CN104002509A - Multilayer resin sheet for deep drawing molding, and molded container - Google Patents
Multilayer resin sheet for deep drawing molding, and molded container Download PDFInfo
- Publication number
- CN104002509A CN104002509A CN201310057159.2A CN201310057159A CN104002509A CN 104002509 A CN104002509 A CN 104002509A CN 201310057159 A CN201310057159 A CN 201310057159A CN 104002509 A CN104002509 A CN 104002509A
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- CN
- China
- Prior art keywords
- layer
- styrene resin
- deep drawing
- sheet material
- modified olefin
- 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.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 159
- 239000011347 resin Substances 0.000 title claims abstract description 159
- 238000000465 moulding Methods 0.000 title claims abstract description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 185
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 230000003746 surface roughness Effects 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 56
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 56
- 229920005601 base polymer Polymers 0.000 claims description 54
- 230000004888 barrier function Effects 0.000 claims description 30
- 238000003856 thermoforming Methods 0.000 claims description 13
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 abstract 2
- 238000010030 laminating Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 229920001577 copolymer Polymers 0.000 description 9
- 229920001169 thermoplastic Polymers 0.000 description 9
- 239000004416 thermosoftening plastic Substances 0.000 description 9
- 229920005669 high impact polystyrene Polymers 0.000 description 7
- 239000004797 high-impact polystyrene Substances 0.000 description 7
- -1 6-aminocaprolc acid Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004080 punching Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920000007 Nylon MXD6 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WVKHCAOZIFYQEG-ODZAUARKSA-N (z)-but-2-enedioic acid;ethene Chemical group C=C.OC(=O)\C=C/C(O)=O WVKHCAOZIFYQEG-ODZAUARKSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- VJHDPVWEDUCKRQ-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O.NCCCCCCCCCCCC(O)=O VJHDPVWEDUCKRQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004150 EU approved colour Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003354 Modic® Polymers 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a multilayer resin sheet for deep drawing molding, and a molded container, and concretely provides the multilayer resin sheet for deep drawing molding, and the molded container molded by using the multilayer resin sheet. The multilayer resin sheet for deep drawing molding has the advantages of thermal molding, rigidity and oxygen resistance, and easy endowing of the fracture to a thermal-molded groove, and when a deep-drawn container with a complex shape is molded, the container unlikely adheres to a heat source even high heat is endowed to the container. The multilayer resin sheet for deep drawing molding is formed by sequentially laminating a modified olefin polymer layer and a styrene resin layer on two sides of an oxygen resistant resin layer, the groove is formed on one side, the sum of the thickness of the modified olefin polymer layer and the thickness of the styrene resin layer at the one side is 40-350mum, and the surface roughness (Ra) of the styrene resin layer at one side is 0.1-5.0mum.
Description
Technical field
The present invention relates to multi-layer resinous sheet material and container molding that its moulding is formed for a kind of deep drawing moulding.
Background technology
Up to now, as the container of cold drink, fruit drink, fancy food etc., use the styrene resin of hot formability, excellent rigidity always.But, in recent years, multi-layer resinous sheet material and the laminated vessel consisting of it are popularized, described multi-layer resinous sheet material is using styrene resin layer as outermost layer, across adhesive linkages such as modified olefin resinoids, ethylene-vinyl alcohol copolymer resin layer is set therebetween and gives oxygen barrier, suppressed quality that the oxidation due to content causes decline (patent documentation 1).
In recent years, the case of manufacturing these containers by the filling of moulding, content, the coherent operations such as sealing of cladding material is also in increase.In patent documentation 2, propose lamination polystyrene resin layer and polyolefin resin layer, in the operation till forming final products, in the time of preventing punch process, produced the scheme of the multi-layer resinous sheet material of resin burr.
And then, a kind of scheme of multi-layer resinous sheet material is proposed in patent documentation 3, it has been solved because oxygen barrier resin has obdurability and has been caused the inadequate problem of fractureing property of groove after thermoforming by specific layer structure.
In addition, in recent years, complicated design shape, the container of deep drawing shape increase gradually, conventionally, while tackling such container shapes, need to when hot briquetting, to sheet material, give very large heat, thereby make the fully softening moulding of sheet material.But, the multi-layer resinous sheet material of recording in patent documentation 1 to 3, while adopting the direct mode of heating that thermal source contacts with sheet material, if raising hot plate temperature, so sheet surface likely with thermal source blocking under warming, existence cannot be for the problem of deep drawing moulding that need to be higher than hot plate temperature in the past.
Patent documentation 1: Japanese kokai publication hei 11-58619 communique
Patent documentation 2: TOHKEMY 2006-21409 communique
Patent documentation 3: No. 4758926 communique of Japan Patent
Summary of the invention
The present invention is In view of the foregoing and the invention proposing, its object is to provide a kind of have hot formability, rigidity, oxygen barrier, not only be easy to give fractureing property of the groove after thermoforming, and when being shaped to the container of complicated shape, deep drawing, even if give high heat, be also difficult for and multi-layer resinous sheet material and container molding that its moulding is formed for the deep drawing moulding of thermal source blocking under warming.
; the inventor is in order to develop the multi-layer resinous sheet material that has described characteristic and be suitable for deep drawing moulding; after further investigation, find: by the two sides at oxygen barrier resin bed, across modified olefin base polymer, press layer by layer in the multi-layer resinous sheet material that styrene resin layer forms; carry out the adjustment of the modified olefin base polymer layer of groove formation face one side and the adjustment of the thickness of styrene resin layer and the surface roughness (Ra) of the styrene resin layer that groove forms face one side simultaneously; can solve described problem, thereby complete the present invention.
Therefore, according to a scheme of the present invention, provide a kind of deep drawing moulding multi-layer resinous sheet material, by the two sides at oxygen barrier resin bed, across modified olefin base polymer, press layer by layer styrene resin layer to form, from one side side, form groove, it is characterized in that, the summation of the described modified olefin base polymer layer of described one side side and the thickness of described styrene resin layer is 40 to 350 μ m, and the surface roughness of the one side of described styrene resin layer (Ra) is 0.1 to 5.0 μ m.
In foregoing, in an embodiment of invention, oxygen barrier resin bed consists of ethylene-vinyl alcohol copolymer resin.In one embodiment, the thickness of modified olefin base polymer layer is 10 to 50 μ m.In one embodiment, the thickness of oxygen barrier resin bed is 10 to 50 μ m.In one embodiment, styrene resin layer consists of the styrene resin of the butadiene rubber composition that contains 4 to 8 quality %.In one embodiment, multi-layer resinous sheet material has the thickness of 500 to 1200 μ m.
In addition, by other schemes of the present invention, provide a kind of container molding, it is characterized in that, deep drawing moulding forms with multi-layer resinous sheet material described in thermoforming, has the described groove forming from one side side.
The multi-layer resinous sheet material of deep drawing moulding of the present invention, when thering is hot formability, rigidity, oxygen barrier, give fractureing property of the groove after thermoforming, even if give very large heat when hot briquetting, be also difficult for and thermal source blocking under warming, so can easily be shaped to more complicated shape or the container of deep drawing.
Accompanying drawing explanation
Fig. 1 means the longitudinal side generalized section of the laminar construction of multi-layer resinous sheet material for high heat hot briquetting in one embodiment of the present invention.
Fig. 2 means the schematic perspective view of an example of container molding of the present invention.
Fig. 3 means the side schematic view of an example of container molding of the present invention.
Fig. 4 is for the schematic diagram of the stamping procedure of container is described.
description of reference numerals
1 groove, 2 overbending directions, 3 off-positions, 4 direct of travels.
The specific embodiment
Deep drawing moulding in an embodiment of the invention is a kind of thermoplastic multilayer resin sheet with multi-layer resinous sheet material, as shown in Figure 1, by the two sides in oxygen barrier resin bed (10), across modified olefin base polymer layer (11a, 11b) lamination styrene resin layer (12a, 12b) forms.From the one side side of this resin sheet (Fig. 1, the styrene resin layer 12a side of top) form groove, the modified olefin base polymer layer (11a) of this one side side is 40 to 350 μ m with the summation of the thickness of styrene resin layer (12a), and the surface roughness (Ra) that forms the face of exposing of styrene resin layer (12a) is 0.1 to 5.0 μ m.
At this, " deep drawing moulding is used " refers to that sheet material has the characteristic that is suitable for deep drawing moulding, deep drawing is defined as, shape regardless of container molding, the ratio of the degree of depth of container molding and width (if its shape has a plurality of width, selecting so Breadth Maximum), be that pull and stretch ratio is more than 0.5.At this, deep drawing container molding is, this pull and stretch ratio is more than 0.5, preferably more than 0.9, and further preferably more than 1, more than 1.5 container most preferably.
Below, describe above-mentioned thermoplastic multilayer resin sheet and this resin sheet of moulding in detail and the container molding manufactured.
< oxygen barrier resin bed (10) >
As the oxygen barrier resin that forms oxygen barrier resin bed, such as listing, take the material that ethylene-vinyl alcohol copolymer resin, polyamide etc. are representative.Wherein, consider processability, mouldability, optimal ethylene-vinyl alcohol copolymer resin.
Ethylene-vinyl alcohol copolymer resin is generally the material that ethylene-vinyl acetate copolymer saponification is obtained, in order to make it have oxygen barrier, processability, mouldability, ethylene contents is 10 to 65 % by mole, preferably 20 to 50 % by mole, saponification degree is more than 90%, preferably more than 95%.
In addition, as polyamide, can list: the lactam polymers such as caprolactam, lauric lactam; The polymer of the amino carboxylic acids such as 6-aminocaprolc acid, the amino hendecanoic acid of 11-, 12 amino dodecanoic acid; Hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4-or 2,4, the aliphatic diamines, 1 such as 4-trimethylhexamethylenediamine, the condensation polymer of the dicarboxylic acid units such as aromatic dicarboxylic acid such as ester ring type dicarboxylic acids, terephthalic acid (TPA), M-phthalic acid such as aliphatic dicarboxylic acid, cyclohexane dicarboxylic acid such as two amine units such as the aromatic diamines such as ester ring type diamines, m-or p-benzene dimethylamine such as 3-or Isosorbide-5-Nitrae-bis-(aminomethyl) cyclohexane, bis(p-aminocyclohexyl)methane and adipic acid, suberic acid, decanedioic acid; And their copolymer etc.
As polyamide, particularly, there are nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, NYLON610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD 6, nylon 6/66, nylon 6/610, nylon 6/6T, nylon 6I/6T etc., wherein, preferred nylon 6, nylon MXD 6.
The thickness of oxygen barrier resin bed, preferably 10 to 50 μ m, more preferably 20 to 40 μ m.If less than 10 μ m, so likely cannot obtain suppressing the oxygen resistance that quality that the oxidation due to the content of container molding causes reduces degree, in addition, if surpass 50 μ m, so likely when the punching press of thermoformed containers, produce resin burr or fractureing property of groove is insufficient.
< modified olefin base polymer layer (11a, 11b) >
Modified olefin base polymer as forming modified olefin base polymer layer, as representative species, can list, by ethene, propylene, the carbon numbers such as 1-butylene are the homopolymers of the alkene of 2 to 8 left and right, these alkene and ethene, propylene, 1-butylene, 3-methyl-1-butene, amylene-1, 4-methylpentene-1, hexene-1, octene-1, the carbon numbers such as decylene-1 are other alkene of 2 to 20 left and right, vinylacetate, vinyl chloride, acrylic acid, methacrylic acid, acrylate, methacrylate, the olefine kind resins such as copolymer of the vinyl compounds such as styrene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethene-butene-1 copolymer, the olefin rubbers such as propene-1-butene copolymer, pass through acrylic acid, methacrylic acid, crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, the unsaturated carboxylic acids such as tetrahydrophthalic acid or its sour halide, acid amides, imines, acid anhydrides, the derivatives such as ester, particularly, Malaysia acyl chlorides, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, maleic acid ethylene oxidic esters etc. carry out modification and the material that forms under graft reaction condition.
As modified olefin base polymer, wherein, preferably, vinyl resins, propylene resin or the ethylene-propylene or the butene-1 copolymer rubber that use unsaturated dicarboxylic or its acid anhydrides, especially maleic acid or its acid anhydrides to carry out modification.
The thickness of modified olefin base polymer layer, either side is preferred 10 to 50 μ m all, further preferred 20 to 40 μ m.If less than 10 μ m, so likely cannot obtain sufficient layers cementing intensity, in addition, if surpass 50 μ m, so likely when thermoformed containers punching press, produce resin burr, or fractureing property of groove is insufficient.
< styrene resin layer (12a, 12b) >
As the styrene resin that forms styrene resin layer, can list: styrene, AMS, p-methylstyrene, dimethyl styrene, p-tert-butylstyrene, the homopolymers of the styrene monomers such as chlorostyrene or copolymer, the copolymer of these styrene monomers and other monomers, SAN (AS resin) for example, or, described styrene monomer and other polymer, polybutadiene for example, SB, polyisoprene, the graft polymers that carries out glycerol polymerization under the existence of the polydiene matter polymer such as polychloroprene, HTPS (HIPS resin) for example, styrene-acrylonitrile graft polymers (ABS resin) etc.
As styrene resin, wherein, from the rigidity of container molding, the viewpoint of mouldability consider, preferably polystyrene (GPPS resin), HTPS (HIPS resin).
Styrene resin, preferably contains the butadiene rubber composition of 4 to 8 quality %.Butadiene rubber component content is a kind of simple method by GPPS with adjusting mixing of HIPS, but also can adjust in the fabrication stage of HIPS.If less than 4 quality %, so likely cannot obtain in practical vessel strength fully, if surpass 8 quality %, so likely when thermoforming, cause the problems such as adhesion hot plate.
In styrene resin layer, can as required, in not damaging the scope of effect of the present invention, add as colouring agents such as pigment, dyestuffs; The releasing agents such as silicone oil, alkane ester class; Fibee reinforced dose of glass fibre etc.; Talcum, clay, silica equigranular lubricant; Antistatic additive and the ultra-violet absorbers such as the salt compound of sulfonic acid and alkali metal etc., PAG; The additives such as antiseptic.In addition, also can mix and use the waste material resin producing in the manufacturing process of multi-layer resinous sheet material of the present invention, container molding.
As the thickness of styrene resin layer (12a) that forms face one side of groove, preferred 30 to 300 μ m, further preferred 100 to 200 μ m.If less than 30 μ m, while stretching through thermoforming so, likely cause styrene resin fault rupture, expose modified olefin base polymer layer, destroy the lettering correctness of vessel surface.In addition, if surpass 300 μ m, while forming groove so, need to increase the insertion depth of blade, likely reduce retention and the vessel strength of container shapes.
As the thickness of styrene resin layer (12b) that does not form face one side of groove, preferred 300 to 800 μ m, further preferred 400 to 700 μ m.If less than 300 μ m, so likely cause the rigidity of the container that thermoforming obtains insufficient, if surpass 800 μ m, so likely reduce the fractureing property of groove forming after groove.
The surperficial surface roughness (Ra) of exposing of the styrene resin layer (12a) of face one side of formation groove forms 0.1 to 5.0 μ m, and being preferably formed is 0.5 to 3.0 μ m.If less than 0.1 μ m, while so likely causing hot briquetting resin bed easily with thermal source blocking under warming, if surpass 5.0 μ m, so likely cause the products formed obtaining to lose lustrous surface, reduction commodity value.
The surperficial surface roughness (Ra) of exposing of styrene resin layer (12b) that does not form face one side of groove is not particularly limited, but in order not cause the reduction of commodity value, preferably less than 0.1 μ m.
Multi-layer resinous sheet material > for the moulding of < deep drawing
The deep drawing moulding that an embodiment of the invention are relevant forms with the layer of thermoplastic multilayer resin sheet, as previously mentioned, for styrene resin layer/modified olefin base polymer layer/oxygen barrier resin bed/modified olefin base polymer layer/styrene resin layer, in addition, for example, the layer of the waste material resin producing in the manufacturing process at multi-layer resinous sheet material of the present invention, container molding etc. can also be laminated to a contrary side that forms groove.
The deep drawing moulding thermoplastic multilayer resin sheet that an embodiment of the invention are relevant, forming the modified olefin base polymer layer (11a) of face one side of groove and the summation of the thickness of styrene resin layer (12a) is 40 to 350 μ m, preferably 120 to 240 μ m.If less than 40 μ m, form the relative attenuation of thickness of styrene resin layer of face one side of groove so, while stretching through thermoforming, styrene resin fault rupture, the outward appearance of likely damaging container and intensity etc.In addition, if surpass 350 μ m, it is large that the blade insertion depth while needing to make to form groove so becomes, and likely reduces retention and the vessel strength of container shapes.
The thickness of thermoplastic multilayer resin sheet for deep drawing moulding, preferred 500 to 1200 μ m, further preferred 700 to 1000 μ m.If less than 500 μ m, so likely cause the intensity of the container that thermoforming obtains insufficient, if surpass 1200 μ m, likely cause the manufacturing cost of container to uprise.
The forming method of thermoplastic multilayer resin sheet for deep drawing moulding, is not particularly limited, and can adopt conventional method.For example can list and use 4 or 4 above single screw extrusion machines, melt extrude material resin separately, by feed sleeve pipe and T-shaped mould, obtain the method for multi-layer resinous sheet material; Use many menifolds mould to obtain the method for multi-layer resinous sheet material.
As to the styrene resin layer in thermoplastic multilayer resin sheet for deep drawing moulding of the present invention, especially to having formed the surface of exposing of styrene resin layer (12a) of face one side of groove, give the method for the surface roughness of regulation, be not particularly limited, can adopt conventional method.For example can list, while picking up molten resin, use roll, the wheel of having implemented in advance concavo-convex processing to bring the method for picking up.
< container molding >
Fig. 2 and Fig. 3 represent an example of container molding of the present invention.
Container molding of the present invention, forms by thermoforming thermoplastic multilayer resin sheet of the present invention.As thermoforming process, can list general vacuum forming, press empty moulding, and as the application of these methods, make the one side of sheet material contact the chock plug auxiliary law that carries out moulding with chock plug; In addition, the two sides that makes sheet material with become that a pair of former formpiston contacts and method moulding, so-called matched mold (match mold) moulding etc., but be not limited to these methods.In addition, as making the thermoplastic method of sheet material before moulding, the radiation heating of the applicable infrared heater that utilizes noncontact heating etc. etc., known sheet material heating means.
Forming temperature during thermoforming, can suitably set according to the fusing point of resin etc., uses the relevant resin sheet of the present invention, carries out pull and stretch when being more than 0.5 deep drawing moulding, and hot plate temperature is set as more than 170 ℃, is preferably set to 175 to 180 ℃.If 170 ℃ of hot plate temperature less thaies, so because underheat causes the excipient state of container insufficient, if too high, so likely cause and the problems such as hot plate blocking under warming, so not good.
In addition, container molding of the present invention has groove.The section of the groove shape that is in the shape of the letter V, in one side side, the summation of the thickness of modified olefin base polymer layer and styrene resin layer is in a side of 50 to 400 μ m, can heat by hot plate mode etc., then by inserting the blade of V-shape, forms.
Embodiment
Below, by enumerating embodiment and comparative example is described more specifically the present invention, but the present invention is not subject to the restriction of the contents such as embodiment.
The resin raw material using in embodiment is as described below.
(1) oxygen barrier resin bed
Ethylene-vinyl alcohol copolymer " EVAL J-102B " (Kuraray (Co., Ltd.) is manufactured, ethylene contents 32mol%, saponification degree is more than 99%)
(2) modified olefin base polymer layer
" MODIC F502 " (Mitsubishi chemical Co., Ltd's manufacture)
(3) styrene resin layer
HIPS resin: " TOYOSTYROL H850 " (TOYO STYRENE Co., Ltd. manufactures, butadiene content 9.0 quality %)
GPPS resin: " HRM23 " (TOYO STYRENE Co., Ltd. manufactures)
< embodiment 1 >
Use 2 40mm single screw extrusion machines and 1 65mm single screw extrusion machine, by feed tiretube process, obtain following multi-layer resinous sheet material: its layer with styrene resin layer (12a) 165 μ m/ modified olefin base polymer layer (11a) 35 μ m/ oxygen barrier resin bed (10) 15 μ m/ modified olefin base polymer layer (11b) 35 μ m/ styrene resin layer (12b) 650 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 200 μ m with the gross thickness of modified olefin base polymer layer (11a)), to picking up roll, to have implemented surface roughness (Ra) be the metal roller of the concavo-convex processing of 0.5 μ m in use, the surface roughness (Ra) that obtains styrene resin layer (12a) is the multi-layer resinous sheet material of 0.23 μ m.
< embodiment 2 >
Use the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 40 μ m/ modified olefin base polymer layer (11a) 20 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 20 μ m/ styrene resin layer (12b) 800 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 60 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.25 μ m.
< embodiment 3 >
Use the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 285 μ m/ modified olefin base polymer layer (11a) 15 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 15 μ m/ styrene resin layer (12b) 665 μ m forms, thickness is that 1000 μ m(styrene resin layers (12a) are 300 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.30 μ m.
< embodiment 4 >
Use the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 30 μ m/ modified olefin base polymer layer (11a) 15 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 15 μ m/ styrene resin layer (12b) 820 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 45 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.33 μ m.
< embodiment 5 >
Use the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 325 μ m/ modified olefin base polymer layer (11a) 15 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 15 μ m/ styrene resin layer (12b) 525 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 340 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.28 μ m.
< embodiment 6 >
It is the metal roller of the concavo-convex processing of 0.3 μ m that surface roughness (Ra) has been implemented in use, in addition, utilize the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 165 μ m/ modified olefin base polymer layer (11a) 20 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 20 μ m/ styrene resin layer (12b) 675 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 185 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.15 μ m.
< embodiment 7 to 9 >
Use has been implemented surface roughness (Ra) and has been respectively 2, 5, the metal roller of the concavo-convex processing of 10 μ m, in addition, utilize the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 165 μ m/ modified olefin base polymer layer (11a) 35 μ m/ oxygen barrier resin bed (10) 15 μ m/ modified olefin base polymer layer (11b) 35 μ m/ styrene resin layer (12b) 650 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 200 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is respectively 0.95, 2.40, 4.70 μ m.
< comparative example 1 >
Utilize the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 15 μ m/ modified olefin base polymer layer (11a) 15 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 15 μ m/ styrene resin layer (12b) 835 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 30 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.35 μ m.
< comparative example 2 >
Utilize the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 360 μ m/ modified olefin base polymer layer (11a) 15 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 15 μ m/ styrene resin layer (12b) 490 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 375 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is 0.28 μ m.
< comparative example 3 to 6 >
Use has been implemented surface roughness (Ra) and has been respectively 0.1, 0.2, 12, the metal roller of the concavo-convex processing of 15 μ m, in addition, utilize the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 165 μ m/ modified olefin base polymer layer (11a) 35 μ m/ oxygen barrier resin bed (10) 15 μ m/ modified olefin base polymer layer (11b) 35 μ m/ styrene resin layer (12b) 650 μ m forms, thickness is that 900 μ m(styrene resin layers (12a) are 200 μ m with the gross thickness of modified olefin base polymer layer (11a)), the surface roughness (Ra) of styrene resin layer (12a) is respectively 0.04, 0.07, 5.65, 7.60 μ m.
< comparative example 7 >
Utilize the method identical with embodiment 1, obtain following multi-layer resinous sheet material: the layer with styrene resin layer (12a) 570 μ m/ modified olefin base polymer layer (11a) 30 μ m/ oxygen barrier resin bed (10) 20 μ m/ modified olefin base polymer layer (11b) 20 μ m/ styrene resin layer (12b) 360 μ m forms, thickness is that 1000 μ m(styrene resin layers (12a) are 600 μ m with the gross thickness of modified olefin base polymer layer (11a)), additive method is identical with embodiment 1.
And, as styrene resin, use HIPS resin and GPPS resin according to mass ratio 80/20(HIPS/GPPS) and resin (the butadiene rubber component content: 7.2 quality %) that mixes.
Under the following conditions, by this multi-layer resinous sheet material, with moulding, groove formation, container punching press (Fig. 4) series of processes, process, obtain the container shown in Fig. 2.And, about groove, from styrene resin layer 12a mono-side, forming, the degree of depth of groove is adjusted according to the heating-up temperature of groove forming section.
Use machine: CFF-300(CKD Co., Ltd. manufactures)
Upper hot plate temperature: 170 ℃
Lower hot plate temperature: 170 ℃
Groove part heating-up temperature: 160 ℃
Depth of groove: 350 μ m
Container punching press sword upside structure: outside
Container punching press sword downside structure: inner edge
Gap between the upside downside of container punching press sword: 20 μ m
The multi-layer resinous sheet material obtaining and the various evaluations of container are carried out according to following method.Result is as shown in table 1.
(1) surface roughness (Ra)
Measure by the following method the surface roughness (Ra) of sheet material, according to following benchmark, evaluate.
［ assay method ］ is according to JIS B0601 method
Use machine: Tokyo Precision Co., Ltd manufactures SURFCOM120A
(2) completed state
By following benchmark, the mouldability while evaluating thermoformed containers.
Zero: good forming ability
*: find that the moulding causing due to hot plate adhesion is bad, the destruction of superficial layer.
(3) fractureing property of groove
By groove forming section, to the bending of bending direction shown in Fig. 3, by following benchmark, evaluate.
Zero: once bending just can be ruptured.
△: repeatedly bending just can be ruptured.
*: repeatedly bending also cannot be ruptured.
(4) lustrous surface of container
Measure the lustrous surface of the bottom surface sections of container molding.
［ evaluation method ］
Assay method: according to JIS K7105 method
Use machine: Japanese electricity Se Co., Ltd. manufactures digital Grossmeters
［ metewand ］
Zero: glossiness is more than 20%
*: glossiness less than 20%
(5) synthetic determination
Above-mentioned whole evaluation result is zero, and synthetic determination is zero, be in addition *.
Table 1
Claims (7)
1. the multi-layer resinous sheet material of deep drawing moulding, by the two sides at oxygen barrier resin bed, across modified olefin base polymer, press layer by layer styrene resin layer to form, from one side side, form groove, it is characterized in that, the summation of the described modified olefin base polymer layer of described one side side and the thickness of described styrene resin layer is 40 to 350 μ m, and the surface roughness Ra of the one side of described styrene resin layer is 0.1 to 5.0 μ m.
2. the multi-layer resinous sheet material of deep drawing moulding according to claim 1, is characterized in that, described oxygen barrier resin bed consists of ethylene-vinyl alcohol copolymer resin.
3. the multi-layer resinous sheet material of deep drawing moulding according to claim 1 and 2, is characterized in that, the thickness of described modified olefin base polymer layer is 10 to 50 μ m.
4. according to the multi-layer resinous sheet material of deep drawing moulding described in any one in claims 1 to 3, it is characterized in that, the thickness of described oxygen barrier resin bed is 10 to 50 μ m.
5. according to the multi-layer resinous sheet material of deep drawing moulding described in any one in claim 1 to 4, it is characterized in that, described styrene resin layer consists of the styrene resin of the butadiene rubber composition that contains 4 to 8 quality %.
6. according to the multi-layer resinous sheet material of deep drawing moulding described in any one in claim 1 to 5, it is characterized in that, thickness is 500 to 1200 μ m.
7. a container molding, is characterized in that, the deep drawing moulding in thermoforming claim 1 to 6 described in any one forms with multi-layer resinous sheet material, has the described groove forming from one side side.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010135269.6A CN111469497A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing and molded container |
| CN201310057159.2A CN104002509A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing molding, and molded container |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310057159.2A CN104002509A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing molding, and molded container |
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| CN202010135269.6A Division CN111469497A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing and molded container |
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| CN106273953A (en) * | 2015-05-14 | 2017-01-04 | 电气化学工业株式会社 | Multi-layer resinous thin film and container molding |
| CN106273952A (en) * | 2015-05-14 | 2017-01-04 | 电气化学工业株式会社 | Multi-layer resinous thin film and container molding |
| CN107428145A (en) * | 2015-04-08 | 2017-12-01 | 电化株式会社 | Thermoplastic multilayer resin sheet and the container using the thermoplastic multilayer resin sheet |
| CN112895644A (en) * | 2019-12-03 | 2021-06-04 | 电化株式会社 | Multilayer resin sheet and molded container |
| TWI736536B (en) * | 2016-06-21 | 2021-08-21 | 日商電化股份有限公司 | Multilayer resin film and molded container |
| CN112895644B (en) * | 2019-12-03 | 2024-11-08 | 电化株式会社 | Multilayer resin sheet and molded container |
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| CN106273953A (en) * | 2015-05-14 | 2017-01-04 | 电气化学工业株式会社 | Multi-layer resinous thin film and container molding |
| CN106273952A (en) * | 2015-05-14 | 2017-01-04 | 电气化学工业株式会社 | Multi-layer resinous thin film and container molding |
| TWI736536B (en) * | 2016-06-21 | 2021-08-21 | 日商電化股份有限公司 | Multilayer resin film and molded container |
| CN112895644A (en) * | 2019-12-03 | 2021-06-04 | 电化株式会社 | Multilayer resin sheet and molded container |
| CN112895644B (en) * | 2019-12-03 | 2024-11-08 | 电化株式会社 | Multilayer resin sheet and molded container |
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| CN111469497A (en) | 2020-07-31 |
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