CN114007841A - 包含酶的多层制品 - Google Patents
包含酶的多层制品 Download PDFInfo
- Publication number
- CN114007841A CN114007841A CN202080023743.4A CN202080023743A CN114007841A CN 114007841 A CN114007841 A CN 114007841A CN 202080023743 A CN202080023743 A CN 202080023743A CN 114007841 A CN114007841 A CN 114007841A
- Authority
- CN
- China
- Prior art keywords
- layer
- multilayer article
- enzyme
- article according
- multilayer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 55
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 55
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 230000000593 degrading effect Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 70
- 239000004626 polylactic acid Substances 0.000 claims description 32
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 31
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 229920001282 polysaccharide Polymers 0.000 claims description 18
- 239000005017 polysaccharide Substances 0.000 claims description 18
- -1 polybutylene adipate terephthalate Polymers 0.000 claims description 17
- 230000004888 barrier function Effects 0.000 claims description 15
- 229920001610 polycaprolactone Polymers 0.000 claims description 15
- 239000004632 polycaprolactone Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 11
- 229920000954 Polyglycolide Polymers 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 10
- 239000004633 polyglycolic acid Substances 0.000 claims description 10
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 8
- 239000004631 polybutylene succinate Substances 0.000 claims description 8
- 229920002961 polybutylene succinate Polymers 0.000 claims description 8
- 241000023308 Acca Species 0.000 claims description 6
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 6
- 229920001397 Poly-beta-hydroxybutyrate Polymers 0.000 claims description 6
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 229920002792 polyhydroxyhexanoate Polymers 0.000 claims description 6
- 102000014171 Milk Proteins Human genes 0.000 claims description 5
- 108010011756 Milk Proteins Proteins 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 235000021239 milk protein Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 235000013361 beverage Nutrition 0.000 claims description 3
- 239000002775 capsule Substances 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims 3
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 86
- 229940088598 enzyme Drugs 0.000 description 50
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 18
- 150000004804 polysaccharides Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000012528 membrane Substances 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- 239000004310 lactic acid Substances 0.000 description 9
- 235000014655 lactic acid Nutrition 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 244000215068 Acacia senegal Species 0.000 description 3
- 229920000084 Gum arabic Polymers 0.000 description 3
- 235000010489 acacia gum Nutrition 0.000 description 3
- 239000000205 acacia gum Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- 241000194108 Bacillus licheniformis Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- 229920000926 Galactomannan Polymers 0.000 description 2
- 229920002148 Gellan gum Polymers 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 108010022999 Serine Proteases Proteins 0.000 description 2
- 102000012479 Serine Proteases Human genes 0.000 description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 235000010418 carrageenan Nutrition 0.000 description 2
- 239000000679 carrageenan Substances 0.000 description 2
- 229920001525 carrageenan Polymers 0.000 description 2
- 229940113118 carrageenan Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000010492 gellan gum Nutrition 0.000 description 2
- 239000000216 gellan gum Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001069 triethyl citrate Substances 0.000 description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 2
- 235000013769 triethyl citrate Nutrition 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000187643 Amycolatopsis Species 0.000 description 1
- 241001522168 Amycolatopsis sp. Species 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 108010067770 Endopeptidase K Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- 108060003951 Immunoglobulin Proteins 0.000 description 1
- 241001136689 Laceyella Species 0.000 description 1
- 102000004407 Lactalbumin Human genes 0.000 description 1
- 108090000942 Lactalbumin Proteins 0.000 description 1
- 108010063045 Lactoferrin Proteins 0.000 description 1
- 102000010445 Lactoferrin Human genes 0.000 description 1
- 102000008192 Lactoglobulins Human genes 0.000 description 1
- 108010060630 Lactoglobulins Proteins 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 239000005913 Maltodextrin Substances 0.000 description 1
- 241001272720 Medialuna californiensis Species 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 241001523956 Parengyodontium album Species 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102000007562 Serum Albumin Human genes 0.000 description 1
- 108010071390 Serum Albumin Proteins 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000203775 Thermoactinomyces Species 0.000 description 1
- 241000589596 Thermus Species 0.000 description 1
- 241000589497 Thermus sp. Species 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- 229940072221 immunoglobulins Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004790 ingeo Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 229940039371 karaya gum Drugs 0.000 description 1
- CSSYQJWUGATIHM-IKGCZBKSSA-N l-phenylalanyl-l-lysyl-l-cysteinyl-l-arginyl-l-arginyl-l-tryptophyl-l-glutaminyl-l-tryptophyl-l-arginyl-l-methionyl-l-lysyl-l-lysyl-l-leucylglycyl-l-alanyl-l-prolyl-l-seryl-l-isoleucyl-l-threonyl-l-cysteinyl-l-valyl-l-arginyl-l-arginyl-l-alanyl-l-phenylal Chemical compound C([C@H](N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CS)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CS)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)C1=CC=CC=C1 CSSYQJWUGATIHM-IKGCZBKSSA-N 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 235000021242 lactoferrin Nutrition 0.000 description 1
- 229940078795 lactoferrin Drugs 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229940012957 plasmin Drugs 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 235000021241 α-lactalbumin Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0017—Agents activating degradation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
- B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
本发明涉及一种可生物降解多层塑料制品，其包含至少3个层和一个芯，所述芯含有能够降解包围所述芯的层的聚合物的酶。
Description
技术领域
本发明涉及一种可生物降解多层塑料制品，其包含至少3个层和一个芯，所述芯含有能够降解包围其的层的聚合物的酶。
背景技术
生物基且可生物降解的制品是已知的，特别是单层或多层制品，特别用于制造塑料袋。这些袋特别用于包装食品产品，特别是水果和蔬菜。
可以特别提及的是专利和专利申请WO 2007/118828、WO 2002/059202A1、WO2002/059199、WO 2002/059198、WO 2004/052646、WO 2018/233888、US 6,841,597、US 8,751,816、US 5,436,078、US 9,096,758、US 2009/324917和CN 106881929中所述的制品。
为了生产包含能够降解构成其的聚合物的酶的制品，有必要既在制品制备过程中保存酶，例如通过与在不降解所述酶的温度下熔化的聚合物混合，又同时避免干扰机械特性和阻隔(特别是针对气体)的约束条件。
发明内容
本发明涉及一种生物基且可生物降解的多层塑料制品，其包含至少3个层，所述层包括芯，所述芯含有能够降解包围其的层的聚合物的酶。
根据本发明的制品是ABA、ABCA或ACBCA型多层制品，其包含中央层B，中央层B包含至少0.001％的能够降解相邻层A和任选地C的聚合物的酶，所述百分比基于层B的组合物的总质量按质量计表述。
根据本发明的多层制品可以是柔性制品，诸如膜、袋、邮寄膜、覆盖地膜。
本发明的柔性制品将优先地具有小于250μm的厚度。
根据本发明的多层制品还可以涉及一种刚性制品，诸如杯、盘、饮料胶囊、托盘、泡罩包装。
本发明的刚性制品将具有包括在150μm与5mm之间、优先地包括在150μm与3mm之间的厚度。
具体实施方式
根据本发明的制品是ABA、ABCA或ACBCA型多层热塑性制品。中央层B是包含能够降解层A、层B和(如果需要)层C的聚合物的酶的层。
根据本发明，ABA、ABCA或ACBCA型多层热塑性制品被理解为意指一种制品，其层是相互连接的并且不是简单地通过简单的并置相关联的。特别且优选地，所述层通过共挤出相互连接。
除非另有说明，否则百分比和相对比率基于它们定义的组合物的总质量按质量计表述。
层A有利地是单独使用或以任何比例的混合物使用的可生物降解聚酯层。这些聚酯是本领域技术人员熟知的，特别地选自PBAT(聚己二酸对苯二甲酸丁二醇酯)、PHA(聚羟基烷酸酯)、PHB(聚-β-羟基丁酸酯)、PHH(聚羟基己酸酯)、PBS(聚琥珀酸丁二醇酯)、PLA(聚乳酸)、PCL(聚己内酯)、PBSA(聚己二酸琥珀酸丁二醇酯)和增塑淀粉。
根据一个具体实施方案，层A的聚酯选自PBAT、PLA及其任何比例的混合物。根据一个优选的实施方案，层A中PBAT/PLA的重量比的范围是从0/100至25/75、优先地从10/90至20/80、甚至更优先地从13/87至15/85。
层A还可以包含常用于生产塑料制品的其他添加剂，诸如助流剂、增塑剂、成核剂、增容剂、加工助剂、UV稳定剂、冲击抑制剂、矿物或植物填料等。
柔性制品中使用的增塑剂是本领域技术人员熟知的，特别地选自多元醇和酰胺、乳酸低聚物(OLA)和柠檬酸酯。
OLA是技术人员已知的增塑剂，特别是作为生物基材料。它们是分子量低于1500g/mol的乳酸低聚物。它们优选地是乳酸低聚物的酯，其羧酸端通过与醇(特别是直链或支链C1-C10醇、有利地是C6-C10醇、或后者的混合物)酯化而被封闭。可以特别提及的是专利申请EP 2 256 149中所述的OLA及其制备方法，以及由Condensia Quimica公司以商标名
出售的OLA，特别是具有500至600g/mol的分子量的
OLA2产品和具有1000至1100g/mol的分子量的
OLA 8产品。根据本发明的一个优选实施方案，OLA具有至少900g/mol、优选1000至1400g/mol、更优先地1000至1100g/mol的分子量。
柠檬酸酯也是技术人员已知的增塑剂，特别是作为生物基材料。可以特别提及的是柠檬酸三乙酯(TEC)、乙酰基柠檬酸三乙酯(TEAC)、柠檬酸三丁酯(TBC)、乙酰基柠檬酸三丁酯(TBAC)，优选TBAC。
根据本发明的组合物中增塑剂、特别是OLA或柠檬酸酯的含量有利地是至少0.5％、优选从1％至5％、更优先地从2％至4％，有利地约3％。
当PLA与另一种聚酯混合时，增容剂特别用在层A的组合物中。PLA/聚酯增容剂是技术人员熟知的，特别是具有允许接枝反应的环氧基、丙烯酸酯、酸酐、噁唑啉和内酰胺官能团的分子。
在增容剂中，可以更特别提及的是聚丙烯酸酯；乙烯、丙烯酸酯和甲基丙烯酸缩水甘油酯的三元共聚物(例如，由Arkema公司以商标名
出售)；PLA-PBAT-PLA三嵌段共聚物；用马来酸酐接枝的PLA(PLA-g-AM)或用马来酸酐接枝的PBAT(PBAT-g-AM)。
根据本发明的一个优选实施方案，增容剂选自聚丙烯酸酯，有利地选自甲基丙烯酸酯衍生物，优先地，增容剂是聚(乙烯-共-丙烯酸甲酯-共-甲基丙烯酸缩水甘油酯)。此类增容剂是熟知的，并且特别是由Dong等人(International Journal of MolecularSciences,2013,14,20189-20203)和Ojijo等人(Polymer 2015,80,1-17)所述的。优选的增容剂是由BASF公司以商标名
ADR-4468-出售的聚(乙烯-共-丙烯酸甲酯-共-甲基丙烯酸缩水甘油酯)。
根据本发明的层A的组合物中的增容剂含量有利地是基于组合物的总重量按重量计至少0.1％、优选从0.25％至2％、更优先地从0.3％至1.5％、有利地约0.5％。
优先使用的矿物填料是碳酸钙或滑石。
优先使用的植物填料是淀粉以及木质纤维和粉。
根据本发明的一个具体实施方案，特别是对于柔性制品的制备，层A的组合物包含
-按重量计至少25％的PLA(聚乳酸)，优先地至少28％、更优先地至少30％的PLA，
-按重量计至少60％的聚酯，所述聚酯选自PBAT(聚己二酸对苯二甲酸丁二醇酯)、PHA(聚羟基烷酸酯)、PBS(聚琥珀酸丁二醇酯)、PBSA(聚己二酸琥珀酸丁二醇酯)及其混合物，
-在0.25％与1％之间的PLA/聚酯增容剂，特别地选自以上定义的聚丙烯酸酯，和
-在2％与4％之间的增塑剂，特别地选自以上定义的乳酸低聚物(OLA)和柠檬酸酯。
根据本发明的另一个具体实施方案，特别是对于刚性制品，层A的组合物包含
-按重量计至少80％、优先地至少85％、更优先地至少90％的聚酯
-至多30％、优先地至多15％、更优先地至多10％的添加剂。
特别地，层A基本上由如上所述的聚酯或聚酯混合物(特别是PLA)组成。
中央层B包含至少0.001％的能够降解层A和层B的聚合物的酶，无论它们是相邻的还是被层C隔开。
能够降解聚合物的酶是技术人员熟知的。将特别提及的是能够降解聚酯以便改善根据本发明的制品的生物降解性的酶。在本发明的一个具体实施方案中，所述酶能够降解PLA。此类酶及其掺入热塑性制品中的方法是技术人员已知的，特别地描述在专利申请WO2013/093355、WO 2016/198652、WO 2016/198650、WO 2016/146540和WO 2016/062695中。优先地，这些酶选自蛋白酶和丝氨酸蛋白酶。在一个具体实施方案中，丝氨酸蛋白酶选自来自白色念球菌(Tritirachium album)的蛋白酶K；或来自拟无枝酸菌属物种(Amycolatopsissp.)、Actinomadura keratinilytica、高温放线糖莱斯菌(Laceyella sacchari)LP175、栖热菌属物种(Thermus sp.)或地衣芽孢杆菌(Bacillus licheniformis)的PLA降解酶；或已知降解PLA的商业再配制酶，诸如
或枯草杆菌蛋白酶CAS 9014-01-1家族的任何酶或任何功能性变体。
技术人员将根据其降解包围它的层B和层A的聚酯的目的来调整中央层B中的酶含量。有利地，中央层中的酶含量将是至少0.002％、更有利地至少0.05％。这些含量可以高达10％，甚至更高。尽管有可能配制包含多于10％酶的层B组合物，然而对于根据本发明的塑料制品的最频繁用途而言，超过这样的含量是罕见的。有利地，层B组合物中的酶含量是从0.01％至7％、优选从0.02％至5％。
除了酶之外，层B还包含此层的组成聚合物。根据本发明的一个优选实施方案，这些组成聚合物选自能够被它们所含的酶降解的聚合物，特别是上面针对层A定义的聚酯。这些组成聚合物也可以选自单独使用或以与上述聚酯的混合物使用的阻隔材料，诸如PVOH(聚乙烯醇)、PVCD(聚氯乙烯)、PGA(聚乙醇酸)、纤维素及其衍生物、乳蛋白、或多糖及其混合物。
关于层A，聚酯特别地选自可生物降解聚酯及其共聚物，特别是PBAT(聚己二酸对苯二甲酸丁二醇酯)、PHA(聚羟基烷酸酯)、PHB(聚-β-羟基丁酸酯)、PHH(聚羟基己酸酯)、PBS(聚琥珀酸丁二醇酯)、PLA(聚乳酸)、PCL(聚己内酯)、PBSA(聚己二酸琥珀酸丁二醇酯)、和增塑淀粉及其任何比例的混合物。
根据本发明的一个具体实施方案，根据本发明的层B的组成聚合物具有低于层A的组成聚合物的熔融温度的熔融温度。
在其制备过程中可以将酶直接添加到层B的聚合物中，或者作为在低熔点载体聚合物中的浓缩预混物。此类组合物特别描述于申请WO 2019/043134中。它们有利地包含载体，其具有低于140℃的熔融温度和/或低于70℃的玻璃化转变温度的载体聚合物和多糖。
具有低于140℃的熔融温度和/或低于70℃的玻璃化转变温度的聚合物是技术人员熟知的。它们特别是聚己内酯(PCL)、聚己二酸琥珀酸丁二醇酯(PBSA)、聚己二酸对苯二甲酸丁二醇酯(PBAT)、聚羟基烷酸酯(PHA)、聚乳酸(PLA)或其共聚物。它们也可以是天然聚合物，诸如淀粉或可被描述为通用(即，与大范围的聚合物(诸如EVA型共聚物)相容)的聚合物。有利地，载体聚合物具有低于120℃的熔融温度和/或低于30℃的玻璃化转变温度。
多糖特别地选自淀粉衍生物，诸如直链淀粉、支链淀粉、麦芽糊精、葡萄糖浆、糊精和环糊精；天然树胶，诸如阿拉伯树胶、黄蓍胶、瓜尔胶、刺槐豆胶、刺梧桐树胶、豆科树胶、半乳甘露聚糖、果胶或可溶性大豆多糖；海洋提取物，诸如角叉菜胶和海藻酸盐；以及微生物或动物多糖，诸如结冷胶、葡聚糖、黄原胶或壳聚糖；以及其混合物。优选的多糖是阿拉伯树胶。
优选的酶组合物特别地包含从50％至95％、优先地从70％至90％的低熔点聚合物，特别是聚己内酯(PCL)；从0.001％至10％、优先地从1％至6％的酶；和从1％至30％、优先地从10％至25％的阿拉伯树胶。
根据本发明的一个具体实施方案，层B基本上由以上酶组合物(载体聚合物也是组成聚合物)组成。所述组合物可以补充有以下所述的通常的添加剂。
根据本发明的另一个实施方案，根据通常的方法将酶组合物以足以提供针对层B所寻求的希望酶量添加到先前所述的一种或多种组成聚合物中。层B中酶组合物的含量将特别取决于酶组合物中酶的含量，有利地是基于层B组合物的总重量从1％至10％。
根据一个具体实施方案，除了构成层B的聚合物和酶之外，层B还包含如上定义的载体聚合物和多糖。
根据本发明的一个具体实施方案，层B包含
-从80％至99％、优选从90％至99％的组成聚合物，
-从0至40％、优选从0.1％至4％的多糖，
-从0至40％、优选从3％至6％的载体聚合物，和
-从0.005％至10％、优选从0.01％至5％、更优先地从0.01％至3％的酶。
根据本发明的一个更具体的实施方案，以上层B组合物中的酶含量的范围是从0.02％至1％。
层B的组合物还可以包含通常的添加剂，如用于层A的组合物的。特别地，当组成聚合物包含PLA和另一种聚酯的混合物时，所述组合物将有利地包含如上定义的增容剂和增塑剂。
根据本发明的柔性制品的一个具体实施方案，层B的组合物包含
-至少20％的PLA、有利地至少25％的PLA
-至少40％的PBAT
-至少0.08％、有利地至少0.5％的如上定义的PLA/PBAT增容剂，
-至少0.4％的增塑剂，特别地选自以上所述的OLA和柠檬酸酯，
-至少0.002％、有利地至少0.05％的酶，
-至少1.4％、有利地至少1.5％的如上所述的载体聚合物，和
-如果需要，多糖。
根据本发明的刚性制品的一个具体实施方案，层B的组合物包含
-至少90％的PLA、有利地至少95％的PLA
-至少0.002％、有利地至少0.05％的酶，
-至少1.4％、有利地至少1.5％的如上所述的载体聚合物，和
-如果需要，多糖。
根据本发明的刚性制品的另一个具体实施方案，层B的组合物包含
-至少40％的PLA、有利地至少50％的PLA
-至少15％的PBAT、有利地至少20％的PBAT
-至少5％的矿物填料、有利地至少10％的矿物填料
-至少0.002％、有利地至少0.05％的酶，
-至少1.4％、有利地至少1.5％的如上所述的载体聚合物，和
-如果需要，多糖。
根据本发明的某些实施方案，多层制品可以包含在外聚酯层A与包含酶的层B之间的一个或两个层C(ABCA或ACBCA)。存在这些层C是为了为根据本发明的制品提供特定的特性，更特别地是为了提供针对气体并且特别是氧气的阻隔特性。
此类阻隔材料是技术人员熟知的，并且特别是PVOH(聚乙烯醇)、PVCD(聚氯乙烯)、PGA(聚乙醇酸)、纤维素及其衍生物、乳蛋白、或多糖及其任何比例的混合物，如上针对也可以进入层B组合物的那些提及的。
在制品的制备中用作阻隔材料的PVOH是熟知的。它是聚合度包括在300与2500之间的聚乙烯醇。其熔点低于210℃，并且其粘度包括在3与60mPa.s之间。
在制品的制备中用作阻隔材料的PVCD是熟知的。它是由偏二氯乙烯(85％)和氯乙烯(15％)的共聚而得到的聚偏二氯乙烯。
在制品的制备中用作阻隔材料的PGA是熟知的。它是熔融温度是220℃并且玻璃化转变温度是40℃的聚乙醇酸。
在纤维素中，可以更特别提及的是微纤化纤维素(MFC)和醋酸纤维素。
用作阻隔材料的MFC具有包括在4与10006nm之间的直径和包括在0.51与1.57g/cm3之间的密度。
在用作阻隔材料的乳蛋白中，可以更特别提及的是酪蛋白、β-乳球蛋白和α-乳白蛋白以及免疫球蛋白、血清白蛋白、乳铁蛋白和酶，包括纤溶酶。
用作阻隔材料的多糖也是技术人员熟知的。可以更特别提及的是半乳甘露聚糖、果胶或可溶性大豆多糖；海洋提取物，诸如角叉菜胶和海藻酸盐；以及微生物或动物多糖，诸如结冷胶、葡聚糖、黄原胶、木聚糖或壳聚糖；以及其混合物。
关于层A和层B，层C还可以包含常用于生产塑料制品的其他添加剂，诸如助流剂、增塑剂、成核剂、增容剂、加工助剂、UV稳定剂、冲击抑制剂、矿物或植物填料等。
根据本发明的一个优选实施方案，以下是层C的组合物
-90％至100％的如上定义的阻隔材料，和
-0至10％的添加剂。
优选地，层C包含多于95％、甚至更优先地99％或更多的阻隔材料。
PVOH是用于根据本发明的制品的层C的优选阻隔材料。
根据本发明的柔性多层制品有利地具有小于250μm，优先地小于100μm、50μm、40μm或30μm的厚度。根据本发明的一个优选实施方案，多层制品的厚度的范围是从10至20μm。
根据本发明的刚性多层制品有利地具有大于150μm、优先地小于5000μm的厚度。根据本发明的一个优选实施方案，多层制品的厚度的范围是从150至3000μm。
根据本发明的ABA、ABCA或ACBCA制品的每个层的相对厚度可以根据针对制品所寻求的最终特性而变化，特别是在强度以及还有生物降解性方面。
有利地，每个层A独立地占制品总厚度的从5％至30％，并且中央层B占制品总厚度的从40％至90％。优选地，中央层B占制品总厚度的从50％至90％。
在本发明柔性制品的一个优选实施方案中，两个层A具有相同的厚度，各占制品总厚度的从15％至30％、优先地从16％至25％。
在本发明刚性制品的一个优选实施方案中，两个层A具有相同的厚度，各占制品总厚度的从2％至20％、优先地从3％至15％。
当存在时，层C通常具有小于15μm的厚度。它们独立地占制品总厚度的小于10％。
根据本发明的一个具体实施方案，当存在时，多层柔性制品的层C具有小于3μm的厚度。它们独立地占制品的小于30％。
根据本发明的一个具体实施方案，当存在时，多层刚性制品的层C具有小于20μm的厚度。它们独立地占制品的小于30％。
层A、层B和层C的组合物通过用于制备聚合物组合物的通常技术来制备。
技术人员将知道如何通过允许其连接的所有通常技术，诸如共挤出、压延、注射、层压，特别是通过挤出来制备根据本发明的多层制品。优选地，制品通过共挤出(技术人员能够确定实施所述过程的条件)各层并且特别是进入每个层的组合物中的组分的混合物来制备。有利地，共挤出在低于200℃的温度下进行。
根据本发明的制品可以用于热塑性制品的所有常见用途，并且特别是用于制备包装或袋或用于覆盖或邮寄。它还可以用于制备一次性餐具(盘、玻璃杯)、包装(托盘、泡罩包装)或饮料胶囊。
有利地，用于生产根据本发明的制品的生物基材料的比率大于30％、优先地大于40％。
实施例
材料和方法
I.PBAT和PLA混合物球粒的制备
在Clextral Evolum 25HT同向旋转双螺杆机上生产球粒。为了引入聚合物(PLA和PBAT)和增容剂，使用两个重量计量加料装置，并且为了加料液体TBAC，使用PCM泵。
在TBAC增塑剂的存在下在螺杆开始处经由加料装置引入PLA和
混合物。将混合物熔融并且进料到PBAT引入区中。
在450rpm的螺杆速度和40kg/h的流速下制备球粒。
用于球粒挤出的参数在表[1]中示出。
表1：用于球粒挤出的温度特征(℃)
| 区 | Z1 | Z2 | Z3 | Z4 | Z5 | Z6 | Z7 | Z8 | Z9 | Z10 | Z11 |
| 温度 | 50 | 195 | 195 | 195 | 195 | 195 | 195 | 195 | 195 | 195 | 195 |
组分的混合物在Z11中的螺杆中熔融，并且立即用湿切系统造粒以获得直径小于3mm的半月形球粒。
制备现有技术组合物，其包含35％的PLA和61％的PBAT、3％的TBAC和1％的
ADR 4468 C(基于组合物的总重量按重量计％)。
II.载体聚合物和酶混合物的制备
从聚己内酯(PCL)球粒和如申请WO 2019/043134中所述的呈液体形式的酶制备载体聚合物和酶混合物。
使用具有11个独立温度控制区的CLEXTRAL EV25HT双螺杆挤出机制造载体聚合物和酶混合物。使用蠕动泵将PCL以16kg/h引入区1，并且将酶溶液以4kg/h引入区5。根据表[2]加热所述区。将20％的酶溶液添加到PCL中(基于总重量按重量计％)。
表2：用于载体聚合物和酶混合物的温度特征(℃)
| 区 | Z1 | Z2 | Z3 | Z4 | Z5 | Z6 | Z7 | Z8 | Z9 | Z10 | Z11 |
| 温度 | 40 | 65 | 75 | 75 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
III.商业产品
在这些实施例中，由NatureWorks公司以产品名称IngeoTM Biopolymer 4043D出售的和由Total Corbion公司以产品名称
LX175出售的PLA、由Perstorp公司以产品名称CapaTM 6500出售的PCL、由BASF公司出售的
ADR 4468、由Jungbunzlauer公司出售的TBAC
BII、由Wango公司以产品名称A400出售的PBAT、由Novamont以产品名称Mater-Bi和由Carbiolice公司以产品名称Biolice.Bags 6040T出售的可生物降解化合物。
IV.膜的生产
对于多层膜的制备，使用Eurexma三层共挤出吹塑生产线，宽度275-300mm并且螺杆L/D＝30。吹塑速率约3.5-3.9。设置和温度详述在表[3]和[4]中。
表3：挤出机和模口温度参数(℃)
表4：挤出机方法参数
| 螺杆A(内部) | 螺杆B(中央) | 螺杆A(外部) | |
| 层分布％ | 20 | 60 | 20 |
| 螺杆速度(rpm) | 25-11 | 80-35 | 25-11 |
V.刚性片材的生产
对于刚性片材的制备，使用三层压延共挤出生产线。对于层B，使用直径45的FAIREX挤出机；对于层A，使用直径30的SCAMEX挤出机和直径30的Davis standard。所使用的平模口是220mm，并且配备有标称开口为1.5mm的可调节唇缘和ABA共挤出箱。设置和温度详述在表5中。
表5：挤出机、模口和压延生产线的温度参数(℃)
表6：挤出机、模口和压延生产线的方法参数
VI.分析方法
根据标准EN ISO 527-3(塑料-拉伸特性的确定-第3部分：膜和片材的测试条件(Plastics-Determination of tensile properties-Part 3:Test conditions forfilms and sheets))测量膜的机械特性。
用根据以下方案进行的解聚测试评估膜的生物降解性：将100mg每个样品引入含有50mL在pH 9.5下的缓冲溶液的塑料小瓶中。通过在以150rpm摇动的培养箱中在45℃下培养每个样品来开始解聚。定期抽取1mL缓冲溶液等分试样，并且通过0.22μm过滤器式注射器过滤以便通过具有Aminex HPX-87H柱的高效液相色谱法(HPLC)进行分析以测量乳酸(LA)及其二聚体的释放。所使用的色谱系统是Ultimate 3000UHPLC系统(Thermo FisherScientific,Inc.沃尔瑟姆，马萨诸塞州，美国)，其包括泵、自动进样器、恒温在50℃的柱和在220nm处的UV检测器。洗脱液是5mM H2SO4。注入20μL样品。从由商业乳酸制定的标准曲线中测量乳酸。
由释放的乳酸和乳酸二聚体计算塑料膜的水解。解聚的百分比是相对于样品中PLA的百分比计算的。
结果
VII.膜组成和结果
用在I中制备的球粒和在II中制备的载体聚合物和酶混合物、PBAT和Biolice.Bags 6040T制备膜。
用在I中制备的球粒和载体聚合物或用在I中制备的球粒和在II中制备的载体聚合物和酶混合物制备中央层B。
外层A由PBAT(100％)或Biolice.bags 6040T(100％)组成。
对于膜，每个A/B/A层的相对厚度是20％/60％/20％。
这些不同膜的组成列出在下表[7]中。
表7：生产的多层膜的汇总
膜1和膜3分别用作本发明膜2和膜4的现有技术参考。
混合物的存在对挤出吹塑过程没有影响。现有技术膜与本发明膜之间的方法参数保持相同。
如此测量的机械特性显示，本发明中公开的膜具有保持的并且与本领域一致的机械特性。结果呈现在表[8]中。
表8：膜的机械特性的表征
(LD＝膜的纵向并且TD＝膜的横向)
根据V中所述的方法评估膜的生物降解性。
不含载体聚合物和酶混合物的膜1和膜3具有零的解聚率。
根据本发明的膜2和膜4在9天后分别具有6.7％和8.4％的解聚率。
VIII.片材组成和结果
用PLA、Biolice.Bags 6040T、Mater-Bi和在II中制备的混合物制备片材。
用PLA或Mater-Bi和载体聚合物或用PLA或Mater-Bi和在II中制备的混合物制备中央层B。
外层A由PLA(100％)或Biolice.bags 6040T(100％)或Mater-Bi(100％)组成。
对于膜，每个A/B/A层的相对厚度是5％/90％/5％。
这些不同片材的组成列出在下表[9]中。
表9：生产的多层片材的汇总
混合物的存在对过程没有影响。现有技术片材或本发明片材之间的方法参数保持相同。
Claims (12)
1.一种ABA、ABCA或ACBCA型可生物降解多层热塑性制品，其特征在于中央层B包含至少0.001％的能够降解包围其的层A的聚合物的酶，所述百分比以基于层B的组合物的总重量按重量计给出。
2.根据权利要求1所述的多层制品，其特征在于层A包含选自以下的聚酯：PBAT(聚己二酸对苯二甲酸丁二醇酯)、PHA(聚羟基烷酸酯)、PHB(聚-β-羟基丁酸酯)、PHH(聚羟基己酸酯)、PBS(聚琥珀酸丁二醇酯)、PLA(聚乳酸)、PCL(聚己内酯)、PBSA(聚己二酸琥珀酸丁二醇酯)、增塑淀粉及其任何比例的混合物。
3.根据权利要求1或2中任一项所述的多层制品，其特征在于层A的聚酯选自PBAT、PLA及其任何比例的混合物。
4.根据权利要求1至3中任一项所述的多层制品，其特征在于层B的组合物包含至少0.002％、更有利地至少0.05％的酶。
5.根据权利要求1至4中任一项所述的多层制品，其特征在于层B的组成聚合物选自聚酯或阻隔材料，诸如PVOH(聚乙烯醇)、PVCD(聚氯乙烯)、PGA(聚乙醇酸)、纤维素、乳蛋白或多糖及其任何比例的混合物。
6.根据权利要求1至5中任一项所述的多层制品，其特征在于层B包含具有低于140℃的熔融温度和/或低于70℃的玻璃化转变温度的酶载体聚合物和多糖。
7.根据权利要求1至6中任一项所述的多层制品，其特征在于所述多层制品包含至少一个层C，其组合物包含气体阻隔材料，所述气体阻隔材料选自PVOH(聚乙烯醇)、PVCD(聚氯乙烯)、PGA(聚乙醇酸)、纤维素、乳蛋白或多糖及其任何比例的混合物。
8.根据权利要求1至7中任一项所述的多层制品，其特征在于所述多层制品是共挤出的。
9.根据权利要求1至8中任一项所述的多层制品，其特征在于所述多层制品具有小于250μm，优先地小于100μm、50μm、40μm或30μm，更优先地从10至20μm的厚度。
10.根据权利要求1至8中任一项所述的多层制品，其特征在于所述多层制品具有大于150μm，优先地小于5000μm，更优先地从250至3000μm的厚度。
11.一种膜，其特征在于所述膜包含根据权利要求9所述的多层制品。
12.根据权利要求10所述的多层材料用于制备杯、盘、饮料胶囊、托盘或泡罩包装的用途。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1903237A FR3094268B1 (fr) | 2019-03-28 | 2019-03-28 | Article multicouche enzymé |
| FRFR1903237 | 2019-03-28 | ||
| PCT/EP2020/058796 WO2020193770A1 (fr) | 2019-03-28 | 2020-03-27 | Article multicouche enzyme |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114007841A true CN114007841A (zh) | 2022-02-01 |
| CN114007841B CN114007841B (zh) | 2024-04-09 |
Family
ID=67875539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080023743.4A Active CN114007841B (zh) | 2019-03-28 | 2020-03-27 | 包含酶的多层制品 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US20220267068A1 (zh) |
| EP (1) | EP3946884B1 (zh) |
| JP (1) | JP7493531B2 (zh) |
| KR (1) | KR20210144743A (zh) |
| CN (1) | CN114007841B (zh) |
| AU (1) | AU2020247473A1 (zh) |
| BR (1) | BR112021019417A2 (zh) |
| CA (1) | CA3135264A1 (zh) |
| DK (1) | DK3946884T3 (zh) |
| ES (1) | ES2974195T3 (zh) |
| FI (1) | FI3946884T3 (zh) |
| FR (1) | FR3094268B1 (zh) |
| MX (1) | MX2021011825A (zh) |
| PT (1) | PT3946884T (zh) |
| WO (1) | WO2020193770A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220184933A1 (en) * | 2020-12-15 | 2022-06-16 | Nava Dimermanas | Biodegradable laminated composite material and method of use |
| US11485849B2 (en) | 2021-03-04 | 2022-11-01 | Balena Ltd. | Composite biodegradable polymeric based material, a product and a method of making same |
| FR3125533A1 (fr) * | 2021-07-20 | 2023-01-27 | Carbiolice | Procédé de Préparation d’un Mélange Maître Enzymé |
| FI20225651A1 (en) * | 2022-07-11 | 2024-01-12 | Sulapac Oy | Flexible multi-layer composite material |
| FR3139569A1 (fr) | 2022-09-14 | 2024-03-15 | Carbiolice | ARTICLE MONOCOUCHE ENZYMÉ ayant des propriétés barrières à l’eau |
| FR3139500B1 (fr) | 2022-09-14 | 2024-09-27 | Carbiolice | ARTICLE MULTICOUCHE ENZYMÉ ayant des propriétés barrières à l’eau |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0579546A2 (fr) * | 1992-07-15 | 1994-01-19 | Roquette FrÀ¨res | Composition thermoformable, son procédé de préparation et son utilisation pour l'obtention d'articles thermoformés |
| US5849401A (en) * | 1995-09-28 | 1998-12-15 | Cargill, Incorporated | Compostable multilayer structures, methods for manufacture, and articles prepared therefrom |
| CN1640649A (zh) * | 2004-01-15 | 2005-07-20 | 朱春英 | 一种高阻隔降解膜及其制造方法 |
| CN101679731A (zh) * | 2007-05-14 | 2010-03-24 | 阿克马法国公司 | 以能再生/能生物降解为基础的共挤出粘结料 |
| CN101687398A (zh) * | 2007-07-03 | 2010-03-31 | 纳幕尔杜邦公司 | 包含生物基材料的多层膜结构 |
| CN102350844A (zh) * | 2011-07-12 | 2012-02-15 | 中国科学院长春应用化学研究所 | 一种聚合物薄膜及其制备方法 |
| EP2583820A1 (en) * | 2011-10-18 | 2013-04-24 | ILFORD Imaging Switzerland GmbH | Biodegradable recording sheets for ink jet printing |
| CN207327742U (zh) * | 2017-06-09 | 2018-05-08 | 天津睿力群塑料制品股份有限公司 | 一种可降解塑料薄膜 |
| WO2018233888A1 (de) * | 2017-06-19 | 2018-12-27 | Basf Se | Biologisch abbaubare dreischichtfolie |
| WO2019043134A1 (en) * | 2017-08-31 | 2019-03-07 | Carbiolice | BIODEGRADABLE POLYESTER ARTICLE COMPRISING ENZYMES |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4133335C2 (de) | 1991-10-08 | 1995-11-02 | Inventa Ag | Stärkemischung, Verfahren zu ihrer Herstellung sowie Verwendung derselben |
| ITTO20010057A1 (it) | 2001-01-25 | 2002-07-25 | Novamont Spa | Miscele ternarie di poliesteri biodegradabili e prodotti da queste ottenuti. |
| ITTO20010059A1 (it) | 2001-01-25 | 2002-07-25 | Novamont Spa | Miscele ternarie di poliesteri alifatici biodegradabili e prodotti daqueste ottenuti. |
| ITTO20010060A1 (it) | 2001-01-25 | 2002-07-25 | Novamont Spa | Miscele ternartie di poliesteri alifatici biodegradabili e prodotti da queste ottenuti. |
| JP2003020025A (ja) * | 2001-07-05 | 2003-01-21 | Toppan Printing Co Ltd | 生分解性紙カップ |
| DE10258227A1 (de) | 2002-12-09 | 2004-07-15 | Biop Biopolymer Technologies Ag | Biologisch abbaubare Mehrschichtfolie |
| DE202007018690U1 (de) * | 2006-04-14 | 2009-02-19 | Bio-Tec Biologische Naturverpackungen Gmbh & Co.Kg | Mehrschichtfolie |
| WO2009014202A1 (ja) * | 2007-07-26 | 2009-01-29 | Alcare Co., Ltd. | 水解性シート及びこれを用いた排泄物収容装具用パウチ |
| CA2712709A1 (en) | 2008-01-25 | 2009-07-30 | Ara, Marco Paolo | Process for the plasticization of lactic acid polymers |
| US8188185B2 (en) | 2008-06-30 | 2012-05-29 | Kimberly-Clark Worldwide, Inc. | Biodegradable packaging film |
| DE112008004045T5 (de) | 2008-10-22 | 2013-01-10 | Hewlett-Packard Development Company, L.P. | Verfahren und System zum Bereitstellen von Berechtigungen einer Aufzeichnungsvorrichtung mittels einer biometrischen Bewertung |
| JP5620190B2 (ja) * | 2010-08-12 | 2014-11-05 | 株式会社クレハ | 生分解性樹脂積層体 |
| US9096758B2 (en) | 2011-07-29 | 2015-08-04 | Basf Se | Biodegradable polyester foil |
| FR2984354A1 (fr) * | 2011-12-20 | 2013-06-21 | Centre Nat Rech Scient | Procede de preparation d'alliage polymere/enzymes |
| CN105916919A (zh) * | 2013-10-27 | 2016-08-31 | 蒂帕有限责任公司 | 可生物降解的片材 |
| PL3209771T3 (pl) | 2014-10-21 | 2021-05-31 | Carbios | Polipeptyd wykazujący działanie rozkładające poliester i jego zastosowania |
| CA2965767A1 (en) * | 2014-10-27 | 2016-05-06 | Tipa Corp. Ltd | Biodegradable sheets |
| EP3268469A1 (en) | 2015-03-13 | 2018-01-17 | Carbios | New polypeptide having a polyester degrading activity and uses thereof |
| JP6907132B2 (ja) | 2015-06-12 | 2021-07-21 | キャルビオスＣａｒｂｉｏｓ | 生分解性ポリエステル組成物及びその使用 |
| CA2991142A1 (en) * | 2015-06-30 | 2017-01-05 | Nanotics, Llc | Compositions and methods related to scavanger particles |
| CN106881929B (zh) | 2017-01-20 | 2019-03-12 | 山东农业大学 | 一种聚己二酸对苯二甲酸丁二酯/淀粉高阻隔复合膜及其制备方法 |
| WO2019122195A1 (en) * | 2017-12-21 | 2019-06-27 | Beaulieu International Group Nv | Biodegradable fabric and use of such fabric |
| CN110791069B (zh) * | 2019-11-08 | 2021-11-16 | 佰信(福建)新材料科技有限公司 | 一种软包装用全降解高阻隔复合材料 |
-
2019
- 2019-03-28 FR FR1903237A patent/FR3094268B1/fr active Active
-
2020
- 2020-03-27 BR BR112021019417A patent/BR112021019417A2/pt unknown
- 2020-03-27 MX MX2021011825A patent/MX2021011825A/es unknown
- 2020-03-27 DK DK20713047.7T patent/DK3946884T3/da active
- 2020-03-27 CA CA3135264A patent/CA3135264A1/fr active Pending
- 2020-03-27 CN CN202080023743.4A patent/CN114007841B/zh active Active
- 2020-03-27 US US17/598,746 patent/US20220267068A1/en active Pending
- 2020-03-27 ES ES20713047T patent/ES2974195T3/es active Active
- 2020-03-27 JP JP2021557515A patent/JP7493531B2/ja active Active
- 2020-03-27 WO PCT/EP2020/058796 patent/WO2020193770A1/fr unknown
- 2020-03-27 EP EP20713047.7A patent/EP3946884B1/fr active Active
- 2020-03-27 PT PT207130477T patent/PT3946884T/pt unknown
- 2020-03-27 FI FIEP20713047.7T patent/FI3946884T3/fi active
- 2020-03-27 AU AU2020247473A patent/AU2020247473A1/en active Pending
- 2020-03-27 KR KR1020217031941A patent/KR20210144743A/ko unknown
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0579546A2 (fr) * | 1992-07-15 | 1994-01-19 | Roquette FrÀ¨res | Composition thermoformable, son procédé de préparation et son utilisation pour l'obtention d'articles thermoformés |
| US5849401A (en) * | 1995-09-28 | 1998-12-15 | Cargill, Incorporated | Compostable multilayer structures, methods for manufacture, and articles prepared therefrom |
| CN1640649A (zh) * | 2004-01-15 | 2005-07-20 | 朱春英 | 一种高阻隔降解膜及其制造方法 |
| CN101679731A (zh) * | 2007-05-14 | 2010-03-24 | 阿克马法国公司 | 以能再生/能生物降解为基础的共挤出粘结料 |
| CN101687398A (zh) * | 2007-07-03 | 2010-03-31 | 纳幕尔杜邦公司 | 包含生物基材料的多层膜结构 |
| CN102350844A (zh) * | 2011-07-12 | 2012-02-15 | 中国科学院长春应用化学研究所 | 一种聚合物薄膜及其制备方法 |
| EP2583820A1 (en) * | 2011-10-18 | 2013-04-24 | ILFORD Imaging Switzerland GmbH | Biodegradable recording sheets for ink jet printing |
| CN207327742U (zh) * | 2017-06-09 | 2018-05-08 | 天津睿力群塑料制品股份有限公司 | 一种可降解塑料薄膜 |
| WO2018233888A1 (de) * | 2017-06-19 | 2018-12-27 | Basf Se | Biologisch abbaubare dreischichtfolie |
| WO2019043134A1 (en) * | 2017-08-31 | 2019-03-07 | Carbiolice | BIODEGRADABLE POLYESTER ARTICLE COMPRISING ENZYMES |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210144743A (ko) | 2021-11-30 |
| CA3135264A1 (fr) | 2020-10-01 |
| PT3946884T (pt) | 2024-03-21 |
| EP3946884A1 (fr) | 2022-02-09 |
| JP7493531B2 (ja) | 2024-05-31 |
| FI3946884T3 (fi) | 2024-03-22 |
| US20220267068A1 (en) | 2022-08-25 |
| DK3946884T3 (da) | 2024-03-25 |
| EP3946884B1 (fr) | 2023-12-20 |
| WO2020193770A1 (fr) | 2020-10-01 |
| ES2974195T3 (es) | 2024-06-26 |
| JP2022526169A (ja) | 2022-05-23 |
| AU2020247473A1 (en) | 2021-10-07 |
| FR3094268A1 (fr) | 2020-10-02 |
| FR3094268B1 (fr) | 2021-03-19 |
| CN114007841B (zh) | 2024-04-09 |
| MX2021011825A (es) | 2021-10-22 |
| BR112021019417A2 (pt) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114007841B (zh) | 包含酶的多层制品 | |
| JP7217267B2 (ja) | 生物学的実体を含む液体組成物及びその使用 | |
| KR102574368B1 (ko) | 효소를 포함하는 생분해성 폴리에스테르 물품 | |
| CN101360783B (zh) | 阻透膜 | |
| JP5420423B2 (ja) | バイオポリマーを含む組成物 | |
| JP5124687B2 (ja) | 脂肪族ポリエステル及び水再分散性ポリマー粉末を基礎とする生分解性成形体を製造するための混合物 | |
| CA2725222A1 (en) | Thermoformed article made from bio-based biodegradable polymer composition | |
| KR20140110865A (ko) | 생체중합체 함유 다층 필름 | |
| KR20220134549A (ko) | 효소 마스터배치의 제조 방법 | |
| CN112384554A (zh) | 包含柠檬酸酯的高pla含量塑料材料 | |
| AU2005297323A1 (en) | Barrier film | |
| KR20240046870A (ko) | 효소 마스터배치를 제조하기 위한 방법 | |
| FR3139500A1 (fr) | ARTICLE MULTICOUCHE ENZYMÉ ayant des propriétés barrières à l’eau | |
| FR3144996A1 (fr) | Melange maitre enzyme comprenant des proteines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |