffee cup according to claim 18, wherein the method comprises exposing the sheet material to temperatures in excess of 50°C.
25. The method according to claim 24, wherein the method comprises loading the container with a hot beverage or foodstuff, or exposing the container to microwave heating. 15
26. The method according to claim 24 or claim 25, wherein primary disintegration occurs substantially within 6 weeks and secondary microbial digestion occurs substantially within 1 year.
27. Use of an additive to initiate degradation of a sheet material following 20 exposure to temperatures in excess of 50°C, wherein the sheet material is formed from a composition comprising: 30 to 80wt% calcium carbonate by weight of the composition; an additive; and the balance a polymer selected from polyethylene, polypropylene and 25 copolymers and blends thereof, wherein the additive comprises, by combined weight of the additive and the polymer: (a) two or more transition metal compounds in a total amount of from 0.15 to 0.6wt%; 30 (b) a mono- or poly-unsaturated C14-C24 carboxylic acid, or an ester, anhydride or amide thereof, in an amount of from 0.04 to 0.08wt%; (c) a synthetic rubber in an amount of from 0.04 to 0.2wt%; and, optionally: 17556843_1 (GHMatters) P111754.NZ (d) dry starch in an amount of from 0 to 20wt%; and/or (e) calcium oxide in an amount of from 0 to 1 wt%; and/or (f) a phenolic antioxidant stabilizer in an amount of from 0 to 0.2 wt%; wherein the two or more transition metal compounds are selected from iron, 5 manganese, copper, zinc, titanium, cobalt and cerium compounds and wherein the transition metals in the two or more transition metal compounds are different.
28. The use of claim 27, wherein the sheet material is in the form of a coffee cup. 10
29. The use of claim 27 or claim 28, wherein the exposure to temperatures in excess of 50°C comprises contacting the sheet material with a hot beverage or foodstuff, or exposing the sheet material to microwave heating. 17556843_1 (GHMatters) P111754.NZ
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17152497.8 | 2017-01-20 | ||
EP17152496.0 | 2017-01-20 | ||
EP17152496 | 2017-01-20 | ||
EP17152497 | 2017-01-20 | ||
PCT/EP2018/050375 WO2018134071A1 (en) | 2017-01-20 | 2018-01-08 | Degradable sheet material |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ756502A NZ756502A (en) | 2021-05-28 |
NZ756502B2 true NZ756502B2 (en) | 2021-08-31 |
Family
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