CN1504391A - Multiple layer plastic container - Google Patents
Multiple layer plastic container Download PDFInfo
- Publication number
- CN1504391A CN1504391A CNA031407382A CN03140738A CN1504391A CN 1504391 A CN1504391 A CN 1504391A CN A031407382 A CNA031407382 A CN A031407382A CN 03140738 A CN03140738 A CN 03140738A CN 1504391 A CN1504391 A CN 1504391A
- Authority
- CN
- China
- Prior art keywords
- plastic container
- resin
- layer
- hydropolymer
- multilayer plastic
- 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
- 229920003023 plastic Polymers 0.000 title claims abstract description 65
- 239000004033 plastic Substances 0.000 title claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 143
- 239000011347 resin Substances 0.000 claims abstract description 143
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 88
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 229920005604 random copolymer Polymers 0.000 claims description 58
- 229920000058 polyacrylate Polymers 0.000 claims description 57
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 37
- 239000005977 Ethylene Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 25
- 239000004711 α-olefin Substances 0.000 claims description 24
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 229920001684 low density polyethylene Polymers 0.000 claims description 16
- 239000004702 low-density polyethylene Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002667 nucleating agent Substances 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 11
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 9
- 229910021332 silicide Inorganic materials 0.000 claims description 9
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 7
- 238000002955 isolation Methods 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 11
- 239000011342 resin composition Substances 0.000 abstract 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract 3
- 239000010410 layer Substances 0.000 description 82
- 239000002650 laminated plastic Substances 0.000 description 31
- 229920003048 styrene butadiene rubber Polymers 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000002174 Styrene-butadiene Substances 0.000 description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000035939 shock Effects 0.000 description 12
- 239000011115 styrene butadiene Substances 0.000 description 12
- 238000000071 blow moulding Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 239000003595 mist Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002952 polymeric resin Substances 0.000 description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 4
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 4
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 4
- 241000251730 Chondrichthyes Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 101150071434 BAR1 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920005673 polypropylene based resin Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Images
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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B1/00—Layered products having a general shape other than plane
-
- 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
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/406—Bright, glossy, shiny surface
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
Abstract
A multi-layer plastic container is provided to have an excellent resistance for an impact such as a falling impact, gloss of a container surface and a transparency. The multi-layer plastic container(1) comprises at least one layer composed of a resin essentially of a propylene based polymer and layers of a resin composition containing a hydrogenation polymer. The layer of the resin composition is placed outside the container. The layer of the resin composition is a main layer of the container. The hydrogenation polymer is contained in a ratio of 1 to 35 wt.% in the resin composition. The polymer is a hydrogenation polymer of a copolymer composed of an aromatic vinyl compound and a vinyl compound with conjugated double bonds.
Description
Technical field
The present invention relates to a kind of plastic container, particularly have the multilayer plastic container of excellent impact strengths such as drop impact degree, vessel surface glossiness and the transparency.
Background technology
At present, various polypropylene-based polymer products are widely used and make plastic container.
But, by the container that polypropylene is made, compare, although good heat resistance is relatively poor at aspects such as Dent resistance such as drop impact degree, glossiness and the transparencys with the container of for example making by polyethylene.
As the method that improves drop impact, once proposed blend shape low density polyethylene (LDPE) (with reference to patent documentation 1), mixed by the ethene-alpha-olefin copolymer (with reference to patent documentation 2) of aromatic ring alkene metal derivative catalyst polymerization etc.In addition, as the method that improves outer field glossiness, also proposed to use specific composition and MFR polypropylene-based resin (with reference to patent documentation 3), add crystallization nucleating agent (with reference to patent documentation 4) etc., but all can not satisfy performance requriements fully.
In addition, in order to obtain, also disclosed the composition molding that the hydrogenated block copolymer by the crystallinity acrylic polymers (120～145 ℃ of fusing points) of 95～80 weight % and 5～20 weight % constitutes and the container (with reference to patent documentation 5) that obtains by having the container that the good transparency, the less acrylic polymer that turns white are made.
[patent documentation 1]: No. the 2691494th, patent
[patent documentation 2]: the spy opens the 2000-190438 communique
[patent documentation 3]: No. the 2135306th, patent
[patent documentation 4]: No. the 3106834th, patent
[patent documentation 5]: the spy opens flat 10-87921 communique
Summary of the invention
The 1st purpose of the present invention is to provide the various character that have polypropylene-based resins such as good rigidity, resistance to effect of heat, the transparency, simultaneously, and the improved plastic container of the drop impact under the Dent resistance such as dropping impact strength, particularly low temperature.And second purpose of the present invention is when being to give security Dent resistance, the plastic container that the transparency, surface gloss are excellent especially.
The present invention is for reaching the scheme that above-mentioned purpose proposes, having following characteristics.That is:
1. multilayer plastic container is characterized by: at least 1 layer is by being matrix resin with the acrylic polymer, and contains the layer that the resin combination of hydropolymer forms.
2. as 1 described multilayer plastic container, it is characterized by: the layer that is formed by above-mentioned resin combination is the skin of container.
3. as 1 described multilayer plastic container, it is characterized by: the layer that is formed by above-mentioned resin combination is the main stor(e)y of container.
4. as 1～3 each described multilayer plastic container, it is characterized by: the contained ratio of the hydropolymer in the above-mentioned resin combination is 1～35 weight %.
5. as 1～4 each described multilayer plastic container, it is characterized by: above-mentioned hydropolymer is the hydropolymer of the copolymer that formed by aromatic ethylene compound and the olefin compound with conjugated double bond.
6. as 1～5 each described multilayer plastic container, it is characterized by: above-mentioned hydropolymer is the hydropolymer of the periodic copolymer that formed by aromatic ethylene compound and the olefin compound with conjugated double bond.
7. as 6 described multilayer plastic containers, it is characterized by: above-mentioned aromatic ethylene compound is a styrene, and above-mentioned olefin compound with conjugated double bond is butadidenne and/or isoprene.
8. as 1～7 each described multilayer plastic container, it is characterized by: the aforesaid propylene based polymer is to be that 2～15mol%, MFR are that the copolymer of the propylene-alpha-olefin more than the 1.0g/10min, below the 15g/10min forms by polypropylene or alpha-olefin composition.
9. as 8 described multilayer plastic containers, it is characterized by: propylene-alpha-olefin copolymers is a random copolymers.
10. as 1～9 each described multilayer plastic container, it is characterized by: above-mentioned resin combination also contains ethylene-based polymer.
11. as 10 described multilayer plastic containers, it is characterized by: above-mentioned ethylene-based polymer is the low density polyethylene (LDPE) of polymerization by aromatic ring alkene metal derivative catalyst.
12. as 1～11 each described multilayer plastic container, it is characterized by: at least 1 layer acrylic polymer layer contains crystallization nucleating agent.
13. as 12 described multilayer plastic containers, it is characterized by: the crystallization heat of fusion of at least 1 layer acrylic polymer layer is 50～175J/g.
14. as each described multilayer plastic container of 1～13, it is characterized by: by the skin that contains hydropolymer, adhesion resin layer, isolate resin bed, adhesion resin layer, acrylic polymer layer or contain acrylic polymer layer, the acrylic polymer internal layer that reclaims resin or the acrylic polymer internal layer that contains hydropolymer constitutes 4 kinds 6 layers or 5 kinds 6 layers.
15., it is characterized by: have the isolation resin bed that is selected from ethylene-vinyl acetate copolymer silicide, polyamide, the cyclic olefin copolymer as 1～14 each described multilayer plastic container.
16. as 15 described multilayer plastic containers, it is characterized by: have and comprise and contain the recovery resin bed of isolating resin
Description of drawings
Fig. 1 is the longitudinal diagram of plastic container of the present invention.
Fig. 2 is the generalized section of 1 example of layer structure of the A part of plastic container of the present invention.
Nomenclature
1 laminated plastics bottle; 2 skins; 3 adhesion resin layers; 4 gas barrier properties resin beds; 5 broken resin layers; 6 internal layers
The specific embodiment
Multilayer plastic container of the present invention is characterised in that at least 1 layer is to be formed by the resin combination that mixes hydropolymer in acrylic polymer.
Acrylic polymer as the main composition in the resin combination, can enumerate polypropylene, propylene-alpha-olefin copolymers, more specifically can enumerate propylene-ethylene block copolymer, the propylene-ethylene random copolymers, wherein the propylene-ethylene random copolymers becomes preferred because of its transparency is good, the preferred ethene composition that uses is that the MFR of 2～15mol% is the propylene-ethylene random copolymers more than the 1.0g/10min, particularly when being used for skin, because of glossiness good, preferably use the ethene composition, the propylene-ethylene random copolymers that MFR3.0g/10min is above as more than the 4mol%.
In the propylene-ethylene random copolymers,, cause the transparency to reduce according to condition of molding if ethylene contents is low.The propylene-alpha-olefin copolymers that ethylene contents surpasses 15mol% then or because be difficult to polymerization, productive rate obviously reduces, or because contain a lot of low molecular weight substances, and causes commercial production extremely difficult.When being used for skin,,, when using the material moulding of narrow molecular weight distribution to a certain degree, can produce shark skin spot etc. in order to ensure glossiness if MFR is difficult to guarantee glossiness at 3.0g/10min with next, thus badly damaged outward appearance.In the scope of Dent resistance, be suitable for using MFR height material to a certain degree.
Be after the first stage polymerization of propylene or propylene and ethene, with the rubber composition of ethene, propylene as the acrylic polymer of next stage polymerization as so-called propylene-ethylene block copolymer, and be that the resin of 0.5～4.0g/10min is used for main stor(e)y or internal layer at 25 moles below the %, MFR with ethylene total content.
By this resin is disposed at interlayer or internal layer, except keeping high impulse strength and rigidity, can also make the bottle that outside mist degree reduces, the transparency is good.
In addition, hydropolymer is mixed with the aforesaid propylene based polymer as a small amount of composition.As hydropolymer, can enumerate the hydropolymer that forms copolymer by aromatic ethylene compound and olefin compound with conjugated double bond.Wherein, especially preferably use the hydropolymer of styrene butadiene random copolymer, the hydropolymer of styrene-butadiene block copolymer, the hydropolymer of styrene-ethylene base isoprene block copolymer.The combined amount of hydropolymer is preferably with respect to the acrylic polymer as main composition, is the ratio of 1～35 weight %.
Shown in following embodiment, when adding less hydropolymer, demonstrate the effect that improves strength under shock.That is, with a small amount of interpolation of 1～10 weight %, because of acting on acrylic polymer as the nucleating agent with nucleus of styrene constitutional repeating unit, so can form fine and close crystalline texture, the result has just improved strength under shock and glossiness.Because this fine and close crystalline texture, surface deficiency reduces significantly, thereby can infer, and has reduced because of falling to produce the possibility of breaking.
At addition is more than the 10 weight %, till 35 weight % the time, can reach high impact by the rubber-like composition that adds hydropolymer., because the increase of soft composition can make hardness reduce, tank capacity produces scar, and it is difficult to slide, and easily stops up during the conveyor line conveyance.Although the addition of increase lubrication prescription has effect to a certain degree, can not ignore influence to the content local flavor.
When addition during more than 35 weight %, the rigidity of container reduces, and the output instability of resin during moulding, can be called as the shaggy situation of the vessel surface of shark skin spot etc. usually.In addition, the transparency that also can generation container, glossiness reduce such problem.
Being characterized as of multilayer plastic container of the present invention, at least skin is to be formed by the resin combination that specific acrylic polymer and hydropolymer mix, at this moment, when the Dent resistance of dropping impact strength etc. was improved, the glossiness of vessel surface, the transparency of container also were improved.
Hydropolymer is to use well-known method, and interpolation hydrogen obtains in the copolymer that the monomer that is had conjugated double bond by aromatic vinyl monomer, isoprene, butadidenne etc. obtains by common solution polymerization process polymerization.
Be preferably and contain the aromatic vinyl monomer that can carry out the granulation degree of treatment, for example when using styrene, be preferably 6～30mol%.If aromatic vinyl monomer consumption very little, not only be difficult to carry out granulation and handle, and lack the effect of the compact crystal nuclear that forms acrylic polymer.If aromatic vinyl monomer consumption is too many, then the raising effect of strength under shock will be cancelled.
Remove and to have the butadidenne that also contains 1,2 structure to a certain degree beyond 1,4 structure raising of the strength under shock of acrylic polymer is had very big effect.In addition, also very effective on this aspect of intermiscibility of isoprene and acrylic polymer.Equally, from control heat stability and elution viewpoint, the hydrogen adding rate also is preferably more than 70%.Aromatic vinyl monomer and conjugated diene monomer adopt which kind of link configuration mode all can, but in order to make the stability that granulation is handled to be had to a certain degree, the aromatic vinyl monomer preferably adopts slightly relatively block configuration.In hydropolymer, can use well-known oxidation inhibitor or anti-ageing agent, shaping assistant etc.
Adding method as hydropolymer can use well-known method.That is, can be in substrate resin the particle of mix predetermined quantities.In addition, also can use powder stock,, use double screw extrusion machine to mix in advance and mix with predetermined ratio.Effective especially under the situation of this method other resin such as mixed olefins resin when being mixed with a small amount of hydropolymer.Although also can use the extruder that is equipped with common full flight screw,, still be suitable for using extruder with big compression ratio from mixed uniformly viewpoint.
In addition, being characterized as of multilayer plastic container of the present invention, main stor(e)y (thickest layer) is to mix the resin combination that forms mutually by acrylic polymer and hydropolymer to form at least, at this moment, can improve the transparency of Dent resistance such as drop strength and container.
The selection of its blending ratio, acrylic polymer etc. is arbitrarily, and the higher glossiness resin of MFR is suitable for using hydropolymer, and to the main stor(e)y of container rigidity effects maximum, then is suitable for the acrylic polymer that uses above-mentioned rigidity to be improved.Because dispose the resin bed of gloss at skin the most effective to improving strength under shock, therefore, be preferably at main stor(e)y and/or the high resin bed of internal layer configuration rigidity.Actv. layer structure is not limited thereto, and also has, contain glossiness resin bed (the skin)/adhesion resin layer/isolation resin bed/adhesion resin layer of hydropolymer/contain broken resin acrylic polymer (
*) layer/contain the glossiness resin bed (internal layer) of hydropolymer, perhaps, contain glossiness resin bed (the skin)/adhesion resin layer/isolation resin bed/adhesion resin layer of hydropolymer/contain broken resin acrylic polymer (
*) layer/acrylic polymer (
*) layer (internal layer) etc.Here
*The high acrylic polymer of expression rigidity.
In addition, in multilayer plastic container of the present invention, because by in acrylic polymer, mixing hydropolymer, can improve strength under shock, anti-falling property, so applicable to the multilayer structure making of the higher acrylic polymer of rigidity, thus obtain rigidity higher, be difficult to produce diastrophic bottle.
As the high acrylic polymer of rigidity, can enumerate, it is the atactic polymer of 0.5～8g/10min that ethene, butylene are compared the MFR that uses as comonomer with the combined polymerization of 0～10mol%; As comonomer, the content in the ethene polymerization in the early stage below 3mol%, and in later stage polymerization and modification, content below 15 weight %, MFR is the periodic copolymer of 0.5～8g/10min.From guaranteeing the viewpoint of resin rigidity, under arbitrary occasion, the crystallization melting heat all is preferably 50～175J/g.The crystallization melting heat is not limited thereto determination method, also can use バ-キ Application ェ Le マ-DSC7 type, carries out heat with the standard test portion and proofread and correct and record under the situation of 10 ℃ of intensifications.
Example as the high acrylic polymer of these rigidity, can enumerate, it is low-level that ethylene comonomer is maintained, use the magnesium chloride load to hold type tacticity polymerization catalyst, promptly, use by with magnesium, titanium, halogen as solid catalyst, organo-aluminum compound that must composition, have antigravity system that the organo-silicon compound that branched alkyl arranged of carbon number more than 4 constitute etc., making the isotacticity branch rate that is calculated by 13C-NMR is high homopolymer resin of the isotacticity more than 0.97 etc.; The perhaps low random copolymer resin of ethylene contents, by being base material with these resins, carry out the continuous combined polymerization of ethylene-propylene, perhaps the ethene-alpha-olefin copolymer of mixed carbon number 4～20 just can obtain rigidity and Dent resistance and obtain well balanced poly-mer.
In multilayer plastic container of the present invention, when content is responsive to oxygen, the oxygen barrier resin bed also can be set as isolating resin bed.As being suitable for use as the material that constitutes the oxygen barrier resin bed, can enumerating ethylene contents is that 20～50mol%, silication degree are the above ethylene-vinyl acetate copolymer silicide of 95mol%.As other isolation resin, also can use in per 100 carbon atoms, the amide group number is 3～30, particularly 4～25 polyamide-based; Cyclic olefin copolymer; Polyacrylinitrile.These isolation resins both can use separately, also can two or more mixing use, and, in the scope of its proterties, also can mix other thermoplastic base resin.
In addition, in the present invention, the broken resin layer that the fragment of flash that produces in the time of can forming by the plastic container moulding and off gauge etc. constitutes (リ グ ラ ィ Application De: REG or recovery resin bed).But the layer that the broken resin layer had both only been formed by broken resin also can be the compound with untapped acrylic polymer.And, can also mix with other hydropolymer.When forming the broken resin layer by the compound that does not use resin in broken resin and the matrix resin, the combined amount of broken resin, being preferably with respect to not using resin is 1～50 weight %.
In addition, when using broken resin, for improving the characteristic of broken resin, the dispersiveness in order to improve broken resin and to sneak in the propylene resin particularly, improve the Dent resistance and the transparency, broken resin also can add for example maleic anhydride modified acrylic polymer (maleic anhydride modified polypropylene) except that using the acrylic polymer.
Usually, contain the isolation resin immiscible owing to contain the layer of broken resin, and reduced the transparency, simultaneously, also reduced strength under shock with substrate resin.Particularly, can not ignore this influence for propylene resin.Use as broken resin by the skin that will contain hydropolymer, perhaps add other hydropolymer, add auxiliary agent, the auxiliary agent resin of other improvement dispersiveness, just can improve the Dent resistance and the transparency.
Multilayer plastic container of the present invention when adopting except having skin, when also having the structure of broken resin layer and/or gas barrier properties resin bed, can be provided with the adhesion resin layer as required between each resin bed.As this adhesion resin layer, there is not restriction especially, preferably use sour modified olefin resin, for example utilize maleic anhydride, acrylic acid, methyl acrylic acid, olefines unsaturated carboxylic acid such as itaconic anhydride or its acid anhydrides carry out polypropylene, ethene-alpha-olefin copolymer of graft modification etc.
In multilayer plastic container of the present invention, contain the ethylene-based polymer that can also add again in the resin combination of aforesaid propylene based polymer and hydropolymer as the 3rd composition.As ethylene-based polymer, can enumerate the straight chain shape low density polyethylene (LDPE) that uses the Z-N series catalysts to be polymerized, low density polyethylene (LDPE), EP rubbers, EPDM, use straight chain shape low density polyethylene (LDPE) that the metal series catalysts is polymerized, straight chain shape ultra-low density polyethylene etc. in addition.
In above-mentioned ethylene-based polymer, the straight chain shape low density polyethylene (LDPE) that particularly uses aromatic ring alkene metal derivative series catalysts to be polymerized is because of it can improve Dent resistance, glossiness, the transparency, so also be preferred.This straight chain shape low density polyethylene (LDPE), be with rare by ethene as the 1-fourth of comonomer, the 1-hexene, in the hot rare grade of the 1-alpha-olefin any carried out the product after the combined polymerization, particularly consider aspects such as effect to the modification of propylene resin, compatibility, the preferred 1-hexene that uses is considered also favourable as comonomer from economic aspect.In addition, it is 1.0～10.0g/10min that straight chain shape ultra-low density polyethylene also is suitable for using MFR, and density 0.850～0.910g/cc is by near the product the molecular weight distribution 3.0 of Mw (weight average molecular weight)/Mn (number-average molecular weight) regulation.The MFR of straight chain shape ultra-low density polyethylene is during greater than 10.0g/10min, because resulting resin combination demonstrates tangible contraction, therefore the forming characteristics variation in the scope of not damaging with the compatibility of matrix resin, is suitable for adopting lower MFR.When being mixed with molecular weight distribution less than 2.5 material, rough surface can take place during blow molding directly, therefore, can produce glossiness, the transparency reduces such problem.In addition, when to use molecular weight distribution be near 4.0 material, because the existence of low-molecular-weight composition, vessel surface such problem that is clamminess can appear.
The blending ratio of straight chain shape ultra-low density polyethylene in resin combination is 2～50 weight %, is preferably 2～30 weight %.If combined amount is less than 2 weight %, at aspects such as the Dent resistance of plastic container, surface gloss, the transparencys, do not have better effect, and, form shark skin spot etc. when combined amount during more than 50 weight %, make the forming characteristics variation of container.
MFR, density are measured according to JIS K6758.Molecular weight distribution is done the standard molecular weight conversion by gel permeation chromatography (GPC) with polystyrene and is recorded.
Be not limited thereto as the layer structure that is suitable for plastic container of the present invention, if Ad represents: adhesion resin, Bar represents: isolate resin, REG represents: reclaim resin,
*Expression: hydropolymer, PP1, PP2, PP3 represent: acrylic polymer (also comprising the situation that contains other vinylite) then by skin to internal layer is
·PP1+
*/PP2+REG
·PP1+
*/PP2+REG/PP3
·PP1+
*/PP2+REG+
*/PP2
·PP1+REG+
*/Ad/Bar/Ad/PP1+REG+
*
·PP1+
*/Ad/Bar/Ad/PP2+REG/PP1+
*
·PP1+
*/Ad/Barl/Ad/PP2+REG/Ad/Bar2
·PP1+
*/PP2+REG/Ad/Bar1/Ad/Bar2/Ad/PP2
·PP1+
*/PP2+REG/Ad/Bar/Ad/PP2+REG/PP1+
*
·PP1+
*/Ad/Bar/Ad/PP2/PP3
·PP1+
*/Ad/Bar/Ad/PP2+REG/PP3
·PP1+
*/PP2+REG/Ad/Bar/Ad/PP3
Notes) Bar1 is the ethylene-vinyl acetate copolymer silicide, and Bar2 is a cyclic olefin copolymer.
In addition, in each resin bed that constitutes plastic container of the present invention, also can add colorants such as the ultraviolet absorbent that often adds in the lubrication prescription that forms by senior fatty acid amides such as oleamide, stearmide, erucyl amide etc., the plastic container, antistatic agent, pigment as required, additives such as oxidation inhibitor, neutralizing agent.
In addition, in the present invention, in the resin combination that contains acrylic polymer and hydropolymer, can also add crystallization nucleating agent.Be accompanied by the interpolation of hydropolymer, obtain the situation of composite effect in addition.
In addition,,, guarantee the viewpoint of rigidity, need in acrylic polymer, to add the small amount of crystalline nucleating agent sometimes to improve strength under shock from using rigidity up to a certain degree acrylic polymer.
As crystallization nucleating agent, can use aromatic carboxylic acid slaine, aromatic phosphoric acid slaine, D-sorbite is slaine of derivant, rosin metal salt, aromatic phosphorus compound etc.In these crystallization nucleating agents, be suitable for using P-t-butyl benzoic acid aluminium, 2,2 '-methene two (4,6-two-t-butylbenzene base) sodium phosphate, 2,2 '-methene two (4,6-two-t-butylbenzene base) aluminium phosphate, p-ethyl-benzylidene D-sorbite, p-ethyl-benzylidene D-sorbite, abietic acid sodium salt etc.In resin combination, crystallization nucleating agent is 0.05～0.5 weight % with respect to the ratio of resin, is preferably 0.2～0.3 weight %.
As plastic container of the present invention, the container that can to enumerate with hollow bottle shown in Figure 1 be the different shape of representative, these plastic container can be by rotation blow molding, common method manufacturings such as shuttle-type blow molding.
As preferred forming method, the parison that obtains by each resin bed coextrusion of using the multiple mould of multilayer will constitute container is arranged, directly blow molding is the method for hollow plastic container in blow molding die.In addition, such layer structure, also can be used for the laminated plastics thin slice by vacuum, press empty moulding, form shapes of containers such as plate, cup.
Plastic container of the present invention except that for example being used for, outside food such as tomato sauce, mayonnaise, the flavoring usefulness bottle, also can be used for common shampoo, rinse or detergent use bottle etc.
[embodiment]
With following embodiment the present invention is further specified, the present invention is not limited only to illustrated embodiment.
In following example, will be according to usual method, the parison that uses the multiple mould of multilayer, obtain through coextrusion again, with rotation blow molding machine direct blow molding, be shaped to container weight 27g, internal volume 680cc, layer constitutes: the multilayer blow moulding bottle of (skin)/(adhesion resin)/(ethylene-vinyl acetate copolymer silicide)/(adhesion resin)/(resin combination that forms by broken resin and acrylic polymer)/(internal layer).
(embodiment 1)
From outside to inside, the cambium layer thickness rate is (density 0.90g/cc, MFR 9.0g/10min, propylene-ethylene random copolymers 95 weight % by ethylene contents 7mol%, ethylene contents is the resin combination layer that the hydropolymer 5 weight % of the styrene butadiene random copolymer of 10 weight % form)/(as the maleic anhydride modified polypropylene of adhesion resin layer)/(ethylene-vinyl acetate copolymer silicide layer)/(as the maleic anhydride modified polypropylene of adhesion resin layer)/(by 50 weight % are used for outer field propylene-ethylene random copolymers (density 0.90g/cc as the broken resin layer, MFR1.5g/10min, ethylene contents 5mol%) off gauge that produces during blow molding, the resin combination that broken resin 50 weight % that flash etc. obtain after grinding again form)/the laminated plastics bottle of (being used for outer field propylene-ethylene random copolymers)=20/2/3/2/63/10.
(embodiment 2)
Remove using styrene-content is that the hydropolymer of the styrene-ethylene base isoprene copolymer of 12 weight % mixes with the ratio of 5 weight %, as being mixed in outer field hydropolymer, replacing being used for beyond the hydropolymer of embodiment 1, other makes the laminated plastics bottle similarly to Example 1.
(embodiment 3)
Remove using styrene-content is that the hydropolymer of the styrene-butadiene block copolymer of 14 weight % mixes with the ratio of 5 weight %, as being mixed in outer field hydropolymer, replacing being used for beyond the hydropolymer of embodiment 1, other makes the multilayer plastic container bottle similarly to Example 1.
(comparative example 1)
Except that formed skin by the propylene-ethylene random copolymers 100 weight % that are used for embodiment 1, other makes the laminated plastics bottle similarly to Example 1.
For the laminated plastics bottle that is obtained by embodiment 1～3, comparative example 1, the evaluation result of its dropping impact strength, appearance characteristics, rigidity is as shown in table 1.
(evaluation method)
1. dropping impact strength
In the laminated plastics bottle, fill saturated aqueous common salt 650cc, take out after in the cold store of 5 ℃ or-5 ℃, keeping 24 hours, its height from 1.0m is fallen to mattess with erectility (the bottle end is downward), confirm damaged bottle number.Numeral in the table is represented in per 10 bottles of used each laminated plastics bottle, the maximum separately bottle number that falls the breakage after 10 times.
2. glossiness, the transparency
According to JIS K 7105, to each multilayer plastic container, glossiness is to use Japanese electric look industry system glossmeter VGS type to measure glossiness (glossiness of 60 ° of minute surfaces), and the transparency then is to use Japanese electric look industry system NDH1001 to measure mist degree (haze: mist degree).
3. rigidity
The laminated plastics bottle is left standstill with erectility, use ォ リ ェ Application テ ッ Network system TENSILON universal testing machine UCT-500, under the condition of compression speed 50mm/min, measure greatest compressive strength.
4. forming characteristics
Form the laminated plastics bottle by direct blow molding method, the range estimation bottle surface is confirmed.
[table 1]
| Dropping impact strength (5 ℃ of products temperatures) | Appearance characteristics | Rigidity kgf/cm 2 | Forming characteristics | ||
| Glossiness % | Mist degree % | ||||
| Embodiment 1 | ????0 | ????80 | ????36 | ????13.2 | ????○ |
| Embodiment 2 | ????0 | ????76 | ????38 | ????13.4 | ????○ |
| | ????0 | ????73 | ????39 | ????13.6 | ????○ |
| Comparative example 1 | ????10 | ????63 | ????35 | ????14.0 | ????○ |
(evaluation result)
Form each laminated plastics bottle outer field, that make by embodiment 1～3 by in the propylene-ethylene random copolymers, adding resin combination that hydropolymer forms, significantly do not reduce without detriment to forming characteristics and rigidity yet, and can improve dropping impact strength, glossiness, the transparency.
And the laminated plastics bottle in the outer comparative example 1 that does not add hydropolymer, in glossiness, not so good aspect transparent, particularly, aspect dropping impact strength, unfixed glassy the breaking of starting point of breaking again and again, 10 bottles all have breakage.
(embodiment 4)
Form the skin except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 1 respectively and styrene butadiene random copolymer mixes with the ratio of 99 weight %, 1 weight %, other makes the laminated plastics bottle similarly to Example 1.
(embodiment 5)
Form the skin except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 1 respectively and styrene butadiene random copolymer mixes with the ratio of 90 weight %, 10 weight %, other makes the laminated plastics bottle similarly to Example 1.
(embodiment 6)
Form the skin except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 1 respectively and styrene butadiene random copolymer mixes with the ratio of 80 weight %, 20 weight %, other makes the laminated plastics bottle similarly to Example 1.
(embodiment 7)
Form the skin except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 1 respectively and styrene butadiene random copolymer mixes with the ratio of 65 weight %, 35 weight %, other makes the laminated plastics bottle similarly to Example 1.
(comparative example 2)
Form the skin except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 1 respectively and styrene butadiene random copolymer mixes with the ratio of 60 weight %, 40 weight %, other makes the laminated plastics bottle similarly to Example 1.
(comparative example 3)
Form the skin except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 1 respectively and styrene butadiene random copolymer mixes with the ratio of 50 weight %, 50 weight %, other makes the laminated plastics bottle similarly to Example 1.
And the laminated plastics bottle that obtains by embodiment 4～7, comparative example 2～3, the evaluation result of its dropping impact strength, appearance characteristics, rigidity is as shown in table 2.
(evaluation result)
Each laminated plastics bottle that the resin combination that is formed by the hydropolymer of the styrene-butadiene block copolymer of propylene-ethylene random copolymers and 1～35 weight % forms is outer field, made by embodiment 4～7, forming characteristics, rigidity can be significantly do not reduced, and dropping impact strength, glossiness and the transparency can be improved.Add hydropolymer with the few additive about 1 weight % and can see significant effect, can think that this demonstrates the function similar to the nuclei of crystallization in some sense.If surpass 10 weight %, although strength under shock further increases, the possibility that also has surfaces of tacky, slickness to reduce is carried in order to realize normal conveyor line, is necessary to increase the lubrication prescription consumption.(embodiment 6,7)
On the other hand, in the combined amount by hydropolymer is in the laminated plastics bottle made of the comparative example 2 and 3 of 40 weight %, 50 weight %, rough surface directly will take place during blow molding in the rigidity of container not within the acceptable range, glossiness will take place thereupon, the transparency reduces.
[table 2]
| Dropping impact strength | Appearance characteristics | Rigidity kgf/cm 2 | Forming characteristics | |||
| 5 ℃ of products temperatures | Products temperature-5 ℃ | Glossiness % | Mist | |||
| Embodiment | ||||||
| 4 | ????0 | ????2 | ????72 | ????35 | ????13.6 | ????○ |
| Embodiment 5 | ????0 | ????0 | ????81 | ????37 | ????12.7 | ????○ |
| Embodiment 6 | ????0 | ????0 | ????81 | ????38 | ????11.8 | ????○ |
| Embodiment 7 | ????0 | ????0 | ????80 | ????39 | ????10.5 | ????○ |
| Comparative example 2 | ????0 | ????0 | ????60 | ????44 | ????7.6 | * rough surface |
| Comparative example 3 | ????0 | ????0 | ????57 | ????49 | ????5.4 | * rough surface |
The embodiment of the laminated plastics bottle of representing below that to be main stor(e)y (thickest layer) form for the resin combination that is mixed by acrylic polymer and hydropolymer.
(embodiment 8)
From outside to inside, the cambium layer thickness rate is (density 0.90g/cc, MFR 8.5/10min, the layer that the propylene-ethylene random copolymers of ethylene contents 8mol% forms)/(as the maleic anhydride modified polypropylene of adhesion resin layer)/(ethylene-vinyl acetate copolymer silicide layer)/(as the maleic anhydride modified polypropylene of adhesion resin layer)/(by being used for outer field propylene-ethylene random copolymers 45 weight %, the hydropolymer 5 weight % of the styrene butadiene random copolymer of styrene-content 10 weight %, and the main stor(e)y that mixes of broken resin 50 weight %)/the laminated plastics bottle of (being used for outer field propylene-ethylene random copolymers layer)=20/2/3/2/63/10.
(comparative example 4)
Remove by density 0.90g/cc, MFR is 8.5g/10min, and the resin that the propylene-ethylene random copolymers 70 weight % of ethylene contents 8mol% and broken resin 30 weight % mix forms beyond the main stor(e)y, and other makes the laminated plastics bottle similarly to Example 8.
And the laminated plastics bottle that obtains by embodiment 8 and comparative example 4, the evaluation result of its dropping impact strength, the transparency, rigidity is as shown in table 3.
[table 3]
| Dropping impact strength (5 ℃ of products temperatures) | Appearance characteristics | Rigidity kgf/cm 2 | Forming characteristics | ||
| Glossiness % | Mist degree % | ||||
| Embodiment 8 | ????0 | ????65 | ????30 | ????13.7 | ??○ |
| Comparative example 4 | ????4 | ????64 | ????36 | ????14.0 | ??○ |
(evaluation result)
Be mixed with the embodiment 8 of hydropolymer in the main stor(e)y,, and can improve dropping impact strength without detriment to appearance characteristics, rigidity, forming characteristics.On the other hand, by the laminated plastics bottle that the comparative example 4 of unmixed hydropolymer is made, its dropping impact strength is not within the acceptable range.
Then, to as the example that further improves dropping impact strength and glossiness, that is, and by acrylic polymer, hydropolymer and form outer field laminated plastics bottle as the composite that the mixed with resin of the ethylene-based polymer of the 3rd composition forms and narrate.
(embodiment 9)
Remove by the propylene-ethylene random copolymers 93 weight % that are used for embodiment 1, the hydropolymer 5 weight % of styrene butadiene random copolymer, and use the 1-hexene as comonomer, and be that resin combination that ethene-alpha-olefin copolymer (m-VLL) the 2 weight % of the aromatic ring alkene metal derivative series catalyzer to catalyse polymerization of 3.5g/10min, Mw/Mn=3.3 mix forms beyond the skin with density 0.898g/cc, MFR, other makes the laminated plastics bottle similarly to Example 1.
(embodiment 10)
The resin combination that mixes with the ratio of 85 weight %, 5 weight %, 10 weight % except that the hydropolymer of the propylene-ethylene random copolymers that will be used for embodiment 8 respectively, styrene butadiene random copolymer and m-VLL forms the skin, and other makes the laminated plastics bottle similarly to Example 1.
(embodiment 11)
Except that the hydropolymer and the ratio mixing formation skin of m-VLL with 65 weight %, 5 weight %, 30 weight % of the propylene-ethylene random copolymers that will be used for embodiment 8 respectively, styrene butadiene random copolymer, other makes the laminated plastics bottle similarly to Example 1.
And the laminated plastics bottle that obtains by embodiment 9～11, the evaluation result of its dropping impact strength, the transparency, rigidity is as shown in table 4.
[table 4]
| Dropping impact strength | Appearance characteristics | Forming characteristics | |||
| 5 ℃ of products temperatures | Products temperature-5 ℃ | Glossiness % | Transparency % | ||
| Embodiment 9 | ????0 | ????1 | ????82 | ????36 | ????○ |
| Embodiment 10 | ????0 | ????0 | ????83 | ????37 | ????○ |
| Embodiment 11 | ????0 | ????0 | ????83 | ????38 | ????○ |
In forming outer field resin combination, also be mixed with among the embodiment 9～11 of m-VLL that uses the polymerization of aromatic ring alkene metal derivative series catalyzer to catalyse as the 3rd composition, without detriment to the transparency, and the dropping impact strength and the glossiness of (5 ℃) can further improve low temperature the time.
(embodiment 12～16)
In the following embodiments, what represent is: by the hydropolymer in the multilayer plastic container being added in the outer field acrylic polymer resin, and at the many high resin of rigidity that uses of other propylene resin layer, thereby when keeping strength under shock, can also improve the example of container rigidity.
Use acrylic polymer resin (ethylene contents 7mol%, MFR is 10g/10min), hydropolymer (the styrene mol wt 1.5 ten thousand of styrene-butadiene block copolymer (SBS), styrene-content 30mol%) and density 0.900g/cc, MFR is that the resin combination that mixes by 90: 7: 3 weight % of the copolymer of the ethene-alpha-olefin of 4.0g/10min is as skin; Use maleic anhydride modified polypropylene (MFR is 4.0g/10min, and sour modification degree is 0.5 weight %) as the adhesion resin layer; Use ethylene-vinyl acetate copolymer silicide (EVOH) (ethylene contents 29mol%, MFR3.8g/10min (210 ℃)) as isolating resin bed; Use composite shown in the table 5 as the acrylic polymer resin of main stor(e)y and internal layer, thickness ratio with skin/adhesion resin layer/EVOH/ adhesion resin layer/main stor(e)y/internal layer=20/2/3/2/63/10, in main stor(e)y, add and reclaim resin 35 weight %, make multilayer plastic container 5 kinds 6 layers, internal volume 680ml, container weight 27g.The evaluating characteristics result of these bottles is as shown in table 6.And, in table 5,, stipulate ethylene contents with A for propylene-ethylene random copolymers and propylene-ethylene block copolymer.In addition, for ethene-alpha-olefin copolymer, stipulate density with A.
Shown in following table 6, can guarantee strength under shock at skin mixing hydropolymer, and, as being used for main stor(e)y or internal layer, particularly as the acrylic polymer that is used for main stor(e)y, the resin that the mixed crystallization heat of fusion is high, the resin that ethylene contents is low (embodiment 13), (embodiment 14 for the ethene-alpha-olefin copolymer that mixes with the acrylic polymer difficulty that perhaps is used to improve impact, 15), with the very high acrylic polymer of isotacticity is base material (embodiment 16), can obtain can not making basically reductions such as the transparency, and the bottle that the container rigidity is largely increased.
[table 5]
| Main stor(e)y A: ethylene contents (%), density (g/cm 3) B:MFR (g/10min) C: heat of fusion (J/g) | Internal layer A: ethylene contents (%), density (g/cm 3) B:MFR (g/10min) C: heat of fusion (J/g) | |
| Embodiment 12 | Propylene-ethylene random copolymers 95 weight % (A:5.0 B:1.0 C:68) ethene-alpha-olefin copolymer 5 weight % (A:0.905 B:4.0) | Propylene-ethylene random copolymers (A:7.0 B:1.0 C:64) |
| Embodiment 13 | Propylene-ethylene random copolymers 95 weight % (A:2.0 B:1.2 C:75) EP rubbers (EPR) 5 weight % | Propylene-ethylene random copolymers (A:5.0 B:1.0 C:68) |
| Embodiment 14 | Propylene-ethylene random copolymers 90 weight % (A:7.0 B:1.3 C:67) ethene-alpha-olefin copolymer 10 weight % (A:0.925 B:4.0) | Propylene-ethylene random copolymers 90 weight % (A:5.0 B:1.0 C:68) ethene-alpha-olefin copolymer 10 weight % (A:0.905 B:3.5) |
| Embodiment 15 | Propylene-ethylene random copolymers 90 weight % (A:2.0 B:1.2 C:130) ethene-alpha-olefin copolymer 10 weight % (A:0.907 B:4.0) | Propylene-ethylene random copolymers (A:5.0 B:1.0 C:68) |
| Embodiment 16 | Propylene-ethylene random copolymers 85 weight % (A:2.0 B:1.2 C:160) ethene-alpha-olefin copolymer 10 weight % (A:0.907 B:4.0) EP rubbers (EPR) 5 weight % | Propylene-ethylene random copolymers 90 weight % (A:5.0 B:1.0 C:68) ethene-alpha-olefin copolymer 10 weight % (A:0.905 B:3.5) |
[table 6]
| Dropping impact strength | Appearance characteristics | Rigidity kgf/cm 2 | |||
| 5 ℃ of products temperatures | Products temperature-5 ℃ | Glossiness % | Mist degree % | ||
| Embodiment 12 | ????0 | ????0 | ????84 | ????32 | ????15.2 |
| Embodiment 13 | ????0 | ????0 | ????83 | ????38 | ????14.9 |
| Embodiment 14 | ????0 | ????0 | ????85 | ????42 | ????16.2 |
| Embodiment 15 | ????0 | ????1 | ????86 | ????34 | ????16.6 |
| Embodiment 16 | ????0 | ????2 | ????83 | ????40 | ????16.0 |
(embodiment 17～19)
Here, use is at acrylic polymer resin (ethylene contents 7mol%, MFR is 10g/10min) in add resin combination that the hydropolymer (styrene mol wt 1.3 ten thousand, styrene-content 35mol%) of the styrene-isoprene block copolymer (SIS) of 3 weight % mixes as skin; Use MFR to be 4.0g/10min, sour modification degree is that the maleic anhydride modified polypropylene of 0.5 weight % is as the adhesion resin layer; Use ethylene-vinyl acetate copolymer silicide (EVOH) (ethylene contents 28mol%, MFR4.8g/10min (210 ℃)) as isolating resin bed; Use composite shown in the table 7 as the acrylic polymer resin of main stor(e)y and internal layer, thickness ratio with skin/adhesion resin layer/EVOH/ adhesion resin layer/main stor(e)y/internal layer=15/3/5/3/64/10, in main stor(e)y, add broken resin 40 weight %, make the cylindrical multi-layer plastic container of internal volume 680ml, container weight 27g.In addition, in embodiment 17, also add the hydropolymer of 5 weight % at internal layer, ectonexine uses and becomes 4 kinds of 6 layers of structures with a kind of resin-shaped, add 2,2 of 0.2 weight % '-methene two (4,6-two-t-butyl) sodium phosphate in the main stor(e)y in embodiment 18,19 or the acrylic polymer of internal layer as crystallization nucleating agent, to guarantee Dent resistance and rigidity, the resin that forms ectonexine is formed 5 kinds of different 6 layers of structures.With the bottle sealing, carry out decompression operation with vacuum pump by bottleneck, the degree of vacuum (mmHg) when measuring bottle portion generation moderate finite deformation is as an index of container rigidity.These results are as shown in table 8.In addition, in table 7,, stipulate ethylene contents with A for propylene-ethylene random copolymers and propylene-ethylene block copolymer.In addition, for ethene-alpha-olefin copolymer, stipulate density with A.
[table 7]
| Main stor(e)y A: ethylene contents (%), density (g/cm 3) B:MFR (g/10min) C: heat of fusion (J/g) | Internal layer A: ethylene contents (%), density (g/cm3) B:MFR (g/10min) C: heat of fusion (J/g) | |
| Embodiment 17 | Propylene-ethylene random copolymers 95 weight % (A:7.0 B:1.3 C:67) ethene-alpha-olefin copolymer 5 weight % (A:0.905 B:6.0) | Propylene-ethylene random copolymers 95 weight % (A:5.0 B:10 C:70) hydropolymer 5 weight % |
| Embodiment 18 | Propylene-ethylene random copolymers 95 weight % (A:7.0 B:1.3 C:67) EP rubbers (EPR) 5 weight % (A:0.905 B:6.0) | Propylene-ethylene random copolymers (A:5.0 B:1.0 C:68) |
| Embodiment 19 | Propylene-ethylene random copolymers 95 weight % (A:2.0 B:1.2 C:130) EP rubbers (EPR) 5 weight % | Propylene-ethylene random copolymers (A:5.0 B:1.0 C:68) |
Shown in following table 8, as acrylic polymer, by at the higher propylene-ethylene random copolymers of isotacticity (embodiment 18), perhaps aggregate into, be all to add crystallization nucleating agent under any situations of so-called propylene-ethylene block copolymer (embodiment 19), just can improve the container rigidity significantly by multistage polymerization.And adding effect as paying of crystallization nucleating agent, the strength under shock and the transparency also are improved.Hence one can see that, and of the present invention 5 kinds 6 layers structure can be brought into play above-mentioned composite effect most effectively.
[table 8]
| Dropping impact strength | Appearance characteristics | Rigidity kgf/cm 2? | Decompression distortion mmHg | |||
| 5 ℃ of products temperatures | Products temperature-5 ℃ | Glossiness % | Mist degree % | |||
| Embodiment 17 | ????0 | ????0 | ????67 | ????44 | ??19.2 | ????13.8 |
| Embodiment 18 | ????0 | ????0 | ????70 | ????38 | ??24.9 | ????16.7 |
| Embodiment 19 | ????0 | ????0 | ????72 | ????33 | ??26.2 | ????15.6 |
The effect of invention
By said structure, in the present invention, can obtain good forming ability, resistance to impact, the multilayer plastic container that vessel surface is glossy, the transparency is excellent. And, because in the present invention, can effectively utilize the broken resin that produces when making container, therefore can reduce manufacturing cost.
Claims (16)
1. multilayer plastic container is characterized by: at least 1 layer be by
With the acrylic polymer is matrix resin, and contains the resin combination formation of hydropolymer.
2. multilayer plastic container as claimed in claim 1 is characterized by: the layer that is formed by described resin combination is positioned at the skin of container.
3. multilayer plastic container as claimed in claim 1 is characterized by: the layer that is formed by described resin combination is the main stor(e)y of container.
4. as each described multilayer plastic container of claim 1～3, it is characterized by: the contained ratio of the hydropolymer in the described resin combination is 1～35 weight %.
5. as each described multilayer plastic container of claim 1～4, it is characterized by: described hydropolymer is the hydropolymer of the copolymer that formed by aromatic ethylene compound and the olefin compound with conjugated double bond.
6. as each described multilayer plastic container of claim 1～5, it is characterized by: described hydropolymer is the hydropolymer of the periodic copolymer that formed by aromatic ethylene compound and the olefin compound with conjugated double bond.
7. multilayer plastic container as claimed in claim 5 is characterized by: described aromatic vinyl based compound is a styrene, and described olefin compound with conjugated double bond is butadidenne and/or isoprene.
8. as each described multilayer plastic container of claim 1～7, it is characterized by: described acrylic polymer is to be that 2～15mol%, MFR are that propylene-alpha-olefin copolymers more than the 1.0g/10min, below the 15g/10min forms by polypropylene or alpha-olefin composition.
9. multilayer plastic container as claimed in claim 8 is characterized by: propylene-alpha-olefin copolymers is a random copolymers.
10. as each described multilayer plastic container of claim 1～9, it is characterized by: described resin combination also contains ethylene-based polymer.
11. multilayer plastic container as claimed in claim 10 is characterized by: described ethylene-based polymer is the low density polyethylene (LDPE) of polymerization by aromatic ring alkene metal derivative catalyst.
12. the described multilayer plastic container of each of claim 1～11 is characterized by: at least 1 layer acrylic polymer layer contains crystallization nucleating agent.
13. the described multilayer plastic container of claim 12 is characterized by: the crystallization heat of fusion of at least 1 layer acrylic polymer layer is 50～175J/g.
14., it is characterized by: by the skin that contains hydropolymer, adhesion resin layer, isolate resin bed, adhesion resin layer, acrylic polymer layer or contain acrylic polymer layer, the acrylic polymer internal layer that reclaims resin or the acrylic polymer internal layer that contains hydropolymer constitutes 4 kinds 6 layers or 5 kinds 6 layers as each described multilayer plastic container of claim 1～13.
15. as each described multilayer plastic container of claim 1～14, it is characterized by: have the isolation resin bed that is selected from ethylene-vinyl acetate copolymer silicide, polyamide, the cyclic olefin copolymer.
16. multilayer plastic container as claimed in claim 15 is characterized by: have and comprise and contain the recovery resin bed of isolating resin
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002345879A JP4694762B2 (en) | 2001-11-29 | 2002-11-28 | Multi-layer plastic container |
| JP2002345879 | 2002-11-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1504391A true CN1504391A (en) | 2004-06-16 |
| CN100503386C CN100503386C (en) | 2009-06-24 |
Family
ID=34260208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031407382A Expired - Lifetime CN100503386C (en) | 2002-11-28 | 2003-06-10 | Multiple layer plastic container |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100974492B1 (en) |
| CN (1) | CN100503386C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103459121A (en) * | 2011-04-01 | 2013-12-18 | 出光统一科技株式会社 | Method for producing transparent recycled sheet, and transparent recycled sheet |
| CN105151474A (en) * | 2015-09-17 | 2015-12-16 | 苏州新区佳合塑胶有限公司 | Convenient-to-stack plastic drum for water dispenser |
| CN109335270A (en) * | 2018-08-27 | 2019-02-15 | 浙江正庄实业有限公司 | Antiultraviolet antistatic emulsion pumps and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102019110210A1 (en) * | 2019-04-17 | 2020-10-22 | Kraiburg Tpe Gmbh & Co. Kg | Thermoplastic elastomer composition as an adhesive system for rubber based on crosslinked rubbers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05270570A (en) * | 1992-03-25 | 1993-10-19 | Toppan Printing Co Ltd | Packaging container for retort |
| JPH09109340A (en) * | 1995-10-13 | 1997-04-28 | Toppan Printing Co Ltd | Multilayer plastic container |
| JP3536698B2 (en) * | 1998-12-25 | 2004-06-14 | 東洋製罐株式会社 | Multilayer plastic container |
-
2003
- 2003-05-27 KR KR1020030033558A patent/KR100974492B1/en active IP Right Grant
- 2003-06-10 CN CNB031407382A patent/CN100503386C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103459121A (en) * | 2011-04-01 | 2013-12-18 | 出光统一科技株式会社 | Method for producing transparent recycled sheet, and transparent recycled sheet |
| CN105151474A (en) * | 2015-09-17 | 2015-12-16 | 苏州新区佳合塑胶有限公司 | Convenient-to-stack plastic drum for water dispenser |
| CN109335270A (en) * | 2018-08-27 | 2019-02-15 | 浙江正庄实业有限公司 | Antiultraviolet antistatic emulsion pumps and preparation method thereof |
| CN109335270B (en) * | 2018-08-27 | 2024-01-12 | 浙江正庄实业有限公司 | Ultraviolet-proof and antistatic emulsion pump and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040047527A (en) | 2004-06-05 |
| KR100974492B1 (en) | 2010-08-10 |
| CN100503386C (en) | 2009-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1088077C (en) | Resin composition and multilayered structure | |
| KR100906949B1 (en) | Resin composition and multi-layer structures | |
| EP0721481B1 (en) | Dispersible film | |
| WO2014024912A1 (en) | Modified ethylene-(vinyl alcohol) copolymer, method for producing same, and use of same | |
| EP2631270B1 (en) | Film comprising a poly-4-methyl-1-pentene based resin composition and laminated article | |
| CN1168773C (en) | Modified poly propylene composition and laminated material using said composition | |
| KR20130033362A (en) | Polyethylene resin molding material for container lid | |
| CN1823106A (en) | Injection moulding polymer | |
| CN1536019A (en) | Thermoplastic polymer composition, forming article and multilayer sturcture | |
| CN1128705C (en) | Coextrusion binder, its use in multilayer structure and structure thus obtained | |
| CN1138827C (en) | Ethylene-ethenol copolymer constituted resin composition with good adhesiveness between layers | |
| WO2014152662A1 (en) | Multilayered article comprising polypropylene impact copolymers, and method of making same | |
| CN1608841A (en) | Collation shrink | |
| JP4844852B2 (en) | Multi-layer stretched hollow body | |
| CN1946792A (en) | Polyolefin masterbatch and composition suitable for injection molding | |
| CN1200807C (en) | Method for producing foamed resin product and foamed resin product | |
| CN1684827A (en) | Laminated film for stretch packaging | |
| CN1720310A (en) | Release agent and release sheet | |
| CN1504391A (en) | Multiple layer plastic container | |
| JP3574500B2 (en) | Resin composition and multilayer structure | |
| CN1502655A (en) | Resin composition | |
| CN1174064C (en) | Co-extruding adhesive, use for multi-layer structure and the structure | |
| CN1208738A (en) | Propylene block copolymer | |
| CN101085848A (en) | Thermoplastic elastomer composition and laminated material | |
| CN1671791A (en) | Container formed from multimodal ethylene polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20090624 |
|
| CX01 | Expiry of patent term |