JPH0347849A - Partially crosslinked thermoplastic elastomer foam and production thereof - Google Patents
Partially crosslinked thermoplastic elastomer foam and production thereofInfo
- Publication number
- JPH0347849A JPH0347849A JP9791390A JP9791390A JPH0347849A JP H0347849 A JPH0347849 A JP H0347849A JP 9791390 A JP9791390 A JP 9791390A JP 9791390 A JP9791390 A JP 9791390A JP H0347849 A JPH0347849 A JP H0347849A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic elastomer
- weight
- ionizing radiation
- parts
- partially crosslinked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 118
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 84
- 229920003023 plastic Polymers 0.000 claims abstract description 46
- 239000004033 plastic Substances 0.000 claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005060 rubber Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000004132 cross linking Methods 0.000 claims abstract description 26
- 238000005187 foaming Methods 0.000 claims abstract description 26
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 22
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 18
- 238000004898 kneading Methods 0.000 claims description 17
- 239000002480 mineral oil Substances 0.000 claims description 12
- 235000010446 mineral oil Nutrition 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 abstract description 17
- 238000000465 moulding Methods 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 3
- 238000011156 evaluation Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 230000000704 physical effect Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000004088 foaming agent Substances 0.000 description 12
- 229920001684 low density polyethylene Polymers 0.000 description 12
- 239000004702 low-density polyethylene Substances 0.000 description 12
- 239000008188 pellet Substances 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 9
- 201000004562 autosomal dominant cerebellar ataxia Diseases 0.000 description 9
- KINULKKPVJYRON-PVNXHVEDSA-N n-[(e)-[10-[(e)-(4,5-dihydro-1h-imidazol-2-ylhydrazinylidene)methyl]anthracen-9-yl]methylideneamino]-4,5-dihydro-1h-imidazol-2-amine;hydron;dichloride Chemical compound Cl.Cl.N1CCN=C1N\N=C\C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1\C=N\NC1=NCCN1 KINULKKPVJYRON-PVNXHVEDSA-N 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000003856 thermoforming Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 methylene norbornene Chemical compound 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 238000007666 vacuum forming Methods 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004156 Azodicarbonamide Substances 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- 235000019399 azodicarbonamide Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011243 crosslinked material Substances 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- UGXAIVCNTXGYSA-UHFFFAOYSA-N 2,2,2-trichloroethyl dihydrogen phosphite Chemical compound OP(O)OCC(Cl)(Cl)Cl UGXAIVCNTXGYSA-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Chemical class 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- FMGUJLASXUBMOP-UHFFFAOYSA-N N-Methyl-N,4-dinitrosoaniline Chemical compound O=NN(C)C1=CC=C(N=O)C=C1 FMGUJLASXUBMOP-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- LJMVJSWRZJYKSO-UHFFFAOYSA-N O=P(OC(CCCl)(CCCl)C(CCCl)(CCCl)O1)OP1=O Chemical compound O=P(OC(CCCl)(CCCl)C(CCCl)(CCCl)O1)OP1=O LJMVJSWRZJYKSO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 208000019960 autosomal dominant cerebellar ataxia type I Diseases 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N dimethylbutene Natural products CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
発明の技術分野
本発明は、部分架橋熱可塑性エラストマー発泡体および
その製造方法に関し、さらに詳しくは、耐熱性、耐薬品
性、引張り特性、柔軟性、ゴム弾性に優れるとともに、
熱成形加工性に優れる、低発泡倍率ないし高発泡倍率の
部分架橋熱可塑性エラストマー発泡体およびその製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a partially crosslinked thermoplastic elastomer foam and a method for producing the same, and more particularly, it relates to a partially crosslinked thermoplastic elastomer foam and a method for producing the same, and more particularly, to a partially crosslinked thermoplastic elastomer foam that has excellent heat resistance, chemical resistance, tensile properties, flexibility, and rubber elasticity. ,
The present invention relates to a partially crosslinked thermoplastic elastomer foam having excellent thermoformability and a low to high expansion ratio, and a method for producing the same.
発明の技術的背景
従来より、エラストマー発泡体の製造方法として、天然
ゴムあるいは合成ゴムに加硫剤と発泡剤を加えて混練し
た後、この混線物を所定の形状に成形して加熱すること
により加硫と発泡を行なってエラストマー発泡体を得る
という方法が知られている。Technical Background of the Invention Conventionally, elastomer foams have been produced by adding a vulcanizing agent and a blowing agent to natural rubber or synthetic rubber, kneading the mixture, and then molding the mixture into a predetermined shape and heating it. A method of obtaining an elastomer foam by vulcanization and foaming is known.
しかしながら、上記のような方法では、連続押出しで上
記ゴムを所定の形状に成形する場合、原料がゴムである
ため、予め発泡剤等の配合物をゴムにバッチ的に練り込
んで混線物を得る工程と、連続押出しする前に行なう必
要があり、またこの混練物を押出機に供給し易くするた
め、予め混練物をリボン状に成形する工程を、連続押出
しする前に行なう必要がある。また上記のような方法で
は、広幅のシート状および複雑な異形形状の成形体を得
ることはできないという問題点があり、また発泡時にお
いて成形体の形状が変形し易いため一定形状の発泡体が
得られないという問題点かあり、さらに得られた発泡体
の熱成形加工が困難であるという問題点がある。However, in the above method, when the rubber is molded into a predetermined shape by continuous extrusion, since the raw material is rubber, a compound such as a blowing agent is kneaded into the rubber in advance in batches to obtain a mixed material. It is necessary to perform this step before continuous extrusion, and in order to make it easier to feed this kneaded material to the extruder, it is necessary to perform a step of previously forming the kneaded material into a ribbon shape before continuous extrusion. In addition, the above method has the problem that it is not possible to obtain a wide sheet-like molded product or a molded product with a complex irregular shape, and the shape of the molded product is easily deformed during foaming, so it is difficult to obtain a foamed product with a fixed shape. There is a problem that the foamed product cannot be obtained, and furthermore, it is difficult to thermoform the obtained foamed product.
このような問題点を解消する方法として天然ゴム、合成
ゴムの代わりに、軟質オレフィン系プラスチック、たと
えばエチレン−酢酸ビニル共重合体、低密度ポリエチレ
ンなどの熱可塑性樹脂を用いる方法が既に知られている
が、この方法によれば、上述の工程を省略することがで
きるだけでなく、連続で押出される混線物の成形体形状
の自由度が高い。また、さらに混線物の成形体を放射線
照射あるいは化学架橋剤による処理により一旦架橋して
から発泡させれば、発泡時における成形体の形状保持性
が良くなる。As a method to solve these problems, it is already known to use soft olefin plastics, such as thermoplastic resins such as ethylene-vinyl acetate copolymer and low-density polyethylene, instead of natural rubber or synthetic rubber. However, according to this method, not only can the above-mentioned steps be omitted, but also there is a high degree of freedom in the shape of the molded product of the mixed wire product that is continuously extruded. Moreover, if the molded product of the hybrid mixture is once crosslinked by radiation irradiation or treatment with a chemical crosslinking agent and then foamed, the shape retention of the molded product during foaming will be improved.
しかしながら、基本的に、軟質オレフィン系プラスチッ
クにはゴムに比べて耐熱性や引張特性が劣る等の欠点が
あり、得られる発泡体の用途が大きく制限されるという
問題点がある。However, basically, soft olefin plastics have drawbacks such as inferior heat resistance and tensile properties compared to rubber, and there is a problem that the uses of the resulting foams are greatly limited.
また、特開昭４９−１２９７５７号公報には、架橋性の
樹脂であるエチレン−プロピレン系エラストマーとポリ
エチレン樹脂のみからなる発泡基材と、熱分解型発泡剤
との混合物を所望の形状に成形した後、電離性放射線で
架橋を施して加熱発泡させることにより高発泡の合成樹
脂発泡体を得る製造方法が提案されている。Furthermore, Japanese Patent Application Laid-Open No. 49-129757 discloses that a mixture of a foamed base material consisting only of a crosslinkable resin, an ethylene-propylene elastomer and a polyethylene resin, and a pyrolyzable foaming agent is molded into a desired shape. A production method has been proposed in which a highly foamed synthetic resin foam is obtained by crosslinking with ionizing radiation and then heating and foaming.
しかしながら、この場合、発泡基材成分として電離性放
射線照射により分解性を有する成分は含まれず電離性放
射線照射により架橋性を有する成分のみを用いるため、
得られる発泡体は、部分架橋発泡体ではなく、完全架橋
発泡体であり、柔軟性に優れるものの、熱成形加工性や
製造安定性あるいは表面平滑性に乏しく、用途的に限ら
れてしまうという問題点がある。However, in this case, as the foam base material component does not contain a component that can be decomposed by irradiation with ionizing radiation, only a component that can be crosslinked by irradiation with ionizing radiation is used.
The resulting foam is not a partially cross-linked foam but a fully cross-linked foam, and although it has excellent flexibility, it has poor thermoformability, manufacturing stability, and surface smoothness, which limits its uses. There is a point.
一方、軟質オレフィン系プラスチックと加硫ゴムとの中
間の性能を示す素材として、ペルオキシド架橋型オレフ
ィン系共重合体ゴムと、ペルオキシド架橋型オレフィン
系プラスチックと、ペルオキシド分解型オレフィン系プ
ラスチックとからなる部分架橋された組成物が熱可塑性
エラスＩ・マーとして使用できることは、たとえば特開
昭４８−２８８３８号公報により公知である。On the other hand, partially crosslinked materials consisting of peroxide crosslinked olefin copolymer rubber, peroxide crosslinked olefin plastics, and peroxide decomposition type olefin plastics are used as materials that exhibit intermediate performance between soft olefin plastics and vulcanized rubber. It is known, for example, from JP-A No. 48-28838, that the resulting composition can be used as a thermoplastic elastomer.
また、このようなポリオレフィン系熱可塑性エラストマ
ーを発泡基材として用いた発泡体の製造方法が特公昭８
０−１１９３７号公報により開示されており、具体的に
は、ペルオキシド分解型オレフィン系プラスチック、軽
度に架橋されたペルオキシド架橋型オレフィン系共重合
体ゴムおよびペルオキシド架橋型オレフィン系プラスチ
・ツクからなる部分架橋熱可塑性エラストマーと、熱分
解型発泡剤とを混練して所望の形状に成形した後、その
まま加熱発泡させて発泡体を得るという製造方法が提案
されている。In addition, a method for manufacturing a foam using such a polyolefin thermoplastic elastomer as a foaming base material was published in 1983.
0-11937, specifically, a partially crosslinked material consisting of a peroxide decomposition type olefin plastic, a lightly crosslinked peroxide crosslinked olefin copolymer rubber, and a peroxide crosslinked olefin plastic. A manufacturing method has been proposed in which a thermoplastic elastomer and a thermally decomposable foaming agent are kneaded and molded into a desired shape, and then heated and foamed as they are to obtain a foam.
しかしながら、上記の方法では、発泡時に部分架橋させ
るのではなく、既に部分架橋させた原料であ４）部分架
橋熱可塑性エラストマーに発泡剤を単に混合し発泡させ
ているため、発泡倍率が高々３倍程度と低発泡倍率の発
泡体しか得られない。したがって、この方法により得ら
れる発泡体は、車輌外装材等の大型肉厚製品の用途に限
られてしまうという問題点がある。However, in the above method, instead of partially crosslinking at the time of foaming, the foaming agent is simply mixed with the partially crosslinked thermoplastic elastomer and foamed with the raw material that has already been partially crosslinked, so the foaming ratio is at most 3 times. Only foams with low expansion ratios can be obtained. Therefore, there is a problem in that the foam obtained by this method is limited to use in large, thick-walled products such as vehicle exterior materials.
また、日本ゴム協会誌第６１巻第２号第７０頁にも熱可
塑性エラストマー発泡体の製造方法が照会されているが
、この場合も架橋させた後の熱可塑性エラストマーを基
材としているため、化学発泡剤と気体を併用する等の発
泡方法で工夫をしても、高々比重０．２程度、実用的に
は比重０．７と極めて低発泡の発泡体しか得られない。Additionally, the Japan Rubber Association Journal, Vol. 61, No. 2, Page 70, also refers to the manufacturing method of thermoplastic elastomer foam, but in this case as well, the thermoplastic elastomer after crosslinking is used as the base material. Even if a foaming method such as using a chemical foaming agent and a gas in combination is devised, only a foam with a specific gravity of about 0.2 at most, and in practical terms a specific gravity of 0.7, can only be obtained with extremely low foaming.
したかって、この方法により得られる発泡体も、車輌外
装材等の大型肉厚製品の用途に限られてしまうという問
題点がある。Therefore, there is a problem in that the foam obtained by this method is also limited to use in large, thick-walled products such as vehicle exterior materials.
本発明者らは、上記のような問題点を解決すべく鋭意研
究し、電離性放射線により架橋を生じる電離性放射線架
橋型オレフィン系共重合体ゴムのほかに、電離性放射線
により架橋を生じない電離性放射線分解型オレフィン系
プラスチックを必須成分とする電離性放射線部分架橋性
熱可塑性エラストマーに、熱分解型発泡剤を加えて発泡
性組成物とし、この発泡性組成物の成形体に電離性放射
線を照射し、さらに加熱して発泡させたところ、柔軟性
に優れるだけでなく、製造安定性および表面平滑性にも
優れ、また加熱成形時に非架橋部分の流動性により熱加
工性にも優れた、広範囲の用途に利用できる部分架橋熱
可塑性エラストマー発泡体が得られることを見出し、本
発明を完成するに至った。The inventors of the present invention have conducted intensive research to solve the above problems, and have developed an olefin copolymer rubber that does not crosslink due to ionizing radiation, in addition to an ionizing radiation crosslinkable olefin copolymer rubber that crosslinks due to ionizing radiation. A thermally decomposable blowing agent is added to an ionizing radiation partially crosslinkable thermoplastic elastomer containing an ionizing radiation decomposable olefin plastic as an essential component to form a foamable composition, and a molded article of this foamable composition is exposed to ionizing radiation. When the material was irradiated and further heated to foam, it not only showed excellent flexibility, but also excellent manufacturing stability and surface smoothness, as well as excellent heat processability due to the fluidity of the non-crosslinked portion during thermoforming. They have discovered that a partially crosslinked thermoplastic elastomer foam can be obtained that can be used in a wide range of applications, and have completed the present invention.
発明の目的
本発明は、上記のような従来技術に伴う問題点を解決し
ようとするものであって、耐熱性、耐薬品性、引張り特
性、柔軟性、ゴム弾性に優れるとともに、熱成形加工性
に優れる、低発泡倍率ないし高発泡倍率の部分架橋熱可
塑性エラストマー発泡体およびその製造方法を提供する
ことを目的としている。Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above. The object of the present invention is to provide a partially crosslinked thermoplastic elastomer foam having a low expansion ratio to a high expansion ratio, and a method for producing the same.
発明の概要
本発明に係る部分架橋熱可塑性エラストマー発泡体は、
（ａ）電離性放射線架橋型オレフィン系共重合体ゴム１
００〜１０重量部、（ｂ）電離性放射線架橋型オレフィ
ン系プラスチックＯ〜９０重量０
部および（ｃ）電離性放射線分解型オレフィン系プラス
チック１〜９０重量部［但し、（ａ）成分、（ｂ）成分
および（ｃ）成分の合計重量は１００重量部とするコか
らなる、メルトインデックス０．１〜１００ ｇ ／
１０分の電離性放射線部分架橋性熱可塑性エラストマー
（Ａ）と、
熱分解型発泡剤（Ｂ）
とからなる発泡性組成物で構成されている未発泡の部分
架橋熱可塑性エラストマー成形体が、発泡してなること
を特徴としている。Summary of the Invention The partially crosslinked thermoplastic elastomer foam according to the present invention comprises:
(a) Ionizing radiation crosslinked olefin copolymer rubber 1
00 to 10 parts by weight, (b) ionizing radiation crosslinkable olefin plastic O to 90 parts by weight, and (c) 1 to 90 parts by weight of ionizing radiation decomposition type olefin plastic [However, component (a), (b) The total weight of components () and (c) is 100 parts by weight, and the melt index is 0.1 to 100 g/
An unfoamed partially crosslinked thermoplastic elastomer molded article composed of a foamable composition consisting of a partially crosslinkable thermoplastic elastomer (A) and a pyrolyzable blowing agent (B) after 10 minutes of ionizing radiation is foamed. It is characterized by the fact that
また本発明に係る部分架橋熱可塑性エラストマー発泡体
の製造方法は、（ａ）電離性放射線架橋型オレフィン系
共重合体ゴム１００〜１０重量部、（ｂ）電離性放射線
架橋型オレフィン系プラスチック０〜９０重量部および
（ｃ）電離性放射線分解型オレフィン系プラスチック１
〜９０重量部［但し、（ａ）成分、（ｂ）成分および（
ｃ）成分の合計重量は１００重量部とするコからなる、
メルトインデックス０．１〜１００ ｇ ／ １０分の
電離性放射線部分架橋性熱可塑性エラストマー（Ａ）に
、熱分解１
型発泡剤（Ｂ）を、熱分解型発泡剤（Ｂ）の分解温度以
下の温度で溶融混練して得られる発泡性組成物を、所定
の形状に成形した後電離性放射線を照射して未発泡の部
分架橋熱可塑性エラストマー成形体を得る工程と、
該未発泡の部分架橋熱可塑性エラストマー成形体を、熱
分解型発泡剤（Ｂ）の分解温度以」二の温度で加熱して
発泡させる工程
とからなることを特徴としている。The method for producing a partially crosslinked thermoplastic elastomer foam according to the present invention includes (a) 100 to 10 parts by weight of an ionizing radiation crosslinked olefin copolymer rubber, and (b) 0 to 10 parts by weight of an ionizing radiation crosslinked olefin copolymer rubber. 90 parts by weight and (c) ionizing radiodegradable olefin plastic 1
~90 parts by weight [However, component (a), component (b) and (
c) The total weight of the ingredients is 100 parts by weight;
A pyrolytic type 1 blowing agent (B) is added to a thermoplastic elastomer (A) partially crosslinkable by ionizing radiation with a melt index of 0.1 to 100 g/10 min at a temperature below the decomposition temperature of the pyrolytic blowing agent (B). a step of molding a foamable composition obtained by melt-kneading at a temperature into a predetermined shape and then irradiating it with ionizing radiation to obtain an unfoamed partially crosslinked thermoplastic elastomer molded body; It is characterized by comprising the step of heating and foaming the plastic elastomer molded article at a temperature equal to or higher than the decomposition temperature of the pyrolyzable foaming agent (B).
発明の詳細な説明
以下、本発明に係る部分架橋熱可塑性エラスＩ・マー発
泡体およびその製造方法について具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION The partially crosslinked thermoplastic elastomer foam and the method for producing the same according to the present invention will be specifically described below.
まず本発明に係る部分架橋熱可塑性エラストマー発泡体
について説明する。First, the partially crosslinked thermoplastic elastomer foam according to the present invention will be explained.
本発明の部分架橋熱可塑性エラストマー発泡体は、未発
泡の部分架橋熱可塑性エラストマー成形体を発泡させた
発泡体であり、この未発泡の部分架橋熱可塑性エラスト
マー成形体は、基本的に、電離性放射線部分架橋性熱可
塑性エラストマー］ ２
（Ａ）と、熱分解型発泡剤（Ｂ）とからなる発泡性組成
物で構成されている。また上記電離性放射線部分架橋性
熱可塑性エラストマー（Ａ）は、（ａ）電離性放射線架
橋型オレフィン系共重合体ゴムと、（ｂ）電離性放射線
架橋型オレフィン系プラスチックと、（ｃ）電離性放射
線分解型オレフィン系プラスチックとから構成され、必
要に応じて（ｄ）鉱物油系軟化剤を含めることができる
。The partially crosslinked thermoplastic elastomer foam of the present invention is a foam obtained by foaming an unfoamed partially crosslinked thermoplastic elastomer molded product, and this unfoamed partially crosslinked thermoplastic elastomer molded product basically has ionizable properties. Radiation partially crosslinkable thermoplastic elastomer] 2 (A) and a thermally decomposable foaming agent (B). The ionizing radiation partially crosslinkable thermoplastic elastomer (A) comprises (a) an ionizing radiation crosslinkable olefin copolymer rubber, (b) an ionizing radiation crosslinkable olefin plastic, and (c) an ionizing radiation crosslinkable olefin copolymer rubber. (d) A mineral oil softener can be included as necessary.
電離性放射線部分架橋性
熱可塑性エラストマー（Ａ）
本発明において、電離性放射線部分架橋性熱可塑性エラ
ストマー（Ａ）とは、オレフィン系熱可塑性エラストマ
ーに電離性放射線を照射した際に生じる分解反応と架橋
反応の競争反応において、架橋反応が多い結果、組成物
中の重合体の分子量が増大する部分と、分解反応が多い
結果、組成物中の重合体の分子量が減少する部分とが共
存す４）部分架橋熱可塑性エラストマーをいう。Ionizing radiation partially crosslinkable thermoplastic elastomer (A) In the present invention, ionizing radiation partially crosslinkable thermoplastic elastomer (A) refers to the decomposition reaction and crosslinking that occur when an olefinic thermoplastic elastomer is irradiated with ionizing radiation. In competitive reactions, there are parts where the molecular weight of the polymer in the composition increases as a result of many crosslinking reactions, and parts where the molecular weight of the polymer in the composition decreases as a result of many decomposition reactions4) Partially crosslinked thermoplastic elastomer.
（ａ）電離性放射線架橋型オレフィン系共重合体ゴム
］ ３
本発明で用いられる（ａ）電離性放射線架橋型オレフィ
ン系共重合体ゴムとは、たとえばエチレン−プロピレン
−非共役ジエンゴム、エチレン−ブタジェン共重合体ゴ
ムの如く、オレフィンを主成分とする無定形ランダムな
弾性共重合体であって、電離性放射線を照射することに
よって架橋して流動性が低下するか、あるいは流動しな
くなるオレフィン系共重合体ゴムをいう。これらのうち
ではエチレン−プロピレン−非共役ジエンゴム（ここで
、非共役ジエンとは、ジシクロペンタジェン、１．４−
へキサジエン、シクロオクタジエン、メチレンノルボル
ネン、エチリデンノルボルネンなどをいう）が好ましく
、特にエチレン−プロピレン−非共役ジエン共重合体ゴ
ム、中でもエチレン−プロピレン−エチリデンノルボル
ネン共重合体ゴムが適度な架橋構造を有す４）部分架橋
熱可塑性エラストマ発泡体が得られる点で特に好ましい
。(a) Ionizing radiation crosslinked olefin copolymer rubber] 3 The (a) ionizing radiation crosslinked olefin copolymer rubber used in the present invention is, for example, ethylene-propylene-nonconjugated diene rubber, ethylene-butadiene rubber, etc. Copolymer rubber is an amorphous random elastic copolymer mainly composed of olefins, and when irradiated with ionizing radiation, it crosslinks and its fluidity decreases or becomes non-flowable. Refers to polymer rubber. Among these, ethylene-propylene-nonconjugated diene rubber (here, nonconjugated diene refers to dicyclopentadiene, 1.4-
Hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, etc.) are preferred, and ethylene-propylene-nonconjugated diene copolymer rubber, especially ethylene-propylene-ethylidene norbornene copolymer rubber, has an appropriate crosslinked structure. (4) Particularly preferred in that a partially crosslinked thermoplastic elastomer foam can be obtained.
この共重合体ゴム（ａ）のムーニー粘度ＭＬ１＋４（１
００°Ｃ）は１０〜１゜８０、特に４０〜１４０の範囲
内にあることが好ましく、ムーニー粘度が４
４０未満になると、得られる発泡性組成物の溶融張力が
低くなり、得られる発泡体の気泡の径が大きくなる場合
がある。一方、ムーニー粘度が１４０を超えると、発泡
性組成物の成形性（流動性）が劣り、得られる発泡体の
外観が悪化する場合がある。Mooney viscosity ML1+4(1
00°C) is preferably in the range of 10 to 1°80, particularly 40 to 140. If the Mooney viscosity is less than 440, the melt tension of the foamable composition obtained will be low, and the resulting foam will be The diameter of the bubbles may become larger. On the other hand, if the Mooney viscosity exceeds 140, the moldability (fluidity) of the foamable composition may be poor, and the appearance of the resulting foam may deteriorate.
またこの共重合体ゴムのヨウ素価（不飽和度）は、好ま
しくは１６以下である。ヨウ素価が上記のような範囲に
ある共重合体ゴムを用いると、発泡化と架橋化とのバラ
ンスが良好な部分架橋熱可塑性エラストマー発泡体か得
られる。The iodine value (degree of unsaturation) of this copolymer rubber is preferably 16 or less. When a copolymer rubber having an iodine value within the above range is used, a partially crosslinked thermoplastic elastomer foam with a good balance between foaming and crosslinking can be obtained.
本発明では、（ａ）電離性放射線架橋型オレフィン系共
重合体ゴムは、（ａ）電離性放射線架橋型オレフィン系
共重合体ゴム、（ｂ）電離性放射線架橋型オレフィン系
プラスチックおよび（ｃ）電離性放射線分解型オレフィ
ン系プラスチックの合計重量１００重量部に対し、１０
〜１００重量部、好ましくは４０〜９０重量部、さらに
好ましくは５０〜８０重量部の量で用いられる。In the present invention, (a) ionizing radiation crosslinkable olefin copolymer rubber includes (a) ionizing radiation crosslinking olefin copolymer rubber, (b) ionizing radiation crosslinkable olefin plastic, and (c) 10 parts by weight per 100 parts by weight of the ionizing radiolytic olefin plastic
It is used in an amount of ~100 parts by weight, preferably 40-90 parts by weight, more preferably 50-80 parts by weight.
５
（ｂ）電離性放射線架橋型オレフィン系プラスチック
本発明で用いられる（ｂ）電離性放射線架橋型オレフィ
ン系プラスチックとは、電離性放射線を照射することに
よって架橋して流動性が低下するか、あるいは流動しな
くなるオレフィン系プラスチックをいい、具体的には、
高圧法低密度ポリエチレン、中低圧性低密度ポリエチレ
ン、高密度ポリエチレン、その他のエチレン・α−オレ
フィンの共重合体、あるいはα−オレフィンと１５モル
％以下の他の重合性単量体との共重合体、たとえばエチ
レン−酢酸ビニル共重合体、エチレン−アクリル酸共重
合体、エチレン−アクリル酸メチル共重合体、エチレン
−アクリル酸エチル共重合体、エチレン−メタクリル酸
共重合体、エチレン−メタクリル酸メチル共重合体等で
ある樹脂状高分子物質が挙げられる。これらの中でも、
特に低密度ポリエチレンが適度な架橋構造を有す４）部
分架橋熱可塑性エラストマー発泡体が得られる点で好ま
しい。5 (b) Ionizing radiation crosslinked olefinic plastic The (b) ionizing radiation crosslinked olefinic plastic used in the present invention is one that is crosslinked by irradiation with ionizing radiation and has reduced fluidity, or Refers to olefin-based plastics that no longer flow, specifically:
High-pressure low-density polyethylene, medium-low-pressure low-density polyethylene, high-density polyethylene, other ethylene/α-olefin copolymers, or copolymers of α-olefin and 15 mol% or less of other polymerizable monomers copolymer, such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate Examples include resinous polymeric substances such as copolymers. Among these,
In particular, low-density polyethylene is preferred in that 4) a partially crosslinked thermoplastic elastomer foam having an appropriate crosslinked structure can be obtained.
この（ｂ）電離性放射線架橋型オレフィン系プラ６
スチックのメルトインデックス（ＡＳＴＭ Ｄ １２３
８−６５Ｔ、１９０°Ｃ）は、０．１〜５０ ｇ ／
１０分、好ましくは２〜２０ｇ／１０分の範囲である。(b) Melt index of ionizing radiation crosslinked olefin plastic (ASTM D 123)
8-65T, 190°C) is 0.1-50 g/
10 minutes, preferably in the range of 2 to 20 g/10 minutes.
本発明では、（ｂ）電離性放射線架橋型オレフィン系プ
ラスチックは、（ａ）電離性放射線架橋型オレフィン系
共重合体ゴム、（ｂ）電離性放射線架橋型オレフィン系
プラスチックおよび（ｃ）電離性放射線分解型オレフィ
ン系プラスチックの合計重量１００重量部に対し、０〜
９０重量部、好ましくは５〜５０Ｔｆ！量部、さらに好
ましくは１０〜３０重量部の量で用いられる。In the present invention, (b) ionizing radiation crosslinkable olefinic plastic includes (a) ionizing radiation crosslinking olefinic copolymer rubber, (b) ionizing radiation crosslinkable olefinic plastic, and (c) ionizing radiation crosslinkable olefinic plastic. 0 to 100 parts by weight of the total weight of decomposable olefin plastic
90 parts by weight, preferably 5-50 Tf! parts by weight, more preferably 10 to 30 parts by weight.
（ｃ）電離性放射線分解型オレフィン系プラスチック
本発明で用いられる（ｃ）電離性放射線分解型オレフィ
ン系プラスチックとは、電離性放射線を照射することに
よって分子量が減じ、流動性が増加するオレフィン系プ
ラスチックであって、具体的には、アイソタクチックポ
リプロピレンあるいはプロピレンと他の少量のα−オレ
フィンとの共重合体、たとえばプロピレン−エチレン共
重合体、７
プロピレンー１−ブテン共重合体、プロピレン・１−ヘ
キセン共重合体、プロピレン・４−メチル刊−ペンテン
共重合体などが用いられる。(c) Ionizing radiation decomposition type olefin plastic The (c) ionizing radiation decomposition type olefin plastic used in the present invention is an olefin type plastic whose molecular weight decreases and fluidity increases by irradiation with ionizing radiation. Specifically, isotactic polypropylene or a copolymer of propylene and a small amount of other α-olefin, such as propylene-ethylene copolymer, 7-propylene-1-butene copolymer, propylene-1- Hexene copolymers, propylene/4-methyl-pentene copolymers, etc. are used.
この（ｃ）電離性放射線分解型オレフィン系プラスチッ
クのメルトインデックス（ＡＳＴＭ Ｄ １２３８：２
３０℃、２］［Ｏｇ）は、１〜８０ ｇ／ｌ ０分、好
ましくは５〜５０ ｇ ／ １０分の範囲である。(c) Melt index of ionizing radiodegradable olefin plastic (ASTM D 1238:2
30°C, 2][Og) ranges from 1 to 80 g/l 0 min, preferably from 5 to 50 g/10 min.
本発明で用いられる（ｃ）電離性放射線分解型オレフィ
ン系プラスチックは、発泡性組成物の流動性および耐熱
性を向上させる役割を持つ。The (c) ionizing radiation-degradable olefin plastic used in the present invention has the role of improving the fluidity and heat resistance of the foamable composition.
本発明では、（ｃ）電離性放射線分解型オレフィン系ブ
スチックは、（ａ）電離性放射線架橋型オレフィン系共
重合体ゴム、（ｂ）電離性放射線架橋型オレフィン系プ
ラスチックおよび（ｃ）電離性放射線分解型オレフィン
系プラスチックの合計重量１００重量部に対し、１〜９
０重量部、好ましくは１０〜８０重量部、さらに好まし
くは２０〜５０重量部の量で用いられる。（ｃ）電離性
放射線分解型オレフィン系プラスチックの量が５０重量
部を超えると、得られ４）部分架橋熱可塑性エラストマ
ー発８
泡体の柔軟性およびゴム弾性が低下する場合がある。一
方（ｃ）電離性放射線分解型オレフィン系プラスチック
の量が２０重量部未満になると、発泡性組成物の耐熱性
、流動性が損なわれ、得られ４）部分架橋熱可塑性エラ
ストマー発泡体の耐熱性および熱成形加工性が悪化する
場合がある。In the present invention, (c) ionizing radiation-degradable olefin-based plastics include (a) ionizing radiation-crosslinked olefin-based copolymer rubber, (b) ionizing radiation-crosslinked olefin-based plastic, and (c) ionizing radiation-crosslinked olefin-based plastics. 1 to 9 parts per 100 parts by weight of the total weight of decomposable olefin plastic
It is used in an amount of 0 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 50 parts by weight. (c) If the amount of the ionizing radiolytic olefin plastic exceeds 50 parts by weight, the flexibility and rubber elasticity of the foam obtained may decrease. On the other hand, if the amount of (c) ionizing radiodegradable olefin plastic is less than 20 parts by weight, the heat resistance and fluidity of the foamable composition will be impaired, resulting in 4) Heat resistance of partially crosslinked thermoplastic elastomer foam and thermoformability may deteriorate.
（ｄ）鉱物油系軟化剤
（ｄ）鉱物油系軟化剤としては、通常ゴムをロール加工
する際にゴムの分子間作用力を弱め、加工を容易にする
とともに、カーボンブラック、ホワイトカーボン等の分
散を助けたり、あるいは加硫ゴムの硬さを低下せしめて
、柔軟性あるいは弾性を増す目的で使用されている高沸
点の石油留分が用いられ、具体的には、パラフィン系、
ナフテン系、あるいは芳香族系等の鉱物油が用いられる
。(d) Mineral oil-based softeners (d) Mineral oil-based softeners are used to weaken the intermolecular forces of rubber during roll processing, making it easier to process, and to soften carbon black, white carbon, etc. High boiling point petroleum fractions are used to aid in dispersion, or to reduce the hardness of vulcanized rubber and increase its flexibility or elasticity.Specifically, paraffinic,
A naphthenic or aromatic mineral oil is used.
このような（ｄ）鉱物油系軟化剤は、上記成分（ａ）
、（ｂ） 、（ｃ）および（ｄ）の合計型ｆｆ１ｌｏＯ
重量部に対し、０〜５０重量部、好ましくは１０〜２０
重量部の量で用いられる。（ｄ）鉱物油系軟化剤の量が
１０重量部未満になると、充分な流動性 ９
改善効果が得られなくなる場合があり、一方２０重量部
を超えると、得られ４）部分架橋熱可塑性エラストマー
発泡体の耐熱性および引張り特性が低下する場合があり
、また（ｄ）鉱物油系軟化剤が発泡体の表面に滲出して
発泡体の外観を損なう等好ましからぬ影響を与える場合
がある。Such (d) mineral oil-based softener contains the above component (a).
, (b), (c) and (d) sum type ff1loO
0 to 50 parts by weight, preferably 10 to 20 parts by weight
Used in parts by weight. (d) If the amount of the mineral oil softener is less than 10 parts by weight, sufficient fluidity improvement effect may not be obtained; on the other hand, if it exceeds 20 parts by weight, the partially crosslinked thermoplastic elastomer may not be obtained. The heat resistance and tensile properties of the foam may deteriorate, and (d) the mineral oil softener may ooze out onto the surface of the foam, resulting in unfavorable effects such as impairing the appearance of the foam.
本発明で用いられる電離性放射線部分架橋性熱可塑性エ
ラストマー（Ａ）のメルトインデックス（ＡＳＴＭ−Ｄ
−１２３８−６５Ｔ 、 ２３０℃）は、０．１〜１０
０ ｇ ／ １０分、好ましくは５〜８０ｇ／ｌ。Melt index (ASTM-D) of the ionizing radiation partially crosslinkable thermoplastic elastomer (A) used in the present invention
-1238-65T, 230℃) is 0.1 to 10
0 g/10 min, preferably 5-80 g/l.
分、さらに好ましくは１０〜４０ ｇ ／ １０ 分の
範囲内である。電離性放射線部分架橋性熱可塑性エラス
トマー（Ａ）のメルトインデックスが上記範囲内にある
と、配合混線時における、あるいは架橋発泡前の所望形
状に成形加工する際における電離性放射線部分架橋性熱
可塑性エラストマー（Ａ）の熱的流動特性が優れている
。minutes, more preferably within the range of 10 to 40 g/10 minutes. When the melt index of the ionizing radiation partially crosslinkable thermoplastic elastomer (A) is within the above range, the ionizing radiation partially crosslinkable thermoplastic elastomer can be used during blending or when molding into a desired shape before crosslinking and foaming. (A) has excellent thermal flow properties.
上記のような電離性放射線部分架橋性熱可塑性エラスト
マー（Ａ）は、従来公知の混練装置、たとえば開放型の
ミキシングロール、非開放型のバ０
ンバリーミキサー、押出機、ニーダ−１連続ミキサー好
ましくは非開放型の混線装置を用いて、上記（ａ） 、
（ｂ）および（ｃ）の各成分または上記（ａ）、（ｂ）
、（ｃ）および（ｄ）の各成分を溶融混合することに
よって得ることができる。The ionizing radiation partially crosslinkable thermoplastic elastomer (A) as described above is preferably prepared using a conventionally known kneading device, such as an open type mixing roll, a non-open type Banbury mixer, an extruder, or a kneader-1 continuous mixer. uses a non-open crosstalk device to perform the above (a),
Each component of (b) and (c) or the above (a), (b)
, (c) and (d) are melt-mixed.
上記の溶融混練は、窒素、炭酸ガスなどの不活性ガスの
雰囲気下で行なうことが好ましい。また、上記の溶融混
線の条件は、通常、混線温度が１５０〜２８０℃、好ま
しくは１７０〜２４０℃であり、混線時間が１〜２０分
、好ましくは３〜１０分である。The above melt-kneading is preferably carried out in an atmosphere of an inert gas such as nitrogen or carbon dioxide. Moreover, the conditions for the above-mentioned melt cross-wire are that the cross-wire temperature is usually 150 to 280°C, preferably 170 to 240°C, and the cross-wire time is 1 to 20 minutes, preferably 3 to 10 minutes.
熱分解型発泡剤（Ｂ）
本発明で用いられる熱分解型発泡剤（Ｂ）としては、従
来公知の熱分解型発泡剤を用いることができ、具体的に
は、ジエチルアゾジカルボキシレート、アゾジカルボン
アミド、アゾジカルボン酸バリウム、４．４”−オキシ
ビス（ベンゼンスルホニルヒドラジド） 、３．３’−
ジスルホンヒドラジドフェニルスルホン酸、Ｎ、Ｎ’−
ジニトロソペンタメチレンテトラミン等を挙げることが
できる。中で１
も、本発明で用いる樹脂組成物の成形に適した樹脂温度
との兼ね合いから、アゾジカルボンアミドを用いるのが
最も好ましい。熱分解型発泡剤の配合量は、目的とする
発泡体の発泡倍率にもよるが、通常、前記（ａ）電離性
放射線架橋型オレフ、イン系共重合体ゴム、（ｂ）電離
性放射線架橋型オレフィン系プラスチックおよび（ｃ）
電離性放射線分解型オレフィン系プラスチックの合計重
量１００重量部に対し、１〜５０重量部、好ましくは１
〜３０重量部の量で用いられる。発泡剤の配合量が少な
過ぎると、発泡成形が困難となり、一方、多過ぎると脱
泡を生じやすく、発泡体表面に凹凸を生じるようになる
。Pyrolytic foaming agent (B) As the pyrolytic foaming agent (B) used in the present invention, conventionally known pyrolytic foaming agents can be used. Specifically, diethyl azodicarboxylate, azo Dicarbonamide, barium azodicarboxylate, 4.4"-oxybis(benzenesulfonylhydrazide), 3.3'-
Disulfone hydrazidophenyl sulfonic acid, N, N'-
Examples include dinitrosopentamethylenetetramine. Among them, it is most preferable to use azodicarbonamide in view of the resin temperature suitable for molding the resin composition used in the present invention. The amount of the pyrolytic blowing agent to be blended depends on the expansion ratio of the desired foam, but it usually includes the above-mentioned (a) ionizing radiation crosslinked OLEF, in-based copolymer rubber, and (b) ionizing radiation crosslinking. type olefin plastic and (c)
1 to 50 parts by weight, preferably 1 to 100 parts by weight of the total weight of the ionizing radiolytic olefin plastic.
It is used in an amount of ˜30 parts by weight. If the amount of the foaming agent is too small, foam molding becomes difficult, while if it is too large, defoaming is likely to occur, resulting in unevenness on the surface of the foam.
本発明では、未発泡の部分架橋熱可塑性エラストマー成
形体を構成する発泡性組成物に、硫黄、ｐ−キノンジオ
キシム、Ｉ）、Ｉ）−ジベンゾイルキノンジオキシム、
Ｎ−メチル−Ｎ、４−ジニトロソアニリン、ニトロベン
ゼン、ジフェニルグアニジン、トリメチロールプロパン
−Ｎ、Ｎ’−＋ｎ−フェニレンジマレイミドのような電
離性放射線架橋助剤、あるいはジビ２
ニルベンゼン、エチレングリコールジメタクリレート、
ジエチレングリコールジメタクリレート、ポリエチレン
グリコールジメタクリレート、トリメチロールプロパン
トリメタクリレート、アリルメタクリレートのような多
官能性ビニルモノマーを配合することができる。このよ
うな化合物により、効率の良い架橋反応が期待できる。In the present invention, the foamable composition constituting the unfoamed partially crosslinked thermoplastic elastomer molded article includes sulfur, p-quinonedioxime, I)-dibenzoylquinonedioxime,
Ionizing radiation crosslinking coagents such as N-methyl-N,4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N,N'-+n-phenylene dimaleimide, or divinylbenzene, ethylene glycol dimethacrylate. ,
Polyfunctional vinyl monomers such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate can be blended. Efficient crosslinking reactions can be expected with such compounds.
本発明においては、上記のような架橋助剤あるいは多官
能性ビニルモノマーは、電離性放射線部分架橋性熱可塑
性エラストマー（Ａ）１００重量部に対し、好ましくは
０．０５〜５．０重量部、さらに好ましくは０．１〜１
．５重量部の量で用いられる。架橋助剤あるいは多官能
性ビニルモノマーの量が５．０重量部を超えると、電離
性放射線の照射線量が多い場合は、架橋反応が過度に進
行して発泡体の熱成形加工性が劣り、一方、電離性放射
線の照射線量が少ない場合は、架橋助剤あるいは多官能
性ビニルモノマーが未反応モノマーとして未発泡の部分
架橋熱可塑性エラストマー成形体中に存在し、この成形
体を発泡成形する際の ３
熱履歴により得られる発泡体の物性が変化する。In the present invention, the crosslinking aid or polyfunctional vinyl monomer as described above is preferably 0.05 to 5.0 parts by weight per 100 parts by weight of the thermoplastic elastomer (A) partially crosslinkable by ionizing radiation. More preferably 0.1 to 1
．． It is used in an amount of 5 parts by weight. If the amount of the crosslinking auxiliary agent or polyfunctional vinyl monomer exceeds 5.0 parts by weight, the crosslinking reaction will proceed excessively and the thermoformability of the foam will be poor if the irradiation dose of ionizing radiation is large. On the other hand, when the irradiation dose of ionizing radiation is small, the crosslinking aid or polyfunctional vinyl monomer exists as an unreacted monomer in the unfoamed partially crosslinked thermoplastic elastomer molded body, and when this molded body is foam-molded, 3. The physical properties of the foam obtained change depending on the thermal history.
したがって、本発明では、上記のような架橋助剤あるい
は多官能性ビニルモノマーの過剰な配合は避けた方が望
ましい。Therefore, in the present invention, it is preferable to avoid excessive blending of the crosslinking aid or polyfunctional vinyl monomer as described above.
また本発明では、未発泡の部分架橋熱可塑性エラストマ
ー成形体を構成する発泡性組成物に、上記電離性放射線
部分架橋性熱可塑性エラストマ（Ａ）および熱分解型発
泡剤（Ｂ）の他に、必要に応じて、さらに発泡助剤、湿
潤剤、粘着（＝Ｉ勾剤、難燃剤などの添加剤を、本発明
の目的を損なわない範囲で配合することができる。Further, in the present invention, in addition to the above-mentioned ionizing radiation partially crosslinkable thermoplastic elastomer (A) and the pyrolyzable blowing agent (B), the foamable composition constituting the unfoamed partially crosslinked thermoplastic elastomer molded article is added. If necessary, additives such as a foaming aid, a wetting agent, an adhesive (=I gradient agent, a flame retardant, etc.) may be added within a range that does not impair the object of the present invention.
発泡助剤としては、具体的には、ステアリン酸、ラウリ
ン酸、サリチル酸等の有機酸系助剤、脂肪酸の亜鉛、カ
ルシウム、鉛、バリウム等の金属塩系助剤、尿素系助剤
などの従来公知の発泡助剤が用いられる。Examples of foaming aids include organic acid aids such as stearic acid, lauric acid, and salicylic acid; metal salt aids such as fatty acid zinc, calcium, lead, and barium; and conventional foaming aids such as urea aids. Known foaming aids are used.
湿潤剤としては、具体的には、ＤＯＰＳＤＢＰ。Specifically, the wetting agent is DOPSDBP.
ＤＩＤＰ、塩素化パラフィン、ポリブテン、流動パラフ
ィン、グリセリンなどの従来公知の湿潤剤が用いられる
。Conventionally known wetting agents such as DIDP, chlorinated paraffin, polybutene, liquid paraffin, and glycerin are used.
４
粘着付与剤としては、塩素化パラフィン、ポリブテン、
流動パラフィン、オイル等の実質的に炭化水素化合物で
ある化合物、ロジン、テルペン樹脂、石油樹脂などの従
来公知の粘着付与剤が用いられる。4 Tackifiers include chlorinated paraffin, polybutene,
Conventionally known tackifiers such as liquid paraffin, compounds that are essentially hydrocarbon compounds such as oil, rosin, terpene resins, and petroleum resins are used.
難燃剤としては、トリクロロエチルフォスファイト、テ
トラキス（２−クロロエチル）エチレンジフォスフオネ
ートなどの液状ないし半固体状の化合物が用いられる。As the flame retardant, liquid or semi-solid compounds such as trichloroethyl phosphite and tetrakis(2-chloroethyl)ethylene diphosphonate are used.
塩素化パラフィン、ポリブテン等の実質的に炭化水素化
合物である化合物、ロジン、テルペン樹脂、石油樹脂、
さらに、フォスファイト、フオスフォネートなどの燐系
難燃剤を用いることにより、防水性、柔軟性および他の
材料表面に対する密着性を向上させることができ、本発
明の部分架橋熱可塑性エラストマー発泡体を防水発泡シ
ール材として利用することができる。Compounds that are essentially hydrocarbon compounds such as chlorinated paraffins and polybutenes, rosins, terpene resins, petroleum resins,
Furthermore, by using a phosphorus-based flame retardant such as phosphite or phosphonate, waterproofness, flexibility, and adhesion to other material surfaces can be improved, making the partially crosslinked thermoplastic elastomer foam of the present invention waterproof. It can be used as a sealing material.
また本発明では、未発泡の部分架橋熱可塑性エラストマ
ー成形体を構成する発泡性組成物に、従来公知の耐熱安
定剤、耐候安定剤、帯電防止剤、５
顔料、染料、充填剤、核剤、滑剤、スリ・ツブ剤、ブロ
ッキング防止剤などの添加剤を、本発明の目的を損なわ
ない範囲で配合することができ、る。In addition, in the present invention, the foamable composition constituting the unfoamed partially crosslinked thermoplastic elastomer molded article includes conventionally known heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, pigments, dyes, fillers, nucleating agents, Additives such as lubricants, slipping agents, anti-blocking agents, etc. can be added to the extent that they do not impair the purpose of the present invention.
耐熱安定剤としては、フェノール系、サルファイド系、
フェニルアルカン系、フォスファイト系、アミン系安定
剤のような従来公知の耐熱安定剤が用いられる。As heat-resistant stabilizers, phenol type, sulfide type,
Conventionally known heat-resistant stabilizers such as phenylalkane-based, phosphite-based, and amine-based stabilizers are used.
顔料としては、具体的には、カーボンブラック、酸化チ
タン、亜鉛華、ベンガラ、群青、紺青、アゾ顔料、ニト
ロソ顔料、レーキ顔料、フタロシアニン顔料などの従来
公知の顔料が用いられる。As the pigment, specifically, conventionally known pigments such as carbon black, titanium oxide, zinc white, red iron oxide, ultramarine blue, navy blue, azo pigment, nitroso pigment, lake pigment, and phthalocyanine pigment are used.
充填剤としては、具体的には、炭酸カルシウム、ケイ酸
カルシウム、クレー カオリン、タルク、シリカ、ケイ
ソウ土、雲母粉、アスベスト、アルミナ、硫酸バリウム
、硫酸アルミニウム、硫酸カルシウム、二硫化モリブデ
ン、グラファイト、ガラス繊維、ガラス球、シラスバル
ーン、カーボン繊維などが、発泡性組成物の流動性およ
びゴム的性質を損なわない範囲で用いられる。Specific fillers include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, and glass. Fibers, glass spheres, glass balloons, carbon fibers, etc. may be used within the range that does not impair the fluidity and rubbery properties of the foamable composition.
本発明の部分架橋熱可塑性エラストマー発泡体 ６
におけ４）部分架橋熱可塑性エラストマーの架橋度は、
下記の方法によって測定されたゲル分率（熱キシレン、
１３０℃）で２〜９０％、好ましくは１０〜７０％、さ
らに好ましくは１５〜６０％の範囲である。4) The degree of crosslinking of the partially crosslinked thermoplastic elastomer in the partially crosslinked thermoplastic elastomer foam 6 of the present invention is:
Gel fraction (thermal xylene,
(130°C), the range is 2 to 90%, preferably 10 to 70%, and more preferably 15 to 60%.
熱キシレン抽出ゲル分の測定は、次のようにして行なわ
れる。すなわち試料ペレット（各ペレットの大きさ：
３＋ｎｍＸ ３ｍｍＸ ３ｍｍ）を約０．３ｇ精秤し、
この重量を初期重量（Ｘ）とする。The thermal xylene extracted gel content is measured as follows. i.e. sample pellets (size of each pellet:
Weigh out approximately 0.3g of 3+nmX 3mmX 3mm),
This weight is defined as the initial weight (X).
次にこの試料ペレットを、密閉容器中で８０ｍ１の沸騰
キシレン中に５時間浸漬した後、３２５メツシユのスク
リーンで濾過し、次いでスクリーン上の残渣を風乾した
後、８０℃で５時間真空乾燥し、この乾燥残渣の量を最
終重量（Ｙ）とする。Next, this sample pellet was immersed in 80 ml of boiling xylene in a closed container for 5 hours, filtered through a 325 mesh screen, air-dried the residue on the screen, and then vacuum-dried at 80°C for 5 hours. The amount of this dry residue is defined as the final weight (Y).
なお、熱可塑性エラストマー中に熱キシレン不溶性の充
填剤、顔料なとが含まれている場合には、試料ペレット
の重量および乾燥残渣の重量からこれらの熱キシレン不
溶性の充填剤、顔料などの重量を減じた重量をそれぞれ
初期型ｆｆｉ （Ｘ）および最終重量（Ｙ）とする。If the thermoplastic elastomer contains heat xylene insoluble fillers, pigments, etc., calculate the weight of these heat xylene insoluble fillers, pigments, etc. from the weight of the sample pellet and the weight of the dry residue. Let the reduced weight be the initial type ffi (X) and the final weight (Y), respectively.
これらの初期重量（Ｘ）および最終型ｆｆｉ （Ｙ）７
から、熱キシレン抽出ゲル分は下記式によって決定され
る。From these initial weights (X) and final form ffi (Y)7, the hot xylene extracted gel content is determined by the following formula.
最終重量（Ｙ）
熱キシレン抽出ゲル分（％）＝
Ｘ１００初期重量（Ｘ）
熱可塑性エラストマーのゲル分率が上記のような範囲に
ある部分架橋熱可塑性エラストマー発泡体は、ゴム弾性
および耐熱性に優れている。Final weight (Y) Hot xylene extracted gel content (%) =
X100 Initial Weight (X) A partially crosslinked thermoplastic elastomer foam in which the gel fraction of the thermoplastic elastomer is within the above range has excellent rubber elasticity and heat resistance.
上記のような部分架橋熱可塑性エラストマー発泡体は、
以゛下のような本発明に係る製造方法に従って得られる
。Partially crosslinked thermoplastic elastomer foams as described above are
It is obtained according to the manufacturing method according to the present invention as described below.
本発明に係る製造方法の第１工程として、（ａ）電離性
放射線架橋型オレフィン系共重合体ゴム１００〜１０重
量部、（ｂ）電離性放射線架橋型オレフィン系プラスチ
ック０〜９０重量部および（ｃ）電離性放射線分解型オ
レフィン系プラスチック１〜９０重量部［但し、（ａ）
成分、（ｂ）成分および（ｃ）成分の合計重量は１００
重量部とする］からなる、メルトインデックス０．１〜
１００ｇ／］０分の電離性放射線部分架橋性熱可塑性エ
ラ８
ストマー（Ａ）に、熱分解型発泡剤（Ｂ）を、熱分解型
発泡剤（Ｂ）の分解温度以下の温度で溶融混練して得ら
れる発泡性組成物を、所定の形状に成形した後電離性放
射線を照射して未発泡の部分架橋熱可塑性エラストマー
成形体を得る。As the first step of the production method according to the present invention, (a) 100 to 10 parts by weight of ionizing radiation crosslinkable olefin copolymer rubber, (b) 0 to 90 parts by weight of ionizing radiation crosslinkable olefin plastic, and ( c) 1 to 90 parts by weight of ionizing radiolytic olefin plastic [However, (a)
The total weight of component (b) component and (c) component is 100
Parts by weight], melt index 0.1~
100g/] 0 minute ionizing radiation partially crosslinkable thermoplastic elastic 8 A pyrolytic blowing agent (B) is melt-kneaded into a blower (A) at a temperature below the decomposition temperature of the pyrolytic blowing agent (B). The foamable composition obtained is molded into a predetermined shape and then irradiated with ionizing radiation to obtain an unfoamed partially crosslinked thermoplastic elastomer molded article.
上記の電離性放射線部分架橋性熱可塑性エラストマー（
Ａ）の製造方法は、前述のとおりである。The above ionizing radiation partially crosslinkable thermoplastic elastomer (
The manufacturing method of A) is as described above.
上記の溶融混練の方法としては、たとえば電離性放射線
部分架橋性熱可塑性エラストマー（Ａ）のペレットと熱
分解型発泡剤（Ｂ）とを、−旦Ｖ型ブラベンダー タン
ブラーブラベンダー リボンブラベンダー、ヘンシエル
ブラベンダーなどの公知の混練機を用いて混合した後、
必要であれば押出機、ミキシングロール、ニーダ−、バ
ンバリーミキサ−なとて混練する。混練は熱分解型発泡
剤（Ｂ）の分解温度以下の温度で行なうのが良い。また
、発泡助剤、湿潤剤、耐候安定剤、耐熱安定剤、煮化防
止剤、着色剤などの添加剤を、この溶融混純のいずれの
段階においても配合することができる。The above melt-kneading method includes, for example, mixing pellets of the thermoplastic elastomer (A) partially crosslinkable with ionizing radiation and the pyrolytic blowing agent (B). After mixing using a known kneader such as lavender,
If necessary, knead using an extruder, mixing roll, kneader, or Banbury mixer. The kneading is preferably carried out at a temperature below the decomposition temperature of the thermally decomposable blowing agent (B). Additionally, additives such as foaming aids, wetting agents, weathering stabilizers, heat stabilizers, anti-boiling agents, and coloring agents can be added at any stage of the melt-mixing process.
９
次いで、上記のようにして得られた混練物に、必要に応
じて架橋助剤、加硫促進剤なとを加えて、タンブラーブ
ラベンダー Ｖ型ブラベンダー、ヘンシェルミキサーな
どの公知の混線機で、好ましくは５０℃以下の温度で均
一に混線した後、この混線物を、開放型のミキシングロ
ールあるいは非開放型のバンバリーミキサ−１押出機、
ニーダ−連続ミキサーなどの公知の混練機で混線分散さ
せる。混練は熱分解型発泡剤の分解温度以下の温度で行
なうのが望ましい。9 Next, a crosslinking aid, a vulcanization accelerator, etc. are added to the kneaded product obtained as described above, if necessary, and the mixture is mixed with a known mixing machine such as a tumbler Brabender, V-type Brabender, or Henschel mixer. After uniform mixing, preferably at a temperature of 50° C. or lower, the mixed material is passed through an open mixing roll or a non-open Banbury mixer 1 extruder,
Cross-dispersion is performed using a known kneader such as a kneader-continuous mixer. The kneading is preferably carried out at a temperature below the decomposition temperature of the thermally decomposable blowing agent.
次に、上記のように溶融混練して得られる発泡性組成物
を、熱分解型発泡剤（Ｂ）が分解しない温度で所定の形
状、たとえばシート状、フィルム状、異形状、パイプ状
、チューブ状に成形して未架橋未発泡の熱可塑性エラス
トマー成形体を得る。Next, the foamable composition obtained by melt-kneading as described above is heated to a temperature at which the pyrolyzable blowing agent (B) does not decompose and is shaped into a predetermined shape, such as a sheet, a film, an irregular shape, a pipe, or a tube. A non-crosslinked, non-foamed thermoplastic elastomer molded product is obtained.
上記成形は、熱プレス、射出成形機、押出機、カレンダ
ーロールなどの従来公知の成形機を用いて行なうことが
できる。The above-mentioned molding can be performed using a conventionally known molding machine such as a hot press, an injection molding machine, an extruder, or a calender roll.
また、本発明においては、前記電離性放射線部分架橋性
熱可塑性エラストマー（Ａ）の（ａ）０
（ｂ）および（ｃ）の各成分または（ａ）、（ｂ）、（
ｃ）および（ｄ）の各成分の溶融混練、電離性放射線部
分架橋性熱可塑性エラストマー（Ａ）と熱分解型発泡剤
（Ｂ）などの添加剤との溶融混練、さらに、この溶融混
練によって得られる発泡性組成物の成形に至る工程を、
射出成形機、単軸押出機、多軸押出機などを用いて一段
階で行なうことができる。Further, in the present invention, each component (a) 0 (b) and (c) of the ionizing radiation partially crosslinkable thermoplastic elastomer (A) or (a), (b), (
Melt-kneading of each component c) and (d), melt-kneading of the ionizing radiation partially crosslinkable thermoplastic elastomer (A) and additives such as a pyrolytic blowing agent (B), and further melt-kneading of the components obtained by this melt-kneading. The process leading to the molding of the foamable composition is
It can be carried out in one step using an injection molding machine, a single screw extruder, a multi-screw extruder, etc.
次に、上記のようにして得られる未架橋未発泡の熱可塑
性エラストマー成形体に電離性放射線を照射して未発泡
の部分架橋熱可塑性エラストマー成形体を得る。本発明
で用いられる電離性放射線としては、たとえばα線、β
線、γ線、Ｘ線、中性子線、電子線などが適当であり、
電離性放射線の照射量は、吸収線量で０．１〜１０．０
Ｍｒａｄであり、特に０．２５〜５．０Ｍｒａｄの範囲
内であることが好ましい。上記電離性放射線のうち、本
発明では、電子線およびγ線が好ましく用いられる。Next, the uncrosslinked, unfoamed thermoplastic elastomer molded article obtained as described above is irradiated with ionizing radiation to obtain an unfoamed, partially crosslinked thermoplastic elastomer molded article. Ionizing radiation used in the present invention includes, for example, α rays, β rays,
rays, gamma rays, X-rays, neutron beams, electron beams, etc. are suitable;
The irradiation dose of ionizing radiation is 0.1 to 10.0 in terms of absorbed dose.
Mrad, particularly preferably within the range of 0.25 to 5.0 Mrad. Among the above-mentioned ionizing radiations, electron beams and gamma rays are preferably used in the present invention.
次に、本発明に係る製造方法の第２工程として、上記工
程により得られる未発泡の部分架橋熱可塑１
性エラストマー成形体を、熱分解型発泡剤（Ｂ）の分解
温度以上の温度で加熱して発泡させる。Next, as the second step of the production method according to the present invention, the unfoamed partially crosslinked thermoplastic elastomer molded article obtained in the above step is heated at a temperature equal to or higher than the decomposition temperature of the pyrolytic blowing agent (B). to foam.
上記発泡は、通常、未発泡の部分架橋熱可塑性エラスト
マー成形体を、熱風循環加熱、ソルト浴加熱、赤外線加
熱、熱プレスによる加熱などの従来公知の加熱方法で、
未発泡の部分架橋熱可塑性エラストマー成形体中に含ま
れる熱分解型発泡剤（Ｂ）を加熱分解して発泡させると
いう方法が採られる。The above-mentioned foaming is usually carried out by heating the unfoamed partially crosslinked thermoplastic elastomer molded article by a conventionally known heating method such as hot air circulation heating, salt bath heating, infrared heating, or heating using a hot press.
A method is adopted in which the thermally decomposable foaming agent (B) contained in the unfoamed partially crosslinked thermoplastic elastomer molded article is thermally decomposed and foamed.
発明の効果
本発明に係る部分架橋熱可塑性エラストマー発泡体は、
特定の電離性放射線部分架橋性熱可塑性エラストマー（
Ａ）と、熱分解型発泡剤（Ｂ）とからなる発泡性組成物
で構成されている未発泡の部分架橋熱可塑性エラストマ
ー成形体を発泡させてなる発泡体であるので、耐熱性、
耐薬品性、引張り特性、柔軟性、ゴム弾性に優れるとと
もに、熱成形加工性に優れるという効果がある。Effects of the Invention The partially crosslinked thermoplastic elastomer foam according to the present invention has
Certain ionizing radiation partially crosslinkable thermoplastic elastomers (
Since it is a foam formed by foaming an unfoamed partially crosslinked thermoplastic elastomer molded article composed of a foamable composition consisting of A) and a pyrolyzable foaming agent (B), it has excellent heat resistance,
It has excellent chemical resistance, tensile properties, flexibility, and rubber elasticity, as well as excellent thermoforming processability.
また、本発明に係る製造方法によれば、上記のような効
果を有する部分架橋熱可塑性エラスト２
マー発泡体が得られるとともに、３倍以下という低発泡
倍率および３倍を超える高発泡倍率の部分架橋熱可塑性
エラストマー発泡体が得られるという効果がある。Further, according to the manufacturing method of the present invention, a partially crosslinked thermoplastic elastomer foam having the above-mentioned effects can be obtained, and a part with a low expansion ratio of 3 times or less and a high expansion ratio of more than 3 times can be obtained. The effect is that a crosslinked thermoplastic elastomer foam is obtained.
本発明の部分架橋熱可塑性エラストマー発泡体は、３倍
以下という低発泡倍率から３倍を超える高発泡倍率の発
泡体まであり、耐熱性、耐候性、耐薬品性、引張特性、
柔軟性、ゴム弾性のみならず、熱成形加工性に優れてお
り、この特性を活かして、車輌等の内外装材、車輌、家
電製品、土木建築等のシール材、および吸音遮音材の用
途に広範に適用できる。たとえば、車輌内外装材の用途
では、高発泡倍率の発泡体が、上述した発泡体の緒特性
の他に、感触性、クツション性、復元性、吸音性等の特
性を有するので、ドア表皮材、天井材、座席シートレザ
ーなどに好適であり、また低発泡倍率の発泡体は、ダツ
シュボード、ウェザ−ストリップなどに使用できる。ま
た、これらの用途に本発明の発泡体を用いる場合に、本
発明の発泡体が熱成形加工性に優れているので、真空成
形、３
圧空成形、熱プレス成形、ウエルダー加工成形などで複
雑な形状の成形が容易に行なえる。またシール材の用途
では、低発泡体から高発泡体まで、車輌、家電製品、土
木建築等の防水、防風、防音に使用されるシール材に適
用でき、吸音遮音材の用途では、特に自動車エンジンル
ームの吸音材等の耐熱性吸音遮音材に好適である。The partially crosslinked thermoplastic elastomer foam of the present invention ranges from a low expansion ratio of 3 times or less to a high expansion ratio of over 3 times, and has excellent heat resistance, weather resistance, chemical resistance, tensile properties,
It not only has flexibility and rubber elasticity, but also has excellent thermoforming processability. Taking advantage of this property, it can be used as interior and exterior materials for vehicles, sealing materials for vehicles, home appliances, civil engineering construction, etc., and sound absorbing and sound insulating materials. Widely applicable. For example, in applications for vehicle interior and exterior materials, high expansion ratio foams have properties such as feel, cushioning, resilience, and sound absorption, in addition to the above-mentioned properties of foam, so they can be used as door skin materials. The foam is suitable for materials such as ceiling materials, seat leather, etc., and the foam with a low expansion ratio can be used for dash boards, weather strips, etc. In addition, when using the foam of the present invention for these applications, the foam of the present invention has excellent thermoforming processability, so it can be used in complex processes such as vacuum forming, pressure forming, hot press forming, welding process forming, etc. Shapes can be easily formed. In addition, in the application of sealing materials, from low-foam to high-foam materials, it can be applied to sealing materials used for waterproofing, windproofing, and soundproofing of vehicles, home appliances, civil engineering construction, etc.; Suitable for heat-resistant sound absorbing and sound insulating materials such as room sound absorbing materials.
以下、本発明を実施例により説明するが、本発明はこれ
ら実施例に限定されるものではない。なお、実施例にお
ける発泡体の成形および基本物性の評価は、下記の条件
および評価方法に従って行なった。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. In addition, molding of the foam and evaluation of basic physical properties in Examples were performed according to the following conditions and evaluation methods.
［発泡体の成形］
（１）押出成形
下記の装置、条件で未架橋未発泡の熱可塑性エラストマ
ーのシートを押出成形した。[Molding of foam] (1) Extrusion molding A sheet of uncrosslinked and unfoamed thermoplastic elastomer was extrusion molded using the following equipment and conditions.
成形機：単軸押出成形機［味日本製鋼所製、型番Ｐ４０
−２５ＡＢ 、 ４０ｍｍφ］、２軸押出成形機［池貝
鉄工■製、型番
ＰＣＭ−３０，３０ｍｍφ］
４
成形温度＝１６０℃
成形速度二０．１〜１０ｍ／分
（２）発泡成形
下記の装置、条件で未架橋未発泡の熱可塑性エラストマ
ーのシートを発泡成形した。Molding machine: Single screw extrusion molding machine [manufactured by Aji Nippon Steel, model number P40
-25AB, 40mmφ], twin-screw extrusion molding machine [manufactured by Ikegai Iron Works ■, model number PCM-30, 30mmφ] 4 Molding temperature = 160°C Molding speed 2 0.1 to 10 m/min (2) Foam molding The following equipment and conditions A sheet of uncrosslinked and unfoamed thermoplastic elastomer was foam-molded.
発泡炉：熱風循環炉［ミクロ電子■製、型番ＭＩＩＶ−
０８Ｌ］
発泡加熱温度：２００〜２３０℃
加熱時間：２分３０秒
［基本物性の評価方法］
（１）発泡倍率
未発泡品の密度０．８９ｇ／ｃｎｔを発泡成形品の見か
け密度で除した値を発泡倍率とする。Foaming furnace: Hot air circulation furnace [manufactured by Micro Denshi ■, model number MIIV-
08L] Foaming heating temperature: 200-230°C Heating time: 2 minutes 30 seconds [Evaluation method of basic physical properties] (1) Expansion ratio Value obtained by dividing the density of unfoamed product, 0.89 g/cnt, by the apparent density of foamed molded product is the foaming ratio.
（２）引張り特性
発泡体の破断点抗張力、破断点伸びを、ＪＩＳ−に−６
３旧に規定されている測定方法に準じて測定する。(2) Tensile properties: Tensile strength at break and elongation at break of foam according to JIS-6
3. Measure according to the measurement method prescribed in the old regulations.
（３）柔軟性 発泡体の柔軟性は、柔軟性指数（Ｎ）で評価する。(3) Flexibility The flexibility of the foam is evaluated by the flexibility index (N).
Ｎ＝（２５％圧縮強さ）×（発泡倍率）５
ここで、２５％圧縮強さは、Ｊ Ｉｓ−に−Ｂ７［１７
−１９７６に規定されている測定方法に準じて測定し、
また発泡倍率は発泡体の見かけ密度の逆数をもって表わ
す。N = (25% compressive strength) x (expansion ratio) 5 Here, the 25% compressive strength is J Is- -B7[17
- Measured according to the measurement method specified in 1976,
Further, the expansion ratio is expressed as the reciprocal of the apparent density of the foam.
（４）平均気泡断面径
５０倍顕微鏡にて、３．３ｍｍ角あたりのセル数が、ｎ
個のとき、平均気泡断面径−（Ｌ３） ２／πｎて表わ
す。(4) Average cell cross-sectional diameter Under a microscope with a magnification of 50 times, the number of cells per 3.3 mm square was n
, it is expressed as the average bubble cross-sectional diameter - (L3) 2/πn.
（５）熟成形加工性
発泡体の熱成形加工性は、真空成形を下記の成形条件に
従って行ない、その成形性で評価する。(5) Aged processability The thermoforming processability of the foam is evaluated by performing vacuum forming according to the following forming conditions.
（真空成形の条件）
表面温度：２６０℃
真空成形時間：１００秒
（評価の仕方）
深絞り成形によるシート切断の有無、シワなどの外観の
変化を調べる。(Vacuum forming conditions) Surface temperature: 260°C Vacuum forming time: 100 seconds (Evaluation method) Examine whether the sheet is cut due to deep drawing and changes in appearance such as wrinkles.
熱成形加工性が優れているものを◎、良好なものを０１
やや良好なものを△、良くないものを×で表わす。Those with excellent thermoforming processability are ◎, and those with good thermoformability are 01.
Fairly good results are represented by △, and poor results are represented by ×.
６
（６）加熱司法変化
発泡体の加熱寸法変化は、Ｊ Ｉｓ−に−Ｂ７［１７に
規定されている測定法に準じて、熱処理による縦、横、
厚さ方向のそれぞれの熱収縮率をもって評価する。6 (6) Heating dimensional changes of foamed materials are determined by heat treatment in accordance with the measuring method specified in J Is-B7 [17].
Evaluate based on each heat shrinkage rate in the thickness direction.
測定試料（発泡体）に縦、横１．Ｏｃ＋ｎ角の正方形の
印を付けて、厚さを測定した後、８０℃、２２時間熱風
オーブン中で熱処理する。次いで、試料を室温に冷却し
た後、縦、横、厚さの寸法を測定し、この処理による寸
法変化（熱収縮率）を求める。Vertical and horizontal 1. After marking a square with Oc+n angles and measuring the thickness, heat treatment is performed in a hot air oven at 80° C. for 22 hours. Next, after cooling the sample to room temperature, the length, width, and thickness dimensions are measured to determine the dimensional change (thermal shrinkage rate) due to this treatment.
（７）成形品の外観
脱泡による表面に凹凸の有無について観察し、表面が平
滑なものを５、表面の凹凸が所々に認められるものを３
、表面の脱泡による膚荒れが顕著なものを１とし、４は
５と３の中間、２は３と１の中間の表面状態であること
を示す。(7) Appearance of the molded product Observe the presence or absence of irregularities on the surface due to degassing. Those with smooth surfaces are ranked 5, and those with irregularities observed here and there are ranked 3.
, 1 indicates that the surface is noticeably rough due to defoaming, 4 indicates a surface condition between 5 and 3, and 2 indicates a surface condition between 3 and 1.
実施例１
分子量３２０００ （Ｍｎ ） 、分子量分布９．３（
Ｍｗ／Ｍｎ）、ムーニー粘度ＭＬ （１００℃）■
＋４
６５、ヨウ素価１２のエチレン−プロピレンノル７
ボルネン共重合体ゴム（以下Ｅ ｌ）Ｄ Ｈと略す）６
０重量部、メルトインデックス（ＡＳＴＭ−Ｄ−１２３
８−８５７゜２３０℃）３．０ｇ／１０分、密度０．９
１０ｇ／−のポリプロピレン（以下１）１〕と略す）１
０重量部、メルトインデックス（ＡＳＴＭ−Ｄ−１２３
８−６５Ｔ、 １９０℃）１．６ｇ／１０分、密度０．
９２］、ｇ／−の低密度ポリエチレン（以下ＬＤＰＥと
略す）２０重量部およびナフテン（パラフィン）系プロ
セスオイル（以下オイルと略す）１０重量部の発泡体基
材となる素原料をヘンシェルミキサーで混合した後、１
６０℃で２軸押出機により、第１混練部で溶融混練し、
次いで、第１混練部と第２混線部の間から発泡剤のアゾ
シカ−ボンアミド（以下ＡＤＣＡと略す）１０重量部、
第２混練部の後の注入口から架橋助剤のトリアリルシア
ヌレート（以下ＴＡＣと略す）０．５重量部を定量的に
供給して混練した。Example 1 Molecular weight 32000 (Mn), molecular weight distribution 9.3 (
Mw/Mn), Mooney viscosity ML (100℃) ■
+4 65, ethylene-propylene nor7 bornene copolymer rubber with an iodine value of 12 (hereinafter abbreviated as El DH) 6
0 parts by weight, melt index (ASTM-D-123
8-857゜230℃) 3.0g/10min, density 0.9
10g/- of polypropylene (hereinafter abbreviated as 1) 1) 1
0 parts by weight, melt index (ASTM-D-123
8-65T, 190°C) 1.6g/10min, density 0.
92], 20 parts by weight of low-density polyethylene (hereinafter abbreviated as LDPE) and 10 parts by weight of naphthene (paraffin)-based process oil (hereinafter abbreviated as oil) were mixed in a Henschel mixer. After that, 1
Melt-kneaded in the first kneading section with a twin-screw extruder at 60°C,
Next, 10 parts by weight of azocica-bonamide (hereinafter abbreviated as ADCA) as a blowing agent was added between the first kneading section and the second mixing section;
0.5 parts by weight of triallyl cyanurate (hereinafter abbreviated as TAC) as a crosslinking aid was quantitatively supplied from the injection port after the second kneading section and kneaded.
このようにして得られた混練物をリップ幅１ ｍ −。The kneaded product thus obtained was prepared with a lip width of 1 m.
リップ厚３ ｍｍのフラットダイスからシート状に押出
して未架橋未発泡の熱可塑性エラストマーの連続シート
を得た。A continuous sheet of uncrosslinked, unfoamed thermoplastic elastomer was obtained by extruding it into a sheet from a flat die with a lip thickness of 3 mm.
８
次いで、この連続シートにＩＭｒａｄの電子線を照射し
た後、熱風循環炉を用いて２００〜２３０℃で連続シー
トを加熱発泡させてシート状の発泡体を得た。8 Next, this continuous sheet was irradiated with an IMrad electron beam, and then the continuous sheet was heated and foamed at 200 to 230°C using a hot air circulation furnace to obtain a sheet-like foam.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例２
実施例１において、フラットダイスの代わりに、丸状の
異形ダイス（ノズル径５ ｍｍφ）を用いた以外は、実
施例１と同様にして、丸棒の異形状の発泡体を得た。Example 2 A round bar shaped foam was obtained in the same manner as in Example 1, except that a round irregularly shaped die (nozzle diameter 5 mmφ) was used instead of the flat die. .
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例３
実施例１における発泡体基材となる素原料をバンバリー
ミキサ−により混練した後、この混練物をロールに通し
、シートカッターによりペレットを製造した。次いで、
このペレット１ｏｏ重量部とＡＤＣＡ １０重量部と
ＴＡＣｏ、５重量部とをヘンシェルミキサーにより混合
した後、この混合物を単軸押出成形機を用い、成形温度
１６０℃でシート状に連続で押出して幅１ ｍ ｓ厚み
３關９
の未架橋未発泡熱可塑性エラストマーの連続シートを得
た。Example 3 After kneading the raw materials for the foam base material in Example 1 using a Banbury mixer, the kneaded product was passed through a roll and pellets were produced using a sheet cutter. Then,
After mixing 10 parts by weight of these pellets, 10 parts by weight of ADCA, and 5 parts by weight of TACo using a Henschel mixer, this mixture was continuously extruded into a sheet shape using a single-screw extruder at a molding temperature of 160°C. A continuous sheet of uncrosslinked, unfoamed thermoplastic elastomer having a thickness of 3 m s and 9 m s was obtained.
次いで、この連続シートにＩＭｒａｄの電子線を照射し
た後、熱風循環炉を用いて２０．０〜２３０℃で連続シ
ートを加熱発泡させてシート状の発泡体を得た。Next, this continuous sheet was irradiated with an IMrad electron beam, and then the continuous sheet was heated and foamed at 20.0 to 230°C using a hot air circulation furnace to obtain a sheet-like foam.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例４
実施例３において、フラットダイスの代わりに、丸状の
異形ダイス（ノズル径５ ｍｍφ）を用いた以外は、実
施例３と同様にして、丸棒の異形状の発泡体を得た。Example 4 A round bar shaped foam was obtained in the same manner as in Example 3, except that a round irregularly shaped die (nozzle diameter 5 mmφ) was used instead of the flat die. .
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例５
実施例１において、ＰＰ、ＬＤＰＥおよびＡＤＣＡの配
合量を、それぞれ３０重量部、０重量部、５重量部とし
た以外は、実施例１と同様にして、シート状の発泡体を
得た。Example 5 A sheet-like foam was obtained in the same manner as in Example 1, except that the amounts of PP, LDPE, and ADCA were changed to 30 parts by weight, 0 parts by weight, and 5 parts by weight, respectively. Ta.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例６
０
実施例５において、フラットダイスの代わりに、丸状の
異形ダイス（ノズル径５ＩＩＩＩＩφ）を用いた以外は
、実施例５と同様にして、丸棒の異形状の発泡体を得た
。Example 6 0 A round bar shaped foam was obtained in the same manner as in Example 5, except that a round irregularly shaped die (nozzle diameter 5IIIφ) was used instead of the flat die. .
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例７
実施例３において、ＰＰ、ＬＤＰＥおよびＡＤＣＡの配
合量を、それぞれ３０重量部、０重量部、５重量部とし
た以外は、実施例３と同様にして、シート状の発泡体を
得た。Example 7 A sheet-like foam was obtained in the same manner as in Example 3, except that the amounts of PP, LDPE, and ADCA were 30 parts by weight, 0 parts by weight, and 5 parts by weight, respectively. Ta.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例８
実施例７において、フラットダイスの代わりに、丸状の
異形ダイス（ノズル径５ ｍｒａφ）を用いた以外は、
実施例７と同様にして、丸棒の異形状の発泡体を得た。Example 8 In Example 7, except that a round irregularly shaped die (nozzle diameter 5 mraφ) was used instead of the flat die.
In the same manner as in Example 7, a foam having an irregular shape of a round bar was obtained.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例９
実施例１において、ＡＤＣＡの配合量を２重量部とした
以外は、実施例１と同様にして、シート１
状の発泡体を得た。Example 9 A sheet-shaped foam was obtained in the same manner as in Example 1, except that the amount of ADCA was changed to 2 parts by weight.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例１０
実施例９において、フラットダイスの代わりに、丸状の
異形ダイス（ノズル径５龍φ）を用いた以外は、実施例
９と同様にして、丸棒の異形状の発泡体を得た。Example 10 A round bar shaped foam was obtained in the same manner as in Example 9, except that a round irregularly shaped die (nozzle diameter 5 mm) was used instead of the flat die. Ta.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例１１
ＥＰＤＭ ６０重量部、メルトインデックス（ＡＳＴ
Ｍ−Ｄ−６５Ｔ、 ２３０℃）２．０ｇ／１０分、密度
０．９１０ｇ／−のＰＰ １０重量部、ＬＤＰＥ２０
重量部およびオイル１０重量部の発泡体基材となる素原
料を用いて、バンバリーミキサ−によりペレットを製造
した。Example 11 EPDM 60 parts by weight, melt index (AST
M-D-65T, 230°C) 2.0 g/10 min, 10 parts by weight of PP with a density of 0.910 g/-, LDPE20
Pellets were produced using a Banbury mixer using the raw material for the foam base material containing 10 parts by weight of oil and 10 parts by weight of oil.
次いで、ＴＡＣｏ、５重量部をジビニルベンゼン０．５
重量部に溶融分散させた溶液を上記ペレット表面に均一
に付着させた後、このペレットを押出機で窒素雰囲気下
、２００℃で押出しした。Next, 5 parts by weight of TACo was added to 0.5 parts by weight of divinylbenzene.
After the solution melted and dispersed in parts by weight was uniformly adhered to the surface of the pellet, the pellet was extruded at 200° C. under a nitrogen atmosphere using an extruder.
以上の方法で得た熱可塑性エラストマー１００重２
置部とＡＤＣＡＩ重量部とをブレンダーミキサーにより
混合して得たペレットを、単軸押出成形機を用い、成形
温度１６０℃でシート状に連続で押出して幅１ ｍ ｓ
厚み３ ｍｍの未架橋未発泡熱可塑性エラストマーの連
続シートを得た。Pellets obtained by mixing 100 parts by weight of the thermoplastic elastomer obtained by the above method and 2 parts by weight of ADCAI in a blender mixer are continuously extruded into a sheet shape at a molding temperature of 160°C using a single screw extruder. Width: 1 m s
A continuous sheet of uncrosslinked, unfoamed thermoplastic elastomer having a thickness of 3 mm was obtained.
次いで、この連続シートにＩＭｒａｄの電子線を照射し
た後、熱風循環炉を用いて２００〜２３０℃で連続シー
トを加熱発泡させてシート状の発泡体を得た。Next, this continuous sheet was irradiated with an IMrad electron beam, and then the continuous sheet was heated and foamed at 200 to 230° C. using a hot air circulation furnace to obtain a sheet-like foam.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例１２
実施例１１において、ＡＤＣＡの配合量を５重量部とし
た以外は、実施例１１と同様にして、シート状の発泡体
を得た。Example 12 A sheet-like foam was obtained in the same manner as in Example 11, except that the amount of ADCA was changed to 5 parts by weight.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例１３
実施例１１において、ＰＰおよびＬＤＰＥの配合量を、
それぞれ３０重量部、０重量部とした以外は、実施例１
１と同様にして、シート状の発泡体を得た。Example 13 In Example 11, the blending amounts of PP and LDPE were
Example 1 except that they were 30 parts by weight and 0 parts by weight, respectively.
A sheet-like foam was obtained in the same manner as in 1.
３ 得られた発泡体の基本物性の評価を表１に示す。3 Table 1 shows the evaluation of the basic physical properties of the obtained foam.
実施例１４
実施例１３において、ＡＤＣＡの配合量を５重量部とし
た以外は、実施例１３と同様にして、シート状の発泡体
を得た。Example 14 A sheet-like foam was obtained in the same manner as in Example 13, except that the amount of ADCA was changed to 5 parts by weight.
得られた発泡体の基本物性の評価を表１に示す。Table 1 shows the evaluation of the basic physical properties of the obtained foam.
４
表１
表１
（続
き）
［註Ｈａ）：電離性放射線架橋型オレフィン系共重合ゴ
ム（ｂ） ：電離性放射線架橋型オレフィン系プラス
チック（ｃ）：電離性放射線分解型オレフィン系プラス
チック（ｄ）：鉱物油
ＡＤＣＡ：アゾジカーボンアミド
ＴＡＣ： ）リアリルシアヌレ−１・
５
６
表
１
（続
７
き）
実施例１５
実施例１において、ＥＰＤＭを５５重量部、ＰＰを１５
重量部、メルトインデックス（ＡＳＴＭ−Ｄ−１２３８
−Ｂ５Ｔ、 １９０℃）１．９ｇ／ｌ、０分、密度０．
９２０ｇ／ｃＪのＬＤＰＥを２５重量部、オイルを５重
量部、ＡＤＣＡを５重量部、ＴＡＣの代りにトリメチロ
ールプロパントリメタクリレ−１・を０．Ｓｆｆｌｆｍ
部とし、１． 、 ５ Ｍ ｒａｄの電子線を照射した
以外は、実施例１と同様にして、シート状の発泡体を得
た。4 Table 1 Table 1 (continued) [Note Ha): Ionizing radiation crosslinkable olefin copolymer rubber (b): Ionizing radiation crosslinking olefin plastic (c): Ionizing radiation decomposition type olefin plastic (d) : Mineral oil ADCA: Azodicarbonamide TAC: ) Realyl cyanuride-1.56 Table 1 (continued) Example 15 In Example 1, 55 parts by weight of EPDM and 15 parts by weight of PP were added.
Parts by weight, melt index (ASTM-D-1238
-B5T, 190°C) 1.9 g/l, 0 min, density 0.
25 parts by weight of 920 g/cJ LDPE, 5 parts by weight of oil, 5 parts by weight of ADCA, and 0.0 parts of trimethylolpropane trimethacrylate-1 instead of TAC. Sfflfm
Section 1. A sheet-like foam was obtained in the same manner as in Example 1, except that irradiation with an electron beam of 5 M rad was performed.
得られた発泡体の基本物性の評価を表２に示す。Table 2 shows the evaluation of the basic physical properties of the obtained foam.
実施例１６
実施例１５において、ＥＰＤＭ、ＰＰおよびＬＤＰＥの
配合量を、それぞれ６５重量部、１０重量部、２０重量
部とした以外は、実施例１５と同様にして、シート状の
発泡体を得た。Example 16 A sheet-like foam was obtained in the same manner as in Example 15, except that the amounts of EPDM, PP, and LDPE were changed to 65 parts by weight, 10 parts by weight, and 20 parts by weight, respectively. Ta.
得られた発泡体の基本物性の評価を表２に示す。Table 2 shows the evaluation of the basic physical properties of the obtained foam.
実施例１７ 実施例１５において、ＥＰＤＭ、ＰＰ。Example 17 In Example 15, EPDM, PP.
ＬＤＰＥおよびオイルの配合量を、それぞれ７０８
重量部、１０重量部、］Ｏ重量部、１０重量部とした以
外は、実施例１５と同様にして、シート状の発泡体を得
た。A sheet-shaped foam was obtained in the same manner as in Example 15, except that the blending amounts of LDPE and oil were 708 parts by weight, 10 parts by weight, ]O parts by weight, and 10 parts by weight, respectively.
得られた発泡体の基本物性の評価を表２に示す。Table 2 shows the evaluation of the basic physical properties of the obtained foam.
表２ 特ｆｌ’ｌ’出願人 ニル石油化学」１田、代金ｉＪ。Table 2 Special fl’l’ Applicant Nil Petrochemical” Ida, Price iJ.
Claims (1)
ム１００〜１０重量部、（ｂ）電離性放射線架橋型オレ
フィン系プラスチック０〜９０重量部および（ｃ）電離
性放射線分解型オレフィン系プラスチック１〜９０重量
部［但し、（ａ）成分、（ｂ）成分および（ｃ）成分の
合計重量は１００重量部とする］からなる、メルトイン
デックス０．１〜１００ｇ／１０分の電離性放射線部分
架橋性熱可塑性エラストマー（Ａ）と、 熱分解型発泡剤（Ｂ） とからなる発泡性組成物で構成されている未発泡の部分
架橋熱可塑性エラストマー成形体が、発泡してなること
を特徴とする部分架橋熱可塑性エラストマー発泡体。 ２）前記電離性放射線部分架橋性熱可塑性エラストマー
（Ａ）が（ｄ）鉱物油系軟化剤を含むことを特徴とする
請求項第１項に記載の部分架橋熱可塑性エラストマー発
泡体。 ３）（ｄ）鉱物油系軟化剤の配合量が、（ａ）成分、（
ｂ）成分、（ｃ）成分および（ｄ）成分の合計重量１０
０重量部に対し、０〜５０重量部の範囲内の量であるこ
とを特徴とする請求項第２項に記載の部分架橋熱可塑性
エラストマー発泡体。 ４）部分架橋熱可塑性エラストマー発泡体における熱可
塑性エラストマーの架橋度が、ゲル分率（熱キシレン、
１３０℃）で２〜９０％であることを特徴とする請求項
第１項〜第３項のいずれかに記載の部分架橋熱可塑性エ
ラストマー発泡体。 ５）部分架橋熱可塑性エラストマー発泡体の発泡倍率が
３倍を超えていることを特徴とする請求項第１項〜第４
項のいずれかに記載の部分架橋熱可塑性エラストマー発
泡体。 ６）（ａ）電離性放射線架橋型オレフィン系共重合体ゴ
ム１００〜１０重量部、（ｂ）電離性放射線架橋型オレ
フィン系プラスチック０〜９０重量部および（ｃ）電離
性放射線分解型オレフィン系プラスチック１〜９０重量
部［但し、（ａ）成分、（ｂ）成分および（ｃ）成分の
合計重量は１００重量部とする］からなる、メルトイン
デックス０．１〜１００ｇ／１０分の電離性放射線部分
架橋性熱可塑性エラストマー（Ａ）に、熱分解型発泡剤
（Ｂ）を、熱分解型発泡剤（Ｂ）の分解温度以下の温度
で溶融混練して得られる発泡性組成物を、所定の形状に
成形した後電離性放射線を照射して未発泡の部分架橋熱
可塑性エラストマー成形体を得る工程と、 該未発泡の部分架橋熱可塑性エラストマー成形体を、熱
分解型発泡剤（Ｂ）の分解温度以上の温度で加熱して発
泡させる工程 とからなることを特徴とする部分架橋熱可塑性エラスト
マー発泡体の製造方法。 ７）前記電離性放射線部分架橋性熱可塑性エラストマー
（Ａ）が（ｄ）鉱物油系軟化剤を含むことを特徴とする
請求項第６項に記載の部分架橋熱可塑性エラストマー発
泡体の製造方法。 ８）（ｄ）鉱物油系軟化剤の配合量が、（ａ）成分、（
ｂ）成分、（ｃ）成分および（ｄ）成分の合計重量１０
０重量部に対し、０〜５０重量部の範囲内の量であるこ
とを特徴とする請求項第７項に記載の部分架橋熱可塑性
エラストマー発泡体の製造方法。 ９）部分架橋熱可塑性エラストマー発泡体における熱可
塑性エラストマーの架橋度が、ゲル分率（熱キシレン、
１３０℃）で２〜９０％であることを特徴とする請求項
第６項〜第８項のいずれかに記載の部分架橋熱可塑性エ
ラストマー発泡体の製造方法。 １０）部分架橋熱可塑性エラストマー発泡体の発泡倍率
が３倍を超えていることを特徴とする請求項第６項〜第
９項のいずれかに記載の部分架橋熱可塑性エラストマー
発泡体の製造方法。[Scope of Claims] 1) (a) 100 to 10 parts by weight of ionizing radiation crosslinkable olefin copolymer rubber, (b) 0 to 90 parts by weight of ionizing radiation crosslinkable olefin plastic, and (c) ionizable A melt index of 0.1 to 100 g/10 consisting of 1 to 90 parts by weight of a radiodegradable olefin plastic [however, the total weight of components (a), (b) and (c) is 100 parts by weight] An unfoamed partially crosslinked thermoplastic elastomer molded article composed of a foamable composition consisting of a thermoplastic elastomer (A) partially crosslinked by ionizing radiation and a pyrolyzable blowing agent (B) is foamed. Partially cross-linked thermoplastic elastomer foam characterized by: 2) The partially crosslinked thermoplastic elastomer foam according to claim 1, wherein the ionizing radiation partially crosslinkable thermoplastic elastomer (A) contains (d) a mineral oil softener. 3) (d) The blending amount of mineral oil-based softener is (a) component, (
Total weight of component b), component (c) and component (d) 10
3. The partially crosslinked thermoplastic elastomer foam according to claim 2, wherein the amount is in the range of 0 to 50 parts by weight relative to 0 parts by weight. 4) The degree of crosslinking of the thermoplastic elastomer in the partially crosslinked thermoplastic elastomer foam is determined by the gel fraction (thermal xylene,
4. The partially crosslinked thermoplastic elastomer foam according to any one of claims 1 to 3, characterized in that the crosslinked thermoplastic elastomer foam has a content of 2 to 90% at a temperature of 130°C. 5) Claims 1 to 4, characterized in that the partially crosslinked thermoplastic elastomer foam has a foaming ratio of more than 3 times.
3. The partially crosslinked thermoplastic elastomer foam according to any one of paragraphs. 6) (a) 100 to 10 parts by weight of ionizing radiation crosslinkable olefin copolymer rubber, (b) 0 to 90 parts by weight of ionizing radiation crosslinking olefin plastic, and (c) ionizing radiation decomposition type olefin plastic 1 to 90 parts by weight [however, the total weight of components (a), (b), and (c) is 100 parts by weight], with a melt index of 0.1 to 100 g/10 minutes. A foamable composition obtained by melt-kneading a crosslinkable thermoplastic elastomer (A) and a thermally decomposable blowing agent (B) at a temperature below the decomposition temperature of the thermally decomposable blowing agent (B) is mixed into a predetermined shape. obtaining an unfoamed partially crosslinked thermoplastic elastomer molded article by irradiating it with ionizing radiation; 1. A method for producing a partially crosslinked thermoplastic elastomer foam, comprising the steps of heating and foaming at a temperature above. 7) The method for producing a partially crosslinked thermoplastic elastomer foam according to claim 6, wherein the ionizing radiation partially crosslinkable thermoplastic elastomer (A) contains (d) a mineral oil softener. 8) (d) The blending amount of mineral oil softener is (a) component, (
Total weight of component b), component (c) and component (d) 10
8. The method for producing a partially crosslinked thermoplastic elastomer foam according to claim 7, wherein the amount is in the range of 0 to 50 parts by weight relative to 0 parts by weight. 9) The degree of crosslinking of the thermoplastic elastomer in the partially crosslinked thermoplastic elastomer foam is determined by the gel fraction (thermal xylene,
130° C.) from 2 to 90%. 10) The method for producing a partially crosslinked thermoplastic elastomer foam according to any one of claims 6 to 9, wherein the expansion ratio of the partially crosslinked thermoplastic elastomer foam is more than 3 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9791390A JP3012277B2 (en) | 1989-04-14 | 1990-04-13 | Partially crosslinked thermoplastic elastomer foam and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-94598 | 1989-04-14 | ||
| JP9459889 | 1989-04-14 | ||
| JP9791390A JP3012277B2 (en) | 1989-04-14 | 1990-04-13 | Partially crosslinked thermoplastic elastomer foam and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0347849A true JPH0347849A (en) | 1991-02-28 |
| JP3012277B2 JP3012277B2 (en) | 2000-02-21 |
Family
ID=26435871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9791390A Expired - Lifetime JP3012277B2 (en) | 1989-04-14 | 1990-04-13 | Partially crosslinked thermoplastic elastomer foam and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3012277B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001114917A (en) * | 1999-10-20 | 2001-04-24 | T S Tec Kk | Foamed substrate for vehicle, its preparation method and sheet for vehicle |
| JP2001279013A (en) * | 2000-03-29 | 2001-10-10 | Nhk Spring Co Ltd | Gasket for hdd having low moisture permeability |
| JP2006008860A (en) * | 2004-06-25 | 2006-01-12 | Daicel Novafoam Ltd | Foam molding and method for producing the same |
| JP2011074263A (en) * | 2009-09-30 | 2011-04-14 | Asahi Kasei E-Materials Corp | Sealing resin sheet |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110256378A1 (en) * | 2010-04-13 | 2011-10-20 | Energy Sciences, Inc. | Cross linking membrane surfaces |
| KR102138626B1 (en) * | 2018-10-26 | 2020-07-28 | 주식회사 현대케피코 | Method for manufacturing radiation cross linked plastic composite and radiation cross linked plastic composite manufactured thereby |
-
1990
- 1990-04-13 JP JP9791390A patent/JP3012277B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001114917A (en) * | 1999-10-20 | 2001-04-24 | T S Tec Kk | Foamed substrate for vehicle, its preparation method and sheet for vehicle |
| JP2001279013A (en) * | 2000-03-29 | 2001-10-10 | Nhk Spring Co Ltd | Gasket for hdd having low moisture permeability |
| JP2006008860A (en) * | 2004-06-25 | 2006-01-12 | Daicel Novafoam Ltd | Foam molding and method for producing the same |
| JP2011074263A (en) * | 2009-09-30 | 2011-04-14 | Asahi Kasei E-Materials Corp | Sealing resin sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3012277B2 (en) | 2000-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1197521B1 (en) | Thermoplastic elastomer composition, foam made from the same, and process for producing foam | |
| JP5475991B2 (en) | Soft polyolefin with high heat resistance | |
| US20020086946A1 (en) | Polyolefin foam and polyolefin resin composition | |
| JPH08231816A (en) | Polypropylene resin composition, its foam, and its production | |
| JP4025423B2 (en) | Thermoplastic elastomer foam | |
| JP4300868B2 (en) | Damping foam molding resin composition and damping foam | |
| CN108884257B (en) | Crosslinked polyolefin resin foam and molded article using same | |
| JPH0347849A (en) | Partially crosslinked thermoplastic elastomer foam and production thereof | |
| JP2665373B2 (en) | Partially crosslinked thermoplastic elastomer foam and method for producing the same | |
| JP5017740B2 (en) | Polyolefin resin cross-linked foam and method for producing the same | |
| JP3671320B2 (en) | Rubber-like olefin soft resin cross-linked foam | |
| JP2005041913A (en) | Olefin elastomer composition for foam and its use | |
| JPS6261222B2 (en) | ||
| US20070082962A1 (en) | Resin composition for foam molding, foam and method for producing the foam | |
| JPS6011937B2 (en) | Method for producing thermoplastic elastomer foam | |
| JPS6011938B2 (en) | Method for manufacturing thermoplastic resin foam | |
| JP2005220303A (en) | Polypropylene-based resin composition for forming foamed article and peroxide-cross-linked foamed article consisting of the same | |
| JP2002146075A (en) | Polyolefin-based resin foam and polyolefin based resin composition | |
| JPH059325A (en) | Production of crosslinked foam of olefinic elastomer composition | |
| JP2005154732A (en) | Foam molding resin composition, foamed product, and method for producing the foamed product | |
| JP7377047B2 (en) | Polyolefin resin foam sheet and manufacturing method thereof | |
| JP3588545B2 (en) | Method for producing polyolefin resin foam | |
| JP2004217681A (en) | Ethylenic resin composition for cross-linked foam and ethylenic resin cross-linked foam comprising the same | |
| JPH08109277A (en) | Cross-linked polyolefin resin foam | |
| JPH03139535A (en) | Composition for crosslinked polyolefin foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071210 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081210 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081210 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091210 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091210 Year of fee payment: 10 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091210 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101210 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101210 Year of fee payment: 11 |