CN100513468C - Polyolefin resin foam and manufacturing method thereof - Google Patents
Polyolefin resin foam and manufacturing method thereof Download PDFInfo
- Publication number
- CN100513468C CN100513468C CNB2005100040230A CN200510004023A CN100513468C CN 100513468 C CN100513468 C CN 100513468C CN B2005100040230 A CNB2005100040230 A CN B2005100040230A CN 200510004023 A CN200510004023 A CN 200510004023A CN 100513468 C CN100513468 C CN 100513468C
- Authority
- CN
- China
- Prior art keywords
- polyolefin resin
- foam
- antistatic agent
- weight parts
- resin
- 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.)
- Active
Links
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000006260 foam Substances 0.000 title claims description 178
- 239000002216 antistatic agent Substances 0.000 claims abstract description 120
- 229920005989 resin Polymers 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 53
- 238000005187 foaming Methods 0.000 claims description 38
- 230000004927 fusion Effects 0.000 claims description 30
- 239000000155 melt Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229920000098 polyolefin Polymers 0.000 claims description 26
- 239000004925 Acrylic resin Substances 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 23
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 abstract description 122
- 239000000463 material Substances 0.000 abstract description 33
- 239000005022 packaging material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 229920000570 polyether Polymers 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 238000007664 blowing Methods 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 229920001684 low density polyethylene Polymers 0.000 description 16
- 239000004702 low-density polyethylene Substances 0.000 description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 12
- -1 glycerol fatty acid ester Chemical class 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000003475 lamination Methods 0.000 description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001477 hydrophilic polymer Polymers 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 6
- 235000013844 butane Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000003856 thermoforming Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) 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
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-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
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 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
- 238000001149 thermolysis Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/86—Antistatics
Abstract
The present invention provides a manufacturing method of a polyolefin resin foamed body which, when used as a packaging material, has least possibility of contaminating the surface of a contacting material, which excels in appearance and which shows antistatic characteristics uniform over the entire surface, and provides the polyolefin resin foamed body. The present invention comprises a specific mount of a polymer type antistatic agent whose apparent density may be 15 to 65 g/L, whose specific surface inherent resistance rate is 1 X 108 to 1 X 1013 (ohm), and whose average foamed body diameter meets a specific relationship.
Description
Technical field
The present invention relates to a kind of polyolefin resin foam and manufacture method thereof, particularly relate to chargeding performance excellence, polyolefin resin foam and manufacture method thereof that apparent density is low with antistatic performance.
Background technology
The foam of existing polyolefin resin system is owing to be rich in flexibility and resiliency, makes packaged body be difficult to breakage and is widely used as cushioning material, wrapping material.Particularly polyvinyl resin system foam is owing to height foaming easily, low price manufacturing are widely used.But this foam is owing to have because of the electrostatic interaction undesirable property of dust suction very easily, has the polyolefin resin foam that improves the antistatic performance of electroconductibility with antistatic agent and is developed application gradually.
As the means of giving above-mentioned antistatic performance, the surfactant type antistatic agent is widely used owing to can cheapness buying.As the surfactant type antistatic agent, for example can listing, the spy opens the described glycerol fatty acid ester of flat 9-169072 communique, poly-oxyethylene alkyl ammonia, alkyl diglycollic amide etc.
But the anti-static effect of surfactant type antistatic agent is to be exuded to the surface by antistatic agent from resin, and the moisture in the absorbed air manifests.Therefore the surfactant type antistatic agent has the problem that anti-static effect is difficult to manifest under the lower environment of humidity.On the other hand, in the higher environment of humidity,, shift to packaged body, make phenomenons such as packaged surface becomes sticky, whiting, cause the scope of the pollution of packaged surface owing to absorb the antistatic agent of moisture though anti-static effect manifests.
Summary of the invention
The present invention produces in view of the above problems.The purpose of this invention is to provide when using as wrapping material, the possibility of polluting the contact object surface is low, outward appearance is excellent, be subjected to humidity effect little, can stablize and good polyolefin resin foam that manifests antistatic performance and manufacture method thereof.
People of the present invention, as the purpose that addresses the above problem, test is supplied with polymer antistatic agent and polyolefin resin to make foam to forcing machine.At this moment, the apparent density of foam is made as particular value, uses specific polyolefin resin foam and polymer antistatic agent, even the unexpected usage quantity of polymer antistatic agent of finding is for also having found antistatic performance on a small quantity.That is, the invention provides a kind of good polyolefin resin foam and manufacture method thereof of antistatic performance as follows.
[1] a kind of polyolefin resin foam, it is characterized in that, with respect to polyolefin resin 100 weight parts, the number-average molecular weight that contains 2～12 weight parts is 2000～100000 polymer antistatic agent, apparent density is 15～65g/L, and the surperficial intrinsic resistance rate after the use alcoholic acid ultrasonic cleaning is 1 * 10
8～1 * 10
13(Ω), average bubble directly satisfies following (1), (2) and (3) formula.
0.35≦Z/X≦1.2?...(1)
0.35≦Z/Y≦1.2?...(2)
0.2≦Z≦1.4 ...(3)
(wherein, X, Y and Z are respectively: the average bubble footpath of extruding direction: X (mm), the average bubble footpath of width: the average bubble footpath of Y (mm) and thickness direction: Z (mm).)
As above-mentioned [1] described polyolefin resin foam, it is characterized in that [2] with respect to polyolefin resin 100 weight parts, the content of the polymer antistatic agent in the polyolefin resin foam is 2～11 weight parts.
As above-mentioned [1] described polyolefin resin foam, it is characterized in that [3] with respect to polyolefin resin 100 weight parts, the content of the polymer antistatic agent in the polyolefin resin foam is 2～9 weight parts.
[4] as the manufacture method of above-mentioned [1] described polyolefin resin foam, be with polyolefin resin, number-average molecular weight be 2000～100000 polymer antistatic agent, bubble adjust agent and pneumatogen mixing in forcing machine, form foaminess polyolefin resin melts, the manufacture method of the polyolefin resin foam of this foaminess polyolefin resin melts of extrusion foaming; It is characterized in that,
The addition of above-mentioned polymer antistatic agent is 2～14 weight parts with respect to polyolefin resin 100 weight parts;
The Tc of above-mentioned polymer antistatic agent is below 110 ℃;
The mensuration temperature of said polyolefins resin is that 190 ℃, velocity of shear are 100 seconds
-1The time the melt viscosity Ma (Pas) and the mensuration temperature of above-mentioned polymer antistatic agent be that 190 ℃, velocity of shear are 100 seconds
-1The time the relation of melt viscosity Mb (Pas) satisfy following (4) and (5) formula:
Ma>Mb (4)
80Pa·s≤Mb≤1000Pa·s (5)
As the manufacture method of above-mentioned [4] described polyolefin resin foam, it is characterized in that [5] polyolefin resin is that the fusion tension force under 190 ℃ is the polyvinyl resin of 30～400mN.
As the manufacture method of above-mentioned [4] described polyolefin resin foam, it is characterized in that [6] polyolefin resin is that the fusion tension force under 230 ℃ is the acrylic resin of 30～400mN.
[1] of the present invention described polyolefin resin foam contains a spot of polymer antistatic agent, show little apparent density and specific bubble shape, according to the shown specific value of surperficial intrinsic resistance rate after the usefulness ethanol ultrasonic cleaning, the possibility of polluting institute's surface in contact during as wrapping material reduces, outward appearance is good, be subjected to humidity effect not quite can stably manifest the good anti-static performance, flexibility and resiliency are also excellent.In addition, the said polyolefins foamed resin even the washing foam can not lost antistatic performance yet, therefore also is suitable for utilizing again.
[2] of the present invention or [3] described polyolefin resin foam even the content of polymer antistatic agent still less, also can manifest sufficient antistatic performance, and the possibility of polluting institute's surface in contact during as wrapping material is extremely low.And, owing to the usage quantity of expensive polymer antistatic agent still less makes production cost reduce.
Manufacture method according to the polyolefin resin foam of [4] of the present invention described invention, have specific Tc and specific melt viscosity and use the polymer antistatic agent that satisfies with the particular kind of relationship of polyolefin resin by use, add a spot of polymer antistatic agent and can be easy to make [1] described polyolefin resin foam for melt viscosity.
According to [5] of the present invention described manufacture method, especially easily obtain separated foam rate height, outward appearance excellence, polyethylene resin foaming body that apparent density is low, according to the manufacture method of [6] of the present invention described invention, obtain separated foam rate height, outward appearance excellence, expandable polypropylene resin body that apparent density is low especially easily.
Embodiment
Below describe polyolefin resin foam of the present invention (following also abbreviate as " foam ") in detail.
As the shape of foam of the present invention, for example can enumerate bar-shaped, sheet, tabular.Wherein from being easy to pack packed article as wrapping material, the easy this point of the thermoforming preferred sheet or tabular of setting out.
Foam of the present invention is made up of polyolefin resin.Polyolefin resin because low, the flexibility of surface hardness is good, to the functional and advantageous applications of the surface protection of packaged body.Can enumerate for example polyvinyl resin, acrylic resin etc. as the said polyolefins resin.
In addition, the polyolefin resin among the present invention is meant and contains alkene composition unit at 50 moles more than the %, preferred 75 moles more than the %, more preferably 85 moles of resins more than the %.
As above-mentioned polyvinyl resin, for example can enumerate ethene composition unit at 50 moles of resins more than the %, can list high density polyethylene(HDPE), new LDPE (film grade), the ethylene single-polymer of straight chain shape new LDPE (film grade) etc., ethylene-vinyl acetate copolymer, the mixture of ethylene-vinyl acetate copolymer and high-density polyethylene resin, ethylene-propylene copolymer, ethylene-propylene-1-Butylene copolymer, ethene-1-Butylene copolymer, ethene-hexene-1 multipolymer, ethene-4-methylpentene-1 multipolymer, the vinyl copolymer of ethylene-octene-1 multipolymer etc., and the mixture more than 2 kinds in them.
In these polyvinyl resins, the polyvinyl resin of preferred density below 935g/L.Specifically, preferred new LDPE (film grade), straight chain shape new LDPE (film grade) etc., the more preferably good new LDPE (film grade) of foaminess.In addition, be limited to 890g/L, 910g/L more preferably under the density of preferably polyethylene resin.
As above-mentioned acrylic resin, can enumerate propene polymer for example or can with the multipolymer of other alkene of propylene polymerization.As can with other alkene of copolymerization of propylene, but examples example such as ethene, 1-butylene, iso-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3, the ethene of 4-dimethyl-1-butylene, 1-heptene, 3-methyl 1-hexene etc. or the alpha-olefin of carbonatoms 4～10.In addition, above-mentioned multipolymer can be random copolymers, also can be segmented copolymer, and can be copolymer or terpolymer.In addition, these acrylic resins can use in independent or two or more mixing.
When above-mentioned multipolymer is used as the resin that constitutes foam, preferably contain in the multipolymer can with other alkene of copolymerization of propylene below 25 weight %, particularly preferably in the ratio of 15 weight %.On the other hand, lower value is 0.3 weight %.
As the resin that in above-mentioned acrylic resin, also is suitable for extrusion foaming, preferably compare the high high fusion tensile acrylic resin of fusion tension force with general acrylic resin.Specifically, but examples example such as spy open the acrylic resin of putting down in writing in the flat 7-53797 communique has following feature: (1) has the polypropylene of branch's exponential sum significant deformation less than 1, sclerosis, extension, viscosity; Or (2) (a) Z molecular weight (Mz) 1.0 * 10
6More than, and the ratio (Mz/Mw) of Z molecular-weight average (Mz) and weight-average molecular weight (Mw) is more than 0.3; (b) and compliance J
01.2 * 10
-3Pa
-1More than, and the shearing strain of per unit stress recovery Sr/S is 1 second
-1The time J
05 * 10
-4Pa
-1More than.
Perhaps, the present invention also can use the modified polypropylene resin that (3) acrylic resin and radical polymerization initiator and styrene monomer melting mixing form; (4) the improvement acrylic resin that forms of acrylic resin and isobutylene monomer and radical polymerization initiator melting mixing.
In addition, use the low said polyolefins resin of insoluble components in proportions.The meaning of insoluble components in proportions is, with the foam is sample, in 145 ℃ dimethylbenzene, drop into sample, after boiling in 8 hours, filter rapidly with 100 purpose wire cloths, the loft drier of subsequently ebullient dimethylbenzene insolubles residual on the wire cloth being put into 20 ℃ is after dry 24 hours, measure the weight G (g) of insoluble composition, the insoluble components in proportions of trying to achieve by following (6) formula is the combination of 0～10 weight %, is preferably 0～5 weight %, more preferably 0～2 weight %.The angle good from circular form, that cost reduces is considered the low material of preferred insoluble components in proportions.
Dried insoluble component proportions (weight %)=[G (g)/sample weight (g)] * 100
...(6)
Among the present invention, in the scope of not damaging purpose of the present invention and effect, can in polyolefin resin, add the elastomerics of the styrene resin, ethylene propylene rubber etc. of polystyrene etc.The addition of this moment is preferably below 40 weight %, more preferably below 25 weight %, below 10 weight %.
Foam of the present invention contains the polymer antistatic agent.The used polymer antistatic agent of the present invention will describe in detail in the back.
Foam of the present invention is in the polymer antistatic agent that contains 2～12 weight %, and apparent density is 15～65g/L.Apparent density is in this scope the time, polyolefin resin stretches when foaming, simultaneously, the polymer antistatic agent that homogeneous contains in the polyolefin resin is also directed, the network of formation antistatic agent, therefore, even the few addition of the content of polymer antistatic agent below 12 weight %, it is 1 * 10 that foam of the present invention also can manifest surperficial intrinsic resistance rate
8～1 * 10
13(Ω) this good antistatic performance.In addition, because the addition of polymer antistatic agent is few, therefore, foam of the present invention causes that the possibility of surface contamination of packaged body is low.
If the content of polymer antistatic agent surpasses 12 weight %, then may occur: the bubble footpath is thick, degraded appearance, and the separated foam rate also can reduce.Viewpoint is set out thus, the following % of preferred 10 weight of the content of polymer antistatic agent, the more preferably following % of 8 weight, the further following % of preferred 7 weight, the following % of preferred especially 6.5 weight.On the other hand, the polymer antistatic agent contain quantity not sufficient 2 weight % the time, probably can't manifest surperficial intrinsic resistance rate is 1 * 10
8～1 * 10
13(Ω) this good antistatic performance.Viewpoint is set out thus, more than the preferred 3.5 weight %, more preferably more than the 4 weight %.And the content of the polymer antistatic agent in the foam can be obtained by infrared spectroscopic analysis.As long as do not decompose during polymer antistatic agent extrusion foaming, just can obtain its content from the addition of polymer antistatic agent.
When the apparent density of foam surpasses 65g/L, the drawing effect forfeiture of the polyolefin resin that contains the polymer antistatic agent that the bubble growth in the time of may making by foaming causes, antistatic performance variation.From this viewpoint, preferably below 61g/L, more preferably below 51g/L, further preferred 44g/L.On the other hand, apparent density is during less than 15g/L, and the excessive physical strength of wrapping material requirement that may make of expansion ratio reduces.From this viewpoint, preferably more than 15g/L, more preferably more than 18g/L, further preferably more than 21g/L.
The measuring method of the apparent density of foam is as described below among the present invention.
Foam at first, determines the thickness of foam in the form of sheets or when tabular in advance by the following method.
Along cutting off foam with extruding the straight vertical direction of direction, at thickness, measure the thickness of the foam of taking each point with microscope at equally spaced 10 the above-mentioned cut surfaces of photographs of width, get the thickness of arithmetical av with income value as foam.
Measure the level ground amount (g/m of foam again
2).The level ground amount of foam obtains by the following method, cuts out the test film of long 25mm * wide 25mm * foam thickness, and the weight of determination test sheet (g), this weight multiply by 1600 times promptly.
Level ground amount (g/m with above-mentioned foam
2) carry out unit conversion divided by the value of the thickness (mm) of foam, as the apparent density (g/L) of foam.
In addition, on foam during the lamination polyolefin resin layer, the level ground amount of the level ground of foam amount by the lamination foam deducts the level ground amount of polyolefin resin layer and tries to achieve.And the level ground of polyolefin resin amount (g/m
2) identical with the thickness measuring method of above-mentioned foam, by the cut surface of microscope photographing lamination foam, the thickness of asking polyolefin resin layer be multiply by the density of the resin that constitutes polyolefin resin layer, carry out unit conversion again and try to achieve.But when polyolefin resin layer contained a large amount of inorganics, the foam level ground amount of removing polyolefin resin layer from the lamination foam adopts to be measured identical method with the level ground of above-mentioned foam and asks the calculation method to wait to calculate.
And when measuring apparent density without aforesaid method, apparent density can be by calculating the weight of this foam test film divided by the volume that the foam test film is sunken to the part that makes the water level rising in the water.
Foam of the present invention is 1 * 10 with using the surperficial intrinsic resistance rate after the alcoholic acid ultrasonic cleaning
8～1 * 10
13(Ω).
When surperficial intrinsic resistance rate greater than 1 * 10
13In the time of (Ω), antistatic performance is insufficient, and dust is accumulated, adhered to easily to foam surface electrostatic lotus.For making dust be difficult to adhere to, above-mentioned surperficial intrinsic resistance rate is preferably 5 * 10
12(Ω), more preferably 1 * 10
12(Ω).
On the other hand, the surperficial intrinsic resistance rate of foam is less than 1 * 10
8In the time of (Ω), may make the quality of antistatic performance of wrapping material requirement too high, the cost height.
Foam of the present invention promptly uses ethanol to carry out also can not losing antistatic characteristic after the ultrasonic cleaning.In contrast to this, when in foam, adding the antistatic agent of surfactant type such as Zerol, use the ultrasonic cleaning that ethanol carries out after antistatic characteristic disappear.That is, when using the surfactant type antistatic agent, antistatic agent absorbs airborne moisture and manifests antistatic characteristic by oozing out from moulding product surface.Therefore, even can manifest antistatic performance in the normal state, but after using ethanol to carry out ultrasonic cleaning, antistatic agent is washed off from resin surface, and antistatic performance also will be lost.Thus, as the means of the persistence of the antistatic performance of judging resin layer, it is effective measuring the surperficial intrinsic resistance rate of using ethanol to carry out after the ultrasonic cleaning.
" use alcoholic acid ultrasonic cleaning " is meant the ethanol by add 23 ℃ in beaker in this specification sheets, to wherein sinking to test film (the long 100mm * wide 100mm * thickness: foam thickness) after 24 hours, this test film is placed 36 hours exsiccant cleaning operations under the atmosphere of 30 ℃ of temperature, relative humidity 30% that from foam, cuts out with ultrasonic cleaning.The surperficial intrinsic resistance rate that use ethanol carries out after the ultrasonic cleaning is after above-mentioned ultrasonic cleaning operation back gained test film is carried out the state adjustment, to measure with reference to JIS K6911 (1979).
In the foam of the present invention, extrude the average bubble footpath of direction: the average bubble footpath of X (mm) and width: the average bubble of Y (mm) and thickness direction directly: satisfy following relation between the Z (mm).
0.35≦Z/X≦1.2...(1)
0.35≦Z/Y≦1.2...(2)
As long as the value of Z/X, Z/Y is in the scope shown in above-mentioned (1), (2), even the polymer antistatic agent also can make surperficial intrinsic resistance rate reduce on a small quantity.The value of Z/X, Z/Y is more near 1, and promptly the compressive strength of subglobular foam is good more more for bubble shape.The value of Z/X, Z/Y might make compressive strength worsen less than 0.35 o'clock.Viewpoint thus, the scope of Z/X, Z/Y is preferably more than 0.4, more preferably more than 0.45.On the other hand, the value of Z/X, Z/Y is greater than 1.2 o'clock, may observe the thick spot that is known as ripple in the foam and outward appearance worsens.Viewpoint thus, the scope of Z/X, Z/Y is preferably below 1.1, more preferably below 1.0.
In addition, the average bubble of thickness direction footpath: Z (mm) satisfies following relation.
0.2≦Z≦1.4...(3)
As long as the value of Z is in the scope shown in above-mentioned (3), the surface smoothing of foam is good, the outward appearance of foam is good.The value of Z is less than 0.2 o'clock, might make the continuous foamed rate of foam that the tendency of rising, the rigidity step-down of compressive strength etc. are arranged.Viewpoint thus, the scope of Z is preferably more than 0.3, more preferably more than 0.4.On the other hand, when Z greater than 1.4 the time, may be known as the thick spot of ripple and outward appearance worsens.Viewpoint thus, the scope of Z is preferably below 1.3, more preferably below 1.2.
During foam when foam of the present invention is 1～2mm for its thickness, more when using as cushioning material for packing.At this moment, the scope of the value of above-mentioned Z/X, Z/Y and the Z represented scope of following formula more preferably.
0.5≦Z/X≦0.85...(7)
0.5≦Z/Y≦0.85...(8)
0.3≦Z≦0.6... (9)
As long as the value of Z/X, Z/Y and Z can reach the foam that outward appearance is good and resiliency is good in the scope shown in above-mentioned (7), (8) and (9).
Outside inferior, when foam of the present invention is sheet more than the 3mm at its thickness, carry out the secondary processing of thermoforming or laminating resin layer etc. more.At this moment, the value of Z/X, Z/Y and the Z represented scope of following formula more preferably.
0.7≦Z/X≦1.05...(10)
0.7≦Z/Y≦L05...?(11)
0.6≦Z≦1.2... (12)
As long as the value of Z/X, Z/Y and Z is in the scope shown in above-mentioned (10), (11) and (12), because the restorer of getting back to original state that heat causes is little, during thermoforming, foam is difficult to chap, during secondary processing, it is bad to be difficult to produce the secondary workability that fold causes in the laminate surface of foam and resin layer.
In this specification sheets, extrude the average bubble footpath of direction, the average bubble footpath of width, the average bubble of thickness direction and directly measure by the following method respectively.
Extrude the average bubble footpath of direction: the width centre that cuts off foam along the direction perpendicular with extruding direction, the line segment that direction is drawn a long 30mm is extruded on the edge near the central part of its section, measure the number of bubbles on this line segment, extrude the average bubble footpath of direction: X (mm) with line segment length divided by the value conduct of number of bubbles.
The average bubble of width footpath: extruding the line segment that near the broad ways central part of the orthogonal vertical section of direction is drawn a long 30mm with bubble, measure the number of bubbles on this line segment, with line segment length divided by the value of number of bubbles average bubble footpath: Y (mm) as width.
The average bubble footpath of thickness direction: in foam thickness direction vertical section, thickness direction along foam draws the long straight-line segment of a full thickness, measure the number of bubbles on this line segment, with line segment length divided by the value of number of bubbles average bubble footpath: Z (mm) as thickness direction.
And the starting point of this line segment is to draw from the outboard end of walls, even the bubble that intersects with the part of line segment also calculates as number of bubbles.
The continuous air bubbles rate of foam of the present invention is preferably below 65%.
The continuous air bubbles rate is in this scope the time, and the thickness of foam is thin also good as the resiliency of packaging purposes again.And then during thermoforming, the metal pattern circulation ratio is good, and the shape identical with metal pattern can be shaped.Viewpoint thus, the continuous air bubbles rate is preferably below 60%, more preferably below 50%, further preferably below 40%, most preferably below 25%.
The continuous air bubbles rate of foam: S (%) is with reference to the step C of ASTM D 2856-70 record, the actual useful volume of the foam test film of being measured by air comparison expression specific gravity hydrometer 930 types that use Beckman Co., Ltd. of Toshiba system (volumetrical of the volume of separated foam and resin part and): the value that calculates according to following formula (13) among the Vx (L).
S(％)＝(Va-Vx)×100/(Va-W/ρ)...(13)
Wherein, Va, W, the ρ in above-mentioned (13) formula is as described below.
Va: the apparent volume (L) that the outside dimension method by the foam test film (outer cun footpath) calculates
W: the weight of foam test film (g)
ρ: the density (g/L) that constitutes the resin of foam test film
And the weight W (g) that constitutes the density p (g/L) of resin of foam test film and foam test film can make by the heating and pressurizing foam carries out cooling operation after the bubble deaeration and obtains from the gained resin.Because the foam test film must be stored under non-compressed state in the sample cup that has air comparison expression specific gravity hydrometer, the apparent volume of test film is approximately 25cm when long 25mm, wide 40mm
2Piece number of irreducible minimum.
Foam thickness of the present invention is preferably 0.3mm～30mm from the good viewpoint of resiliency, more preferably 0.3mm～20mm, more preferably 0.3mm～10mm.When particularly covering the packed article surface and carrying out bale packing, thickness is preferably 0.3mm～10mm.Thickness may make the rigidity of foam or resiliency insufficient during less than 0.3mm.Viewpoint is set out thus, and the thickness of foam is preferably more than the 0.5mm, more preferably more than the 0.8mm.On the other hand, when the thickness of foam is blocked up, be difficult to operate or be difficult to obtain during thermoforming the shape identical in the time of may making the bale packing packed article with metal pattern.Viewpoint is set out thus, and the thickness of foam is preferably below the 8mm, more preferably below the 6mm.
Under the situation of thickness greater than the foam of 30mm, can become the lamination foam by bonding foam more than 2 layers.In addition, even under the situation of thickness less than the foam of 30mm, also can bondingly become the lamination foam more than 2 layers.When making the lamination foam more than 2 layers, so long as can the identical foam of lamination, also just can laminate thickness, bubble footpath, foam that apparent density is different, even different, different foaies of kind of prescription such as color, substrate resin, function additive.
The microscopical method of putting down in writing in the measuring method of the thickness of foam with above-mentioned apparent density of usefulness is measured.
In addition, when the thickness of the said foam of the present invention is meant polyolefin resin layer lamination described later, the thickness of not resinous layer.Therefore, when lamination polyolefin resin layer on foam, in above-mentioned each photography point, measure the thickness of foam and the thickness of resin layer respectively, with the arithmetical av of gained measured value as the thickness of foam and the thickness of resin layer.
For being become, foam of the present invention is difficult to damaged material, preferably at the polyolefin resin layer (being designated hereinafter simply as resin layer) that is provided with on the single face more than the thickness 5 μ m.The thickness of above-mentioned resin layer is more preferably more than the 8 μ m, more preferably more than the 12 μ m.When the thickness of resin layer is blocked up on the other hand, damage light weight owing to weight is increased, the thickness of resin layer is preferably below 150 μ m, more preferably below 100 μ m.Polyolefin resin layer can form by known laminating methods such as heat bonding polyolefin resines on foam.
Can enumerate for example polyvinyl resin, acrylic resin etc. as the polyolefin resin that constitutes above-mentioned resin layer.
As above-mentioned polyvinyl resin, ethene composition unit is at 50 moles of resins more than the %, can list ethylene single-polymer, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-1-Butylene copolymer, ethene-1-Butylene copolymer, ethene-hexene-1 multipolymer, ethene-4-methylpentene-1 multipolymer, ethylene-octene-1 multipolymer etc. and the mixture more than 2 kinds in them of high density polyethylene(HDPE), new LDPE (film grade), straight chain shape new LDPE (film grade) etc.In addition, as above-mentioned acrylic resin, can enumerate the general acrylic resin except the acrylic resin that constitutes above-mentioned foam.
In constituting the polyolefin resin of polyolefin resin layer, in the scope of not damaging purpose of the present invention and effect, can contain the elastomerics of ethylene propylene rubber etc.The content of this moment is preferably below 40 weight %, more preferably below 25 weight %, below 10 weight %.
Above-mentioned resin layer can contain for example functional additive of nucleator, antioxidant, thermo-stabilizer, weather resisting agent, UV light absorber, fire retardant etc., contain the potassium that is selected from as metal ion,
And the alkali-metal ionic cross-linked polymer resin in the caesium, the various additives of the used polymer antistatic agent of above-mentioned foam, inorganic filler etc.
The polymer antistatic agent that foam of the present invention contains below is described in detail in detail.This polymer antistatic agent by surperficial intrinsic resistance rate less than 1 * 10
12(Ω), preferably less than 1 * 10
10Polymkeric substance (Ω) is formed.
As the number-average molecular weight of polymer antistatic agent among the present invention, preferred more than 2000, more preferably 2000～100000, more preferably 5000～60000, preferred especially 8000～40000, can distinguish mutually with the surfactant type antistatic agent.In addition, the upper limit of the number-average molecular weight of above-mentioned polymer antistatic agent is about 1000000.As long as the number-average molecular weight of polymer antistatic agent is in above-mentioned scope, antistatic performance just can not be affected by environment, understands the more stable antistatic performance that manifests, and the antistatic agent transfer can be polluted packaged surface hardly to packaged body.
In addition, use the high-temperature gel permeation chromatography method to try to achieve above-mentioned number-average molecular weight.For example, the polymer antistatic agent is when being the hydrophilic resin of main component with polyether ester imines or polyethers, and number-average molecular weight is to be that solvent, sample solution concentration are 3mg/ml with the orthodichlorobenzene, and polystyrene is standard substance, the value of measuring under the condition that column temperature is 135 ℃.And above-mentioned solvent types, column temperature are done suitable change according to the kind of polymer antistatic agent.
In addition, preferred 70～270 ℃ from the viewpoint of manifesting property of electrostatic-proof function of the fusing points of polymer antistatic agent, are preferably 80～200 ℃ especially by more preferably 80～230 ℃.
The fusing point of polymer antistatic agent can be measured with reference to the method for JIS K7121 (1987).Promptly in JIS K7121 (1987), carry out pre-treatment according to the condition (wherein, speed of cooling is 10 ℃/minute) of the status adjustment (2) of test film, obtain melting peak by heating up with 10 ℃/minute speed.The temperature on the summit of gained melting peak is as fusing point thus.In addition, melting peak occurs 2 when above, with the temperature on the summit of the melting peak of area maximum as fusing point.Wherein, the melting peak of area maximum exists when a plurality of, with the summit temperature of top temperature side melting peak in these melting peaks as fusing point.
As the polymer antistatic agent that the present invention uses, preferably contain the potassium that is selected from as metal ion,
And the basic metal in the caesium, and be the hydrophilic resin of main component with the ionomer or the polyethers of ethene-unsaturated several acid copolymers etc.
And, in above-mentioned ionomer or the hydrophilic resin, the material that resin preferably of the same race with the said polyolefins resin or that intermiscibility is high carries out block copolymerization.By block copolymerization, improve the intermiscibility of polyolefin resin and polymer antistatic agent, in can the antistatic performance of exhibit excellent, also can suppress to add the rerum natura that the polymer antistatic agent causes and reduce.The concrete example of the polymer antistatic agent that uses as the present invention can be enumerated the spy and open the composition of putting down in writing in the 2001-278985 communique.
It is 10 that the spy opens block and the volume intrinsic resistance value that the composition of putting down in writing in the 2001-278985 communique has polyolefine (a)
5～10
11The block repeated overlapping bonded structure of the hydrophilic polymer of Ω cm (b) is 2000～60000 block polymer (A) for number-average molecular weight (Mn).The block of above-mentioned (a) and block (b) are meant to have by being selected from the material that at least a key in ester bond, amido linkage, ehter bond, urethane bond, the imide bond carries out repeated overlapping bonded structure.
The block of the polyolefine (a) of the above-mentioned block polymer (A) that uses as the polymer antistatic agent can use polymkeric substance two ends to have carbonyl (preferred carbonyl.As the optimal way of following whole carbonyls of giving an example, can enumerate carboxyl) polyolefine (a1), polyolefine (a2), polymkeric substance two ends that polymkeric substance two ends have hydroxyl have amino polyolefine (a3).And, can use polymkeric substance list end to have the polyolefine (a4) of carbonyl, polyolefine (a5), polymkeric substance list end that polymkeric substance list end has hydroxyl have amino polyolefine (a6).Wherein, preferably has the polyolefine (a1) of carbonyl and (a4) from the angle of easy modification.
Block as the hydrophilic polymer (b) that constitutes block polymer (A) can use polyethers (b1), contain hydrophilic polymer (b2), cation property copolymer (b3) and the anionic property polymkeric substance (b4) of polyethers.As (b1), can use the modifier (b1-3) of polyether glycol (b1-1), polyether diamine (b1-2) and above material.As (b2), can use to form composition as polyether segment and have the segmental polyether ester amides of polyether glycol (b1-1) (b2-1), have (b1-1) segmental polyetheramides imide (b2-2) equally, have (b1-1) segmental polyether ester (b2-3) equally, have (b1-2) segmental polyetherimide (b2-4) equally and have (b1-1) equally or (b1-2) segmental polyethers urethane (b2-5).As (b3), can use intramolecularly to have to separate 2～80, the cation property copolymer of preferred 3～60 cationic group (c2) with nonionic molecular chain (c1).As (b4), can use with dicarboxylic acid (e1) with alkylsulfonyl and glycol (b0) or polyethers (b1) as must component unit, and intramolecularly has 2～80, the anionic property polymkeric substance of preferred 3～60 alkylsulfonyls.
As the object lesson of above-mentioned block polymer (A), can enumerate following block polymer (A1)～(A4).
[block polymer (A1)]
Block polymer (A1) is for having the block polymer (A1) of the block of (a1) and (b1) block repeated overlapping integrated structure, contains the repeating unit shown in the general formula (1) of following table 1.In the general formula (1), n is 2～50 integer, R
1And R
2In one be hydrogen atom, another is the alkyl of hydrogen atom or carbonatoms 1～10, y is 15～800 integer, E
1For from glycol (b0), removing the residue of hydroxyl, A1 is the thiazolinyl of carbonatoms 2～4, the integer of m and m ' expression 1～300, X and X ' are the group and the group that is selected from the group shown in corresponding (2 ')～(8 ') of the group shown in general formula (2)～(8) that are selected from following table 1.Be X when being group shown in the general formula (2), X ' is the group shown in the general formula (2 '), and general formula (3)～(8) also have identical relation with general formula (3 ')～(8 ').
Table 1
The general formula of table 1 (2)～(8) and in (2 ')～(8 '), R
3And R
3 'The trivalent hydrocarbon radical of expression carbonatoms 2～3, R
4The bivalent hydrocarbon radical of expression carbonatoms 1～11, R
5The alkyl of expression hydrogen atom or carbonatoms 1～10, R
6The alkyl of expression carbonatoms 2～22, E
2Expression organic diisocyanate residue, r is 1～10, u and v are 0 or 1.In addition, Q, Q ', T and T ' are the represented group of following table 2.
Table 2
Wherein, R
6The alkyl of expression hydrogen atom or carbonatoms 1～10, R
7Expression hydrogen atom or methyl, t represents R
7Be 0 during for methyl, be 1 during for hydrogen atom.Polyether segment { (OA in { } in the repeating unit of general formula (1) expression
1) mOE
1O (A
1O) m ' } constitute E in the formula by the polyether moiety of above-mentioned polyethers (b1)
1, A
1, m and m ' be same as described above.E in the general formula (1)
1Preferably from aliphatic dihydroxy alcohol, dihydric phenol or contain the residue of removing hydroxyl the glycol of tertiary amine groups.
In the general formula (1), X is that the group shown in the general formula (2), X ' are the block polymer (A1) of the group shown in the general formula (2 '), can be obtained by polyolefine with above-mentioned carbonyl (a1) and polyether glycol (b1-1) direct reaction.General formula (2) and the R in (2 ')
3And R
3 'As shown in table 3.R
4Expression hydrogen atom or methyl, t represents R
4During for hydrogen atom be 1, R
4Be 0 during for methyl.When using toxilic acid or fumaric acid in for example polyolefinic carbonyl modification, R
3Be CH
2CH＜, R
3 'For CHCH
2
Table 3
Constitute amount basis (a1) and the total weight (b1) of the polyethers (b1) of block polymer (A1), be generally 20～90 weight %, preferred 25～90 weight % are preferably 30～70 weight % especially.(A1) Mn is generally 2000～60000, is preferably 5000～40000, is preferably 8000～30000 especially.
In the structure of block polymer (A1), the average repeat number (Nn) of the repeating unit of the block of the block of polyolefine (a) and hydrophilic polymer (b) is generally 2～50, is preferably 2.3～30, and more preferably 2.7～20, be preferably 3～10 especially.
[block polymer (A2)]
Block polymer (A2) is combined into (a)-(b) type or (a)-(b)-(a) block polymer that forms of type for the block of the block of polyolefine (a) and hydrophilic polymer (b).(A2) can have polyolefine (a4) reaction of the carbonyl of each expression in general formula (9)～(11) of table 4 and get by (b2) with at single end of polymkeric substance.
Table 4
Table 5
In the formula, R
8Be the polyolefine residue, Q ' is formula CH (R
10) CH=C (R
10) CH
2Shown group, R
9Be the trivalent hydrocarbon radical of carbonatoms 2～3, R
10Be the alkyl of hydrogen atom or carbonatoms 1～10,, R
11Expression hydrogen atom or methyl.As the group shown in the general formula (19) of (b2) preferred table 5.In the formula (19), E3 represents to contain the hydrophilic polymer residue of polyether-based, R
12And R
13Expression hydrogen atom, formula CONHE
2NHCOOR
14NH
2, formula CONHE
2NCO, formula G or formula CH
2CH (OH) CH
2OE
4The group that OG is represented, P represent 0 or 1, A
2The thiazolinyl or the formula (R of expression carbonatoms 2～4
15CO) group represented of r, R
15The bivalent hydrocarbon radical (following also contain saturated hydrocarbyl, unsaturated alkyl any one) of expression carbonatoms 1～11, r represents 1～10 integer, R14 represents the bivalent hydrocarbon radical of carbonatoms 2～12, E
2The residue of expression organic diisocyanate, G represents glycidyl, E
4Expression diglycidylether (GOE
4OG) remove the residue of glycidyl hydroxyl in.In addition, R
12And R
13Preferred hydrogen atom and/or CONHE
2The group that NCO represents.In the general formula (19), E
3The group of general formula (20) expression of preferred table 5.
In the general formula (20), E
5Residue, the D of expression polyethers (b1) represent Sauerstoffatom or imino-, and Z represents to be selected from the polymer segments in polyesteramide, polyamidoimide, polyester, polymeric amide and the poly-urethane, the fragment shown in any of preferred table 5 formula of (21)～(27).U is 0 or 1, and w is generally 2～50, preferred 3～30.In addition, the polyesteramide fragment of Z preferred formula (21) expression.In general formula (21)～(27), E
6For removing the residue of decarboxylate, E in the dicarboxylic acid of carbonatoms 4～20
7Remove the residue of 3 carboxyls in expression ternary or the quaternary aromatic carboxylic acid, E
8The monoamide that expression forms from the diamines of the dicarboxylic acid that is selected from carbonatoms 4～12 and carbonatoms 2～12, and the aminocarboxylic acid of carbonatoms 6～12 polymeric amide form and remove the terminal amino and the residue of carboxyl, E in the composition
9The ester that expression forms from the dicarboxylic acid that is selected from carbonatoms 4～12 and above-mentioned glycol (b0), and the hydroxy acid of carbonatoms 6～12 polyester form and remove the terminal hydroxyl and the residue of base in the composition, s, s ', s " expression 1～50 integer; (s+s ') represent 1 at least, A
3The thiazolinyl or the formula R of expression carbonatoms 2～4
16The group that CO represents, R
16The bivalent hydrocarbon radical of expression carbonatoms 1～11, q represents 0 or 1～10 integer, E
10Expression CODE
11DCONHE
2The group that NH represents, E
2The residue of expression organic diisocyanate, D represents Sauerstoffatom and/or imino-, E
11The residue of expression chain stretching agent.
As block polymer (A2), one side or the both sides that can enumerate the end of hydrophilic polymer (b2) are the structure (by the combination of ester bond) that replaces with the group { when end (b2) is hydroxyl or epoxy group(ing) } that general formula (12)～(14) of table 4 are represented; The structure (by the combination of amido linkage) that the group of representing with general formula (15)～(17) of table 4 { when end (b2) is amino or isocyanate group } replaces; Reach structure (by the combination of imine linkage) with group { when end (b2) the is amino } replacement of general formula (18) expression of table 4.
The polyolefine residue R of above-mentioned table 4
8Preferably use formula R
17{ CH (R
18) CH (R
19) group represented of y (in the formula, R
17Be hydrogen atom or H
2The group that C=CH represents, R
18And R
19A side be hydrogen atom, the opposing party is the alkyl of hydrogen atom or carbonatoms 1～10, y represents 15～800 integer.)。
The amount of the hydrophilic polymer (b2) of formation block polymer (A2) is generally 20～80 weight %, preferred 30～70 weight % according to the weight of (A2).(A2) Mn is generally 2000～60000, is preferably 5000～40000.In the structure of block polymer (A2), the average repeat number (Nn) of the repeating unit of the block of the block of polyolefine (a) and hydrophilic resin (b) is generally 0.4～2.1, is preferably 0.5～2.0, and more preferably 0.6～1.9, be preferably 0.7～1.8 especially.
[block polymer (A3)]
Block polymer (A3) is the material of block of the cation property copolymer (b3) of 2～80 of having that intramolecularly contains that the nonionic molecular chain (c1) that is used as intramolecularly hydrophilic resin (b) separates, preferred 3～60 cationic group (c2), has polyolefine (a) and (b3) repeated overlapping bonded structure.(A3) Mn is generally 2000～60000, is preferably 5000～40000, is preferably 8000～30000 especially.The content of the cationic group (c2) (A3) is to have 2～500 in per 1 molecule (A3), preferred 10～300, and preferred especially 15～250.The Mn of (A3) in each cationic group (c2) is generally 120～30000, is preferably 200～6000, is preferably 300～4000 especially.
In the structure of block polymer (A3), the average repeat number (Nn) of the repeating unit of the block of the block of polyolefine (a) and hydrophilic resin (b) is generally 2～50, is preferably 2.3～30, and more preferably 2.7～20, be preferably 3～10 especially.
[block polymer (A4)]
Block polymer (A4) is to have as hydrophilic resin (b) to have the dicarboxylic acid (e1) of alkylsulfonyl and glycol (b0) or polyethers (b1) for must component unit; and intramolecularly contains 2～80, the material of the block of the anionic property polymkeric substance (b4) of preferred 3～60 alkylsulfonyls, has (a) and (b4) repeated overlapping bonded structure.(A4) Mn is generally 2000～60000, is preferably 5000～40000, is preferably 8000～30000 especially.And (A4) content of the alkylsulfonyl in is to have 2～500 in per 1 molecule (A4), preferred 10～300, and preferred especially 15～250.The Mn of (A4) in each alkylsulfonyl is generally 120～30000, is preferably 200～6000, is preferably 300～4000 especially.
In the structure of block polymer (A4), the average repeat number (Nn) of the repeating unit of the block of the block of polyolefine (a) and hydrophilic resin (b) is generally 2～50, is preferably 2.3～30, and more preferably 2.7～20, be preferably 3～10 especially.
Above-mentioned polymer antistatic agent can be distinguished use separately, also can be used in combination.
The atmospheric condition that foam of the present invention never relies on humidity etc. can manifest antistatic characteristic, the angle that is difficult to adsorb dust and dust is set out, be specially adapted to cushioning material, lagging material for building, containers for food use etc., never pollute the angle on the surface of packed article and set out, as the cushioning material of packing material way of great use.In addition, even therefore foam of the present invention also is suitable for utilizing owing to also can not lose antistatic performance after cleaning foam again.
Below describe the manufacture method of polyolefin resin foam of the present invention in detail.
As manufacture method of the present invention, for example can enumerate, use the extrusion foaming method that the first-class forcing machine of T die head, circular die is installed at the forcing machine front end.Wherein, from can be manifested the angle of antistatic performance, the preferred extrusion foaming method of using the forcing machine that annular die head has been installed by uniformly extension at the foaming thin sheet that obtains the above width of 1000mm easily or foaming plate and foaminess polyolefin resin melts.Specifically, give forcing machine with said polyolefins resin, polymer antistatic agent and bladder regulator from forcing machine raw material supplying confession, with their heating, mixing, in forcing machine, supply with pneumatogen again, further mixing with the polyolefin resin melts, form foaminess polyolefin resin melts, above-mentioned foaminess polyolefin resin melts is adjusted temperature to blowing temperature, extrusion foaming from annular die head, form the tubular foam, by cutting a wherein end, obtain polyolefin resin foam.
Blowing temperature in the forcing machine of above-mentioned foaminess polyolefin resin melts is meant to become for the foam that obtains low bulk density sufficient viscoelastic resin temperature.Specifically, more than [Tc+5 ℃] of blowing temperature preferred polyolefm resin, below [Tc+30 ℃].
In the inventive method, it is 1 * 10 that the enforcement extrusion foaming makes the surperficial intrinsic resistance rate of gained foam
8～1 * 10
13(Ω).
For this reason, add the polymer antistatic agent of 2～14 weight parts with respect to polyolefin resin 100 weight parts.
Hinder foaming when the addition of polymer antistatic agent is too much, the continuous air bubbles rate is low, and can't obtain the foam of low bulk density.The foam resiliency that the continuous air bubbles rate is high is poor, and owing to the thick purposes that makes of bubble is restricted.In view of this, the addition of polymer antistatic agent is preferably below 11 weight parts, more preferably below 9 weight parts, further preferably below 8 weight parts, more further preferably below 7 weight parts, below 6.5 weight parts.
On the other hand, high score is when the addition of type antistatic agent is very few, and the surperficial intrinsic resistance rate of foam can not reach 1 * 10
13(Ω).Therefore the addition of polymer antistatic agent is preferably more than 3 weight parts, more preferably more than 3.8 weight parts.And as the applicable above-mentioned material of polymer antistatic agent.
In the inventive method, extrusion foaming makes the apparent density of gained foam reach 15～65g/L and form foam.Thus, by directed polymer antistatic agent in the developmental process of the bubble of height foaming when foaming, also can be increased sharply antistatic performance even addition is less.Promptly, in specific polyolefin resin, add the specific polymer antistatic agent of aftermentioned, and make the apparent density of foam reach 15～65g/L by extrusion foaming, add a spot of polymer antistatic agent, can make the surperficial intrinsic resistance rate of foam reach 1 * 10
8～1 * 10
13(Ω).And the effect of polymer antistatic agent do not rely on storage period or humidity condition etc., and directly can make the surperficial intrinsic resistance rate of foam after the manufacturing is 1 * 10
8～1 * 10
13(Ω).It should be noted that the excellent results of the fire failure that causes by the static of making the surperficial intrinsic resistance rate that the back directly fully manifests foam, can producing when preventing that the flammable pneumatogen of butane etc. implemented extrusion foaming.
As the method for the apparent density that makes foam in above-mentioned scope, mainly adjust with the addition of pneumatogen.
As above-mentioned pneumatogen, can enumerate the chlorinated hydrocarbon of the aliphatic hydrocarbon, methyl chloride, monochloroethane etc. of for example propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, normal hexane, isohexane, hexanaphthene etc., 1,1,2,2-Tetrafluoroethane, 1, organic pneumatogen of the fluorinated hydrocarbons of 1-C2H4F2 C2H4F2 etc. etc., the inorganic pneumatogen of oxygen, nitrogen, carbonic acid gas, air etc.These pneumatogens can mix use more than 2 kinds.When wherein selecting polyvinyl resin as polyolefin resin, from the intermiscibility of resin, the preferred organic pneumatogen of angle of foaminess, be the material of main component more preferably wherein with normal butane, Trimethylmethane or with their mixture.
In addition, when making foam, add bladder regulator.As bladder regulator, can enumerate borate metal salt, sodium chloride, aluminium hydroxide, talcum, zeolite, silicon-dioxide, lime carbonate, sodium bicarbonate, the phosphoric acid-2 of zinc borate, magnesium borate, borax etc., 2-methylene bis (4, the 6-tert.-butylbenzene) sodium, Sodium Benzoate, calcium benzoate, aluminum benzoate, sodium stearate etc.In addition, also can use the material of combinations such as the alkali salt of Citric Acid and Sodium Hydrogen Carbonate, Citric Acid and sodium bicarbonate as bladder regulator.These bladder regulators also can mix use more than 2 kinds.
The addition that above-mentioned foaming is squeezed is adjusted according to the kind of foam, the apparent density of target foam.In addition, the addition of bladder regulator is mainly directly regulated according to the target bubble.For example, when using the butane mixture of Trimethylmethane 30 weight % and normal butane 70 weight % as whipping agent, the addition of butane mixture has 4～35 weight parts with respect to every polyolefin resin 100 weight parts, preferred 5～30 weight parts, more preferably 6～25 weight parts.In addition, as bladder regulator,, use talcum 11.8 weight parts for example with respect to polyvinyl resin 100 weight parts, during with the use level preparation of Sodium Citrate 5.9 weight parts in enormous quantities.The addition of bladder regulator contains 0.3～10 weight part with respect to every polyolefin resin 100 weight parts, preferred 0.5～5 weight part.
In the used polymer antistatic agent of the present invention, Tc is below 110 ℃, and the melt viscosity (Mb) in the time of 190 ℃ is 80～1000Pas simultaneously.
When Tc surpasses 110 ℃, become insufficient with the mixing property of polyolefin resin, the antistatic characteristic of foam is difficult to manifest.When particularly the Tc of polymer antistatic agent was higher than the Tc of polyolefin resin, the too high forcing machine inside that may make of the Tc of antistatic agent crystallization occurred and hinders foaming.
Wherein, the following of the Tc of polymer antistatic agent is limited to about 60 ℃.Tc is low excessively, and then the rerum natura of resin combination may reduce.
In the inventive method, a spot of content with the polymer antistatic agent, find that foam has good antistatic characteristic, be necessary in directed antistatic agent by forcing machine, in the extrusion foaming operation, the polymer antistatic agent is dispersed in the foaminess polyolefin resin melts uniformly, forms conductive network by extrusion foaming.Therefore, the balance of the viscosity of polyolefin resin in the Tc of above-mentioned polymer antistatic agent, foaminess polyolefin resin melts mixing and polymer antistatic agent is extremely important.
Melt viscosity (Mb) during 190 ℃ of the used polymer antistatic agent of the present invention is 80～1000Pas.That is, melt viscosity (Mb) must satisfy following formula (5).
80Pa·s≦Mb≦1000Pa·s (5)
Because the polymer antistatic agent under this melt viscosity can be fully mixing with polyolefin resin, therefore form the favorable conductive network easily.From the above point of view, preferred 150～800Pas, more preferably 150～500Pas.
The preferred 250～6000Pas of melt viscosity (Ma) during 190 ℃ of the polyolefin resin that the present invention is used, more preferably 300～5000Pas.When melt viscosity (Ma) surpassed 6000Pas, the load that forcing machine bears was too high, and may make becomes when extruding is difficult to control, and resin can not fully stretch during foaming, can't obtain the good foam of outward appearance.On the other hand, melt viscosity (Ma) is during less than 250Pas, may make the mixing property variation with the polymer antistatic agent, hinders the homodisperse of polymer antistatic agent, and anti-static effect reduces.
In addition, when selecting polyvinyl resin as polyolefin resin, the melt viscosity when preferably using 190 ℃ is the material of 300～1600Pas, and more preferably using is 700～1500Pas.Under the foam situation of polyvinyl resin, be used in the purposes that requires resiliency more, bubble is also fine.But, because the melt viscosity of polymer antistatic agent is unsuitable for foaming, for auxiliary this put the polyvinyl resin of preferred high fusion tension-type.
When selecting acrylic resin as polyolefin resin, the melt viscosity when preferably using 190 ℃ is the material in 2000～6000Pas scope, more preferably uses 3000～5500Pas, especially preferably uses the full-bodied material of 4000～5000Pas.As relevant full-bodied acrylic resin, can enumerate the acrylic resin of aforesaid high fusion tension-type.
Must further control among the present invention makes the relation of polymer antistatic agent and the melt viscosity of polyolefin resin in the time of 190 ℃ satisfy following (4) formula.
Ma>Mb (4)
Melt viscosity (Pas) when wherein, the melt viscosity (Pas) when Ma is 190 ℃ of polyolefin resin in (4) formula, Mb are 190 ℃ of polymer antistatic agent.
Shown in above-mentioned (4) formula, also be higher than the melt viscosity (Mb) of polymer antistatic agent by the melt viscosity (Ma) that makes polyolefin resin, be easy to manifest specific antistatic performance.On the other hand, the melt viscosity of polyolefin resin (Ma) then is difficult to form the conductive network structure of polymer antistatic agent if identical or lower with the melt viscosity (Mb) of polymer antistatic agent.
The preferred 0.90Ma of the relation of above-mentioned Ma and Mb〉Mb, more preferably 0.70Ma〉Mb.
On the other hand, Mb is preferably Mb〉0.10Ma, more preferably Mb〉0.15Ma.
Melt viscosity in this specification sheets is measured as follows.
As determinator, for example use the レ オ PVC ス 2100 of チ ア ス ト corporate system, use the sieve aperture of internal diameter 1mm, long 10mm, measuring 190 ℃ of temperature, velocity of shear 100 seconds
-1Condition under measure.
In addition, for forming the conductive network structure of polymer antistatic agent, the Tc of polyolefin resin and polymer antistatic agent satisfies the relation of following (14) formula.
Tb<[Ta+30℃] (14)
Wherein, in (14) formula Tb be the polymer antistatic agent Tc (℃), Ta be the polyolefin resin Tc (℃).
The relation of the Tc by making polymer antistatic agent and polyolefin resin satisfies the following formula requirement, with polymer antistatic agent in the polyolefin resin in foaminess polyolefin resin melts homodisperse more, form the favorable conductive network and be closely related.
The Tc of polyolefin resin in this specification sheets and polymer antistatic agent adopts the value of measuring by the following method.
In this specification sheets,, adopt the value of measuring with reference to the method for JISK7122 (1987), be elaborated as follows as the Tc of polymer antistatic agent.
Take sample 2～4mg,, be warmed up to 230 ℃ from room temperature (about 23 ℃), be cooled to 40 ℃ with 10 ℃/minute speed of cooling again and measure with 10 ℃/minute of rate of heating with differential scanning heat instrument.This moment in the curve that cooling obtains the time, with the temperature of peak maximum as Tc.And when 2 above exothermic peaks occurring, with the summit of the exothermic peak of maximum area as Tc.But when having a plurality of big exothermic peak, with the exothermic peak summit of highest temperature side wherein as Tc.
In the used polyolefin resin of the present invention, as polyvinyl resin, the fusion tension force in the time of preferred 190 ℃ is the material of 30～400mN.Fusion tension force in the time of 190 ℃ is during less than 30mN, foaminess reduced and multiplying power is reduced and continuous air bubblesization.On the other hand, the fusion tension force in the time of 190 ℃ is during greater than 400mN, and the viscosity of resin rises, because the pressure rising in the die head is generated heat when extruding, the continuous air bubbles rate of foam is increased.Fusion tension force during from 190 ℃ of polyolefin resin obtains the angle of low-density foamed body easily, more preferably more than the 35mN, more than the further preferred 40mN.And the angle of the low foam of the continuous foamed rate that is easy to get is calmly set out, below the preferred 300mN of fusion tension force during 190 ℃ of polyolefin resin, more preferably below the 250mN.The reason of measuring in the time of 190 ℃ is because the state of this temperature when foaming with the fusion rerum natura is relevant.
In the used polyolefin resin of the present invention, as acrylic resin, the fusion tension force in the time of preferred 230 ℃ is the material of 30～400mN.Fusion tension force in the time of 230 ℃ is during less than 30mN, foaminess is reduced and makes that multiplying power reduces, continuous air bubblesization.On the other hand, the fusion tension force in the time of 230 ℃ is during greater than 400mN, and the viscosity of resin rises, because the pressure rising in the die head is generated heat when extruding, the continuous air bubbles rate of foam is increased.Fusion tension force during from 230 ℃ of acrylic resin obtains the angle of low-density foamed body easily, more than the preferred 35mN, more preferably more than the 40mN, more than the preferred especially 50mN.And the angle of the low foam of the continuous foamed rate that is easy to get is calmly set out, below the preferred 300mN of fusion tension force during 230 ℃ of acrylic resin, more preferably below the 250mN.The reason of measuring in the time of 230 ℃ is because the state of this temperature when foaming with the fusion rerum natura is relevant.
The fusion tension force of the polyolefin resin among the present invention: MT can make made fusion tonometer II type by the smart mechanism of Toyo Co., Ltd. for example and wait and measure.Specifically, when the polyolefin resin of mensuration is polyvinyl resin, carry out by the following method.
Use is equipped with the fusion tonometer of the sieve aperture of internal diameter 2.095mm, long 8mm, in 190 ℃ of resin temperatures, the velocity of piston extruded is under the 10mm/ condition of dividing, from above-mentioned sieve aperture, extrude knob shape resin, the tension force that this knob shape thing is hung over diameter 45mm detects with after on the pulley, with on one side with 5rpm/ second (knob shape thing furl acceleration: 1.3 * 10
-2M/ second
2) about ratio slowly increase the speed of furling, on one side furl with the spool of diameter 50mm.
Specifically ask the fusion tensile method of calculating polyolefin resin, furl furling under the speed 500 (rpm), by with tension force detect with pulley banded machines through the time mensuration knob shape thing that is detected fusion tension force, getting the longitudinal axis is MT (mN), transverse axis is time (second) mapping, obtains having the figure of amplitude.Obtain the intermediate value (X) of amplitude of the steady component of amplitude then.The present invention is a fusion tension force with this value (X).And the specificity amplitude of ignoring few generation when measuring.
Wherein, hanging over tension force, to detect the speed that furls with the knob shape thing of pulley be when cutting off till 500 (rpm), asks the speed that the furls R (rpm) when calculating the cut-out of knob shape thing.Then in certain furling in the speed of R * 0.7 (rpm), according to the above-mentioned figure that obtains equally, the intermediate value (X) that adopts amplitude is as fusion tension force.
When polyolefin resin is acrylic resin, except that resin temperature is 230 ℃, carry out same mensuration with polyvinyl resin.
In addition, also can in above-mentioned polyolefin resin, add various additives.As various additives, for example can enumerating, tinting material, nucleator, antioxidant, thermo-stabilizer, weather resisting agent, UV light absorber, fire retardant, inorganic filler, antiseptic-germicide, contraction prevent agent etc.Preferred 0.01～10 weight % of addition of this moment, the more preferably following % of 5 weight, the following % of preferred especially 3 weight.
In addition, when making foam of the present invention, as the inflation method in average bubble footpath, can be by the polyolefin resin that uses, for example, the method that average bubble directly diminishes or the content of above-mentioned bladder regulator are adjusted.
In addition, as the inflation method of the bubble shape of Z/X, Z/Y, can be by the polyolefin resin that uses, for example, extrude when bubble is flats on the direction, the value of concrete Z/X is that 0.35 ≦ Z/X＜1.0 o'clock adjust the method for discharge-amount minimizing, pulling speed rising etc.On the other hand, when extruding bubble on the direction and being roughly spherical, the value of concrete Z/X near 1.0 o'clock or be 1.2 make that discharge-amount increases when following more than 1.0, the method for degradation is adjusted under the pulling speed.
When bubble is flats on the width, the value of concrete Z/Y is 0.35 ≦ Z/Y＜1.0 o'clock, method till available foam is extruded into width and broadens is adjusted, when using annular die, become big method with blowing ratio (bore that spues of the diameter/annular die of the refrigerating unit of tubular--core rod) and adjust.On the other hand, when bubble was spherical on the width, the value of concrete Z/Y was near 1.0 o'clock or be more than 1.0 1.2 when following, and the available foam that do not make is adjusted to the extrusion method of width expansion, when using annular die, diminish to method with blowing ratio and to adjust near 1.
According to the inventive method, have specific Tc and specific melt viscosity by use, and this melt viscosity satisfies and the polymer antistatic agent of the specific relation of polyolefin resin, adds a small amount of polymer antistatic agent and promptly may be easy to make foam of the present invention.Promptly, according to the present invention and since above-mentioned polymer antistatic agent can be in foam homodisperse, the gained foam has good anti-static, do not rely on storage period after the manufacturing and humidity condition etc., can manifest the good anti-static performance immediately after the manufacturing.
Embodiment
Following according to the present invention of embodiment more detailed description.
As polyolefin resin, can use material shown below.
PE1: Sumitomo Chemical Company Ltd's system new LDPE (film grade) [F102] (97.8 ℃ of Tcs, density: 922g/l, MFR:0.3g/10 branch (190 ℃, loading 21.17N))
PE2: the You Nijia of Co., Ltd. makes new LDPE (film grade) [NUC8008] (93.5 ℃ of Tcs, density: 917g/l, MFR:4.5g/10 branch (190 ℃, loading 21.17N))
PP1:SunAllomer Co., Ltd. system propylene-ethylene block copolymer [SD632] (128 ℃ of Tcs, density: 900g/l, MFR:3.2g/10 branch (230 ℃, loading 21.17N))
As the polymer antistatic agent, can use material shown below.
Polymer antistatic agent P1: Sanyo Chemical Industries, Ltd.'s system polyethers-polypropylene block copolymer [ペ レ ス Star ト 300] (136 ℃ of fusing points, number-average molecular weight 14000, density 990g/l)
Polymer antistatic agent P2:Ciba Speciality Chemical Co., Ltd.'s system (mixture of polyether ester amides and polymeric amide) [IRGASTAT P18] (180 ℃ of fusing points, number-average molecular weight 19000, density 1043g/l)
Embodiment 1
As polyolefin resin, with respect to PE1 (new LDPE (film grade)) 100 weight parts, cooperate bladder regulator master batch 2 weight parts, with respect to new LDPE (film grade) 100 weight parts, add polymer antistatic agent P1[ペ レ ス Star ト 300] 6.4 weight parts, supply with from the raw material input port of the forcing machine of internal diameter 90mm, add hot milling, under about 200 ℃, become the resin melt of having adjusted.The mixed butanes that is pressed into normal butane 70 weight % and Trimethylmethane 30 weight % in above-mentioned resin melt is 25 weight parts with respect to new LDPE (film grade) 100 weight parts extremely.The forcing machine of the diameter 120mm that connects to the downstream side of the forcing machine of above-mentioned diameter 90mm is supplied with resin melt again, the blowing temperature of regulating cooled polyolefin resin melts is 110 ℃, it is 7～10MPa (G) that die head is pressed, become foaminess polyolefin resin melts, its foaminess polyolefin resin melts is extruded from the annular die of diameter 95mm, forms the tubular foam.The tubular foam of extruding along cooled cylinder traction cuts on one side on one side, obtains foaming thin sheet.And the bladder regulator master batch cooperates talcum (Ishihara Sangyo Kaisha, Ltd.'s system, trade(brand)name [Ha イ Off イ ラ-#12] 11.8 weight parts, Sodium Citrate 5.9 weight parts with respect to new LDPE (film grade) 100 weight parts.
Embodiment 2
Is that all the other were identical with embodiment 1, obtain foaming thin sheet 27 weight parts, blowing temperature were 108 ℃ except use PE2 (new LDPE (film grade)) as polyolefin resin as the use level of main raw material, adjusting mixed butanes.
Embodiment 3
Except the use level of pneumatogen is 23 weight parts, adds P1[ペ レ ス Star ト 300 as the polymer antistatic agent] 4.7 weight parts, to regulate blowing temperature is 111 ℃, all the other are identical with embodiment 1, obtain foaming thin sheet.
Embodiment 4
Except use PP1 as the use level of polyolefin resin, pneumatogen be 8 weight parts, to regulate blowing temperature be that 152 ℃, blowing ratio and pulling speed are adjusted to the value shown in the table 7, all the other are identical with embodiment 1, obtain foaming thin sheet.
Comparative example 1
Except with respect to new LDPE (film grade) 100 weight parts, add the system polymer antistatic agent P1[ペ レ ス of Sanyo Chemical Industries Co., Ltd. Star ト 300] 17.6 weight parts, use level with respect to the mixed butanes of new LDPE (film grade) 100 weight parts is 25 weight parts, regulating blowing temperature is beyond 108 ℃, all the other are identical with embodiment 1, obtain foaming thin sheet.
Comparative example 2
Except the use level of pneumatogen is 8 weight parts, to regulate blowing temperature be 113 ℃, blowing ratio and pulling speed are adjusted to beyond the value shown in the table 7, and all the other are identical with embodiment 1, obtain foaming thin sheet.
Comparative example 3
Except adding polymer antistatic agent P1[ペ レ ス Star ト 300] 1.5 weight parts, to regulate blowing temperature is 111 ℃, all the other are identical with embodiment 1, obtain foaming thin sheet.
Comparative example 4
Except using the polymer antistatic agent to add P2[IRGASTAT P18], carry out the extrusion foaming identical with embodiment 1.But occur the crystallization thing in the foam, can only obtain the foam of concave-convex surface dress, can not measure surperficial intrinsic resistance rate.The crystallization thing of foam is thought to add P2[IRGASTAT P18 by the polymer antistatic agent] material that produces.
In embodiment 1～4, the comparative example 1～4, kind, all rerum naturas of polyolefin resin (main raw material) are as shown in table 6, and it is as shown in table 7 to create conditions.
All rerum naturas of the foaming thin sheet that obtains among embodiment 1-4, the comparative example 1-4 are as shown in table 8.
The average bubble footpath of extruding direction of the foam in embodiment and the comparative example: X (mm), the average bubble footpath of width: the average bubble footpath of Y (mm) and thickness direction: the adjustment of Z (mm), carry out according to blowing temperature, discharge-amount, blowing ratio and pulling speed shown in bladder regulator addition, the table 7.And the blowing temperature in the table 7 is the temperature of annular die through the thermoregulated die head of deep fat.
Followingly carry out the content of polymer antistatic agent in the foam, fusion tension force, the surperficial intrinsic resistance rate after the washing with alcohol and the evaluation of outward appearance of foam.
[content of polymer antistatic agent]
According to the thermal history of the extrusion foaming in embodiment and the comparative example, to confirm also can not reduce after the thermolysis of polymer antistatic agent, the addition of the polymer antistatic agent during by the manufacturing foam is asked calculation.
The fusion tension force of foam
As sample, use the method identical to measure with the foam of thin cut-out with the fusion tensile measuring method of above-mentioned raw materials resin.
[mensuration of the surperficial intrinsic resistance rate after the washing with alcohol]
From foam, cut out long 100mm * wide 100mm * thick: the test film of test film thickness, carry out following state adjustment, immediately under 23 ℃, 50% RH environment is measured surperficial intrinsic resistance rate down with the test film behind the adjustment state.At this moment, obtain the surperficial intrinsic resistance rate after voltage applies 1 minute of applying with reference to the method for above-mentioned JIS K6911 (1979) with 500V.Determinator makes the Tian Li that uses force grind the system ITR8610 of Industrial Co., Ltd].
[the state adjustment of test film]
As informed later, be [BRANSONIC220] with the Branson corporate system, at first at the ethanol of 500ml with weighing 500ml in the beaker, the alcoholic acid temperature maintenance is at 23 ℃.By using wire cloth that the test film in the beaker is sunk, test film is immersed in the above ethanol of purity 99.5Vol% then.The beaker cover lid of being sunk for above-mentioned test film with tinsel then receives the position at the concavity of above-mentioned informed later that 23 ℃ 1.7 liters water is housed and puts into above-mentioned beaker, leaves standstill the back and connects the power supply of informed later and begin to clean.Clean beginning after back 8 hours, begin once more to clean, append the ethanol that 23 ℃ of alcoholic acid are operated in the beaker and reach 500ml through after 16 hours.In addition, this append alcoholic acid operation be since in the ultrasonic washing ethanol volatilization amount of alcohol that exists in the beaker is compared reduce the complement operation of doing the most at the beginning.Cleaning begins to stop informed later through after 24 hours.Take out test film from beaker, immediately this test film was placed 36 hours under the atmosphere of 30 ℃ of relative humidity 30%, temperature, drying is finished the state adjustment to test film.
[evaluation of outward appearance]
Range estimation gained foam carries out ocular estimate according to following judgement criteria.
Zero: the shape of bubble is all even, is trickle bubble, and surface smoothing is good.
△: the shape of bubble is all even, is trickle bubble, but is found everywhere huge a little bubble, the concavo-convex of part occur.
*: huge bubble occurs, the part on surface is the pimple state, all finds concavo-convex.
Claims (6)
1. polyolefin resin foam, it is characterized in that, with respect to polyolefin resin 100 weight parts, the number-average molecular weight that contains 2～14 weight parts is 2000～100000 high molecular type antistatic agent, apparent density is 15～65g/L, and the surperficial intrinsic resistance rate that use ethanol carries out after the ultrasonic cleaning is 1 * 10
8-1 * 10
13Ω, average bubble directly satisfies following (1), (2) and (3) formula,
0.35≦Z/X≦1.2...(1)
0.35≦Z/Y≦1.2...(2)
0.2≦Z≦1.4...(3)
Wherein, X, Y and Z are respectively: the average bubble footpath of extruding direction: X millimeter, the average bubble footpath of width: the average bubble footpath of Y millimeter and thickness direction: Z millimeter.
2. polyolefin resin foam as claimed in claim 1 is characterized in that, with respect to polyolefin resin 100 weight parts, the content of the high molecular type antistatic agent in the polyolefin resin foam is 2～11 weight parts.
3. polyolefin resin foam as claimed in claim 1 is characterized in that, with respect to polyolefin resin 100 weight parts, the content of the high molecular type antistatic agent in the polyolefin resin foam is 2～9 weight parts.
4. the manufacture method of polyolefin resin foam as claimed in claim 1, this method with polyolefin resin, number-average molecular weight be 2000～100000 high molecular type antistatic agent, bubble adjust agent and pneumatogen mixing in forcing machine, form foaminess polyolefin resin melts, and this foaminess polyolefin resin melts of extrusion foaming and make polyolefin resin foam; It is characterized in that,
The addition of above-mentioned high molecular type antistatic agent is 2～14 weight parts with respect to polyolefin resin 100 weight parts;
The Tc of above-mentioned high molecular type antistatic agent is below 110 ℃;
The mensuration temperature of said polyolefins resin is that 190 ℃, velocity of shear are 100 seconds
-1The time the melt viscosity Ma and the mensuration temperature of above-mentioned high molecular type antistatic agent be that 190 ℃, velocity of shear are 100 seconds
-1The time the relation of melt viscosity Mb satisfy following (4) and (5) formula:
Ma>Mb (4)
80Pa·s≤Mb≤1000Pa·s (5)
The unit of Ma, Mb is Pas.
5. the manufacture method of polyolefin resin foam as claimed in claim 4 is characterized in that, polyolefin resin is that the fusion tension force under 190 ℃ is the polyvinyl resin of 30～400mN.
6. the manufacture method of polyolefin resin foam as claimed in claim 4 is characterized in that, polyolefin resin is that the fusion tension force under 230 ℃ is the acrylic resin of 30～400mN.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3391/04 | 2004-01-08 | ||
| JP3391/2004 | 2004-01-08 | ||
| JP2004003391A JP2005194433A (en) | 2004-01-08 | 2004-01-08 | Manufacturing method of polyolefin resin foamed body and polyolefin resin foamed body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1670069A CN1670069A (en) | 2005-09-21 |
| CN100513468C true CN100513468C (en) | 2009-07-15 |
Family
ID=34818316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100040230A Active CN100513468C (en) | 2004-01-08 | 2005-01-07 | Polyolefin resin foam and manufacturing method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2005194433A (en) |
| KR (1) | KR100860251B1 (en) |
| CN (1) | CN100513468C (en) |
| TW (1) | TW200530307A (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007169527A (en) * | 2005-12-22 | 2007-07-05 | Jsr Corp | Thermoplastic elastomer composition, foamed product and its production method |
| JP5294369B2 (en) * | 2006-06-30 | 2013-09-18 | 株式会社ジェイエスピー | Method for producing polyolefin resin foam |
| JP4982168B2 (en) * | 2006-12-21 | 2012-07-25 | 日本ポリプロ株式会社 | Antistatic sheet and molded body using the same |
| JP4195719B2 (en) * | 2007-04-02 | 2008-12-10 | 株式会社ジェイエスピー | Interleaving paper for glass substrate |
| JP4901589B2 (en) * | 2007-06-07 | 2012-03-21 | 株式会社ジェイエスピー | POLYOLEFIN RESIN EXTRUSION FOAM SHEET, GLASS SUBSTRATE COMPOSITION COMPRISING THE FOAM SHEET AND PACKAGING MATERIAL |
| JP4954831B2 (en) * | 2007-09-05 | 2012-06-20 | 積水化成品工業株式会社 | Method for producing polyethylene resin foam sheet |
| JP2009155423A (en) * | 2007-12-26 | 2009-07-16 | Jsp Corp | Extrusion-foamed polyolefin resin sheet and method for producing the same |
| JP5198086B2 (en) * | 2008-02-15 | 2013-05-15 | 積水化成品工業株式会社 | Polypropylene resin foam sheet |
| JP5459781B2 (en) * | 2009-03-25 | 2014-04-02 | 株式会社ジェイエスピー | Laminated polyethylene resin foam sheet |
| JP5557309B2 (en) * | 2009-06-25 | 2014-07-23 | 株式会社ジェイエスピー | Polyolefin resin foam sheet |
| JP5557486B2 (en) * | 2009-07-29 | 2014-07-23 | 積水化成品工業株式会社 | Polyethylene resin foam sheet |
| JP5512331B2 (en) * | 2010-03-03 | 2014-06-04 | 積水化成品工業株式会社 | Foamed sheet and foamed resin container |
| JP5859794B2 (en) * | 2010-09-30 | 2016-02-16 | 酒井化学工業株式会社 | Foam plastic protective sheet |
| JP5370390B2 (en) | 2011-02-14 | 2013-12-18 | Ｊｎｃ株式会社 | Polyolefin antistatic fiber and non-woven fabric comprising the same |
| KR101645610B1 (en) * | 2014-11-19 | 2016-08-05 | 롯데케미칼 주식회사 | Resin composition for preparing polyolefin resin foam and polyolefin resin foam formed therefrom |
| JP6506619B2 (en) * | 2015-03-26 | 2019-04-24 | 株式会社ジェイエスピー | Method for producing extruded extruded polyethylene resin sheet, extruded extruded polyethylene resin sheet, and interlayer for glass plate |
| WO2016152878A1 (en) * | 2015-03-26 | 2016-09-29 | 株式会社ジェイエスピー | Production method for polyethylene-based resin extruded foam sheets, polyethylene-based resin extruded foam sheet, and interleaving paper for glass plates using same |
| JP6078091B2 (en) * | 2015-03-26 | 2017-02-08 | 株式会社ジェイエスピー | Method for producing polyethylene-based resin laminated foam sheet, polyethylene-based resin laminated foam sheet, and interleaf paper for glass plate using the same |
| CN107325324B (en) | 2016-04-28 | 2019-08-20 | 中国石油化工股份有限公司 | Fire retardant, fire-resistant antistatic composition and fire-resistant antistatic polypropylene foaming beads |
| JP7407620B2 (en) | 2020-02-26 | 2024-01-04 | 株式会社ジェイエスピー | Method for manufacturing polyethylene resin extruded foam sheet, and polyethylene resin extruded foam sheet |
| CN112194834B (en) * | 2020-09-30 | 2023-04-28 | 广德祥源新材科技有限公司 | High-temperature-shrinkage-resistant polyethylene foam sheet and preparation method thereof |
| CN113150485A (en) * | 2021-03-20 | 2021-07-23 | 深圳市好亚通防护用品有限公司 | Humidity-independent antistatic material and preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09169072A (en) * | 1995-12-20 | 1997-06-30 | Pooren Kagaku Sangyo Kk | Low foamed ethylene polymer resin laminated antistatic sheet |
-
2004
- 2004-01-08 JP JP2004003391A patent/JP2005194433A/en active Pending
- 2004-12-24 TW TW093140597A patent/TW200530307A/en unknown
-
2005
- 2005-01-06 KR KR1020050001202A patent/KR100860251B1/en active IP Right Grant
- 2005-01-07 CN CNB2005100040230A patent/CN100513468C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1670069A (en) | 2005-09-21 |
| TW200530307A (en) | 2005-09-16 |
| TWI337612B (en) | 2011-02-21 |
| KR20050073557A (en) | 2005-07-14 |
| JP2005194433A (en) | 2005-07-21 |
| KR100860251B1 (en) | 2008-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100513468C (en) | Polyolefin resin foam and manufacturing method thereof | |
| KR101546544B1 (en) | Multi-layered polystyrene resin foamed sheet | |
| TWI461296B (en) | Polyolefin resin-laminated foam | |
| CN101935416A (en) | Polyolefine resin sparkling sheet material | |
| JP4901589B2 (en) | POLYOLEFIN RESIN EXTRUSION FOAM SHEET, GLASS SUBSTRATE COMPOSITION COMPRISING THE FOAM SHEET AND PACKAGING MATERIAL | |
| JP4919371B2 (en) | Co-extrusion laminated foam and molded product thereof | |
| KR20080090294A (en) | Paper to be inserted between glass substrates | |
| CN101134381B (en) | Manufacturing method for foamed sheet, and foamed sheet | |
| JP5075046B2 (en) | Foam sheet | |
| JP2008007670A (en) | Polyolefin-based resin foam and method for producing the same, and package for transporting glass substrates | |
| JP2007186706A (en) | Manufacturing method of polyolefin resin foam and polyolefin resin foam | |
| JP4493000B2 (en) | Polyolefin resin foam sheet | |
| JP4189275B2 (en) | Method for producing foam sheet | |
| CN101638158B (en) | Packaging material | |
| JP4148463B2 (en) | Method for producing polyethylene resin laminated foam and polyethylene resin laminated foam | |
| JP6785066B2 (en) | Polyolefin resin foam sheet | |
| JP4526986B2 (en) | Polyolefin resin foam sheet molding resin composition and polyolefin resin foam sheet obtained therefrom | |
| JP2019064048A (en) | Laminated paper for glass plate | |
| JP4845168B2 (en) | Multi-layer polystyrene resin foam | |
| JP5859794B2 (en) | Foam plastic protective sheet | |
| JP6435217B2 (en) | Polyethylene resin foam sheet | |
| JP5567852B2 (en) | Interleaving paper for glass substrate | |
| EP0920990A2 (en) | Composite olefin resin laminated sheet | |
| JP3755923B2 (en) | Polyolefin resin multilayer shrink film | |
| JP2019059939A (en) | Polyethylene resin foam sheet |
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 |