JPS6361038A - Radiation-resistant polyolefin composition - Google Patents
Radiation-resistant polyolefin compositionInfo
- Publication number
- JPS6361038A JPS6361038A JP20624886A JP20624886A JPS6361038A JP S6361038 A JPS6361038 A JP S6361038A JP 20624886 A JP20624886 A JP 20624886A JP 20624886 A JP20624886 A JP 20624886A JP S6361038 A JPS6361038 A JP S6361038A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- radiation
- polyolefin
- examples
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 230000005855 radiation Effects 0.000 title claims abstract description 16
- -1 phenyl ether compound Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 230000005251 gamma ray Effects 0.000 abstract description 7
- 230000003078 antioxidant effect Effects 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000008280 blood Substances 0.000 abstract description 2
- 210000004369 blood Anatomy 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-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
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000010241 blood sampling Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- RRZCFXQTVDJDGF-UHFFFAOYSA-N dodecyl 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC RRZCFXQTVDJDGF-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005630 sialyl group Chemical group 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
【産業上の利用分野１
本発明は、ポリオレフィン組成物に関し、特にγ線等の
放射線照射による劣化の少ない耐放射線性ポリオレフィ
ン組成物に関するものである。
（従来の技術］
ポリプロピレン等のポリオレフィンは、その成形品が医
療器具などとして使用される場合、殺菌を目的としてγ
線照射等をされることがある。ポリオレフィンはそれ自
体放射線により分子鎖が切断され易く、その際、該成形
品はγ線により劣化を起こし、そのためクラックの発生
や黄変等の問題を起こし、実用上問題があった。
このようなγ線照射によるポリオレフィンの劣化を防止
する手法としては、特開昭５５−１９１９９号公報に示
されるようにヒンダードアミンを添加剤に使用する例が
あるが、γ線照射後の経時劣化の点ではなお満足のいく
ものとは言えない、また、特開昭５８−４９７３７号お
よび同５Ｂ−１８５８５５号各明細書には、それぞれ特
定の構造を有するヒンダードアミンとフェノール系化合
物等を組合せて使用することによりある程度の耐γ線性
が得られることが開示されている。
【発明が解決しようとする問題点１
本発明は、ポリオレフィンにリン系酸化防止剤およびヒ
ンダードアミン系安定剤の他に特殊化合物を配合するこ
とによりγ線の照射に対して耐性を有するポリオレフィ
ン組成物を提供しようとするものである。
【問題点を解決するための手段】
発明者等は、この問題につき鋭意検討をした結果、特定
の酸化防止剤に特定の化合物を配合することにより得ら
れたポリオレフィン組成物が、γ線照射による経時劣化
の防止に有効であり、かつ、着色、物性等の悪化も少な
いことを見い出し本発明を完成した。
即ち本発明は、ポリオレフィン１００重量部に下記（Ａ
）〜（Ｃ）にて示される化合物を配合してなることを特
徴とする耐放射線照射性ポリオレフィン組成物である。
（Ａ）芳香族亜リン酸エステル系酸化防止剤および芳香
族ホスフォナイト系酸化防止剤から選ばれた少なくとも
１種を０．０１〜０．５重量部（Ｂ） ヒンダードア
ミン型安定剤を０．０１−０．５重量部、
（Ｃ）下記構造を有するフェニルエーテル化合物を０．
０３〜１５重量部。
但し、ここでａは １−４の整数、層は０または１、ｎ
は０〜２の整数、Ｒは炭素数３〜４ｏのアルキル基また
はシクロアルキル基を示す。
本発明で用いることのできるポリオレフィンとしては、
エチレン、プロピレン、ブテン、ペンテン、ヘキセン、
４−メチルペンテン、ヘプテン、オクテン等のα−オレ
フィンの単独あるいは共重合体；これらα−オレフィン
の過半重量と酢酸ビニル等のビニルエステル、アクリル
酸や無水マレイン酸やメタクリル酸メチル等の不飽和有
機酸類（塩、アミド、アミンも含む）、ビニルトリメト
キシシラン等のビニルシランなどとのランダム。
ブロックあるいはグラフト共重合体；もしくはこれら重
合体の塩素化、スルホン化、酸化等の変性処理されたも
の等を挙げることができる。
具体的には、例えば低、中あるいは高密度ポリエチレン
、ポリプロピレン、ポリブテン、エチレン・プロピレン
ランダムあるいはブロック共重合体、エチレンφプロピ
レン・ブテン共重合体、エチレン・ブテン共重合体、エ
チレン・４−メチルペンテン共重合体、プロピレン・ヘ
キセン共重合体、プロピレン・ヘキセンφブテン共重合
体などである。
これら重合体の中で、特に本発明の効果の顕著なものは
、ポリプロピレン、プロピレン・エチレンランダムある
いはブロック共重合体、プロピレン・エチレン・ブテン
共重合体等のプロピレン系重合体である。
本発明で用いられる化合物（Ａ）の例としては、（ａ）
）リス−（ミックスト−モノおよびジ−ノニルフェ
ニル）−ホスファイト
（ｂ）トリス−（２，４−ジ−ｔ−ブチルフェニル）ポ
スファイト
（Ｃ）ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタ
エリスリトール−ジホスファイト
（ｄ） １，１．３−トリス（２−メチル−４−ジー
トリデシルホスファイト−５−ｔ−ブチルフェニル）ブ
タン（ｅ） ４．４”−ブチリデン−ビス（３−メチル
−６−を−ブチルフェニル−ジ−トリデシル）ポスファ
イ ト
（ｆ）ビス（２，６−ジーｔ−ブチル−４−メチルフェ
ニル）ペンタエリスリトール−ジ−ポスファイト
（ｇ）テトラキス（２，４−ジ−ｔ−ブチルフェニル）
４゜４−ビフェニレン−ジ−ホスフォナイトなどが挙げ
られるが、これらに限定されるものではない。
本発明で用いられる化合物（Ｂ）の例としては、（ｈ）
２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベン
ジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，８
，＄−ペンタメチル−４−ピペリジル）
（ｉ）ポリ（（８−（１，１，３，３−テトラメチルブ
チル）イミノ−１，３，５−）リアジン−２，４−ジイ
ル）（（２゜２．８．８−テトラメチル−４−ピペリジ
ル）イミノ）へキサメチレン（（２，２，６，Ｅｌ−テ
トラメチル−４−ピペリジル）イミノ）１
既存化学物質Ｎｏ、（７）−２１７０
（Ｄコハク酸ジメチル−１−（２−とドロキシエチル）
−４−ヒドロキシ−２，２，８，８−テトラメチルピペ
リジン重縮合物
（ｋ）テトラキス（２，２，８，８−テトラメチル−４
−ピペリジル）−１，２，３，４−ブタンテトラカルボ
キシレート
（１）トリス（２，２，８，８−テトラメチル−４−ピ
ペリジル）−トリデシル−１，２，３，４−ブタンテト
ラカルボキシレート
（ｆｆｉ）ビス−（２，２，８，Ｂ−テトラメチル−４
−ピペリジル）セバケート
（ｎ）トリス（１，２，２，８，６−ベンタメチルー４
−ピペリジル）−トリデシル−１，２，３，４−ブタン
テトラカルボキシレート
（ｏ） Ｎ、Ｎ’−ビス（２，２，８，１ｌｌ−テトラ
メチル−４ピペリジル）へキサメチレンジアミンと１．
２−ジ−ブロモエタンとの縮合物
（ｐ）ポリ−［２−Ｎ、Ｎ’−ジ（２，２，８，８−テ
トラメチル−４−ピペリジル）ヘキサンジアミン−４−
（トモルフィリノ）シムトリアジン】
などが好例であるが、好ましくは分子量が５００以上の
ものが良い。
本発明で用いられるフェニルエーテル化合物（Ｃ）の例
としては、
（９）αｏ、、：、、ｏ１０ｒｏｃｆｏつなどが挙げら
れる。ここでＲはフルキル基であり、炭素数１２．１３
．１Ｂ、 １８．２２のものなどが好例である。これら
の化合物は松材石油研究所よりモレスコハイラッドシリ
ーズの商品名で耐放射線性潤滑油として市販されている
ものを利用することができる。
これら化合物（Ａ） 、 （Ｂ）および（Ｃ）の配合量
は、ポリオレフィン１００重量部に対して（Ａ）が０．
０１〜０．５重量部、好ましくは０．０３〜０．３重量
部、（Ｂ）が０．０１〜０．５重量部、好ましくは０．
０３〜０．３重量部、および（Ｃ）が０．０３〜１５重
量部、好ましくは０．０５〜ｌＯ重量部である。それぞ
れの配合量が上記範囲未満では十分効果が発揮されず、
超過ではブリード、着色の問題を生ずるおそれがあり、
かつ、コスト面で実際的でない。
本発明組成物には、本発明の効果を損なわない限り、他
の付加的成分を添加することができる。
付加的成分としては、通常用いられる耐化防止剤、透明
化剤、核材、紫外線吸収剤、滑剤、帯電防止剤、アンチ
ブロッキング剤、無滴剤、顔料、過酸化物、架橋助剤、
金属石ケン類等の分散剤。
中和剤等である。
酸化防止剤の例としては、３，５−ジ−ｔ−ブチル−４
−ヒドロキシ−トルエン、テトラキス［メチレン−３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオネートコメタンなどがあるが、これらはγ線照
射時の黄変の原因となるので少量添加が望ましい。
また、ジステアリル−ペンタニルスリトール−ジ−ホス
ファイトは添加しても差支えないばかりか、黄変改良効
果さえある。その他、ジ−テトラデシル−３，３°−チ
オ−ジプロピオネート、ジステアリル−チオ−ジプロピ
オネート、ラウリル−ステアリル−チオ−ジプロピオネ
ート、テトラキス−（メチレン−３−ドデシルチオプロ
ピオネート）メタン等の硫黄系酸化防止剤を添加しても
良い。
透明化剤および核剤の例としては、ソルビトールとベン
ズアルデヒドの縮合物である１、３，２．４−ジベンジ
リデンソルビトールおよびこの化合物のベンゼン環にメ
チル、エチル、ｎ−ブチル、ｔ−プチルなどのアルキル
基またはメトキシ、エトキシ、プロポキシなどのアルコ
キシ基等が置換されたものがある。また、アルミニウム
ーｐ−ｔ−ブチル−ベンゾエート、芳香族酸性リン酸エ
ステル誘導体などがある。
紫外線吸収剤としては、２−ヒドロキシ−４−ｎ−オク
トキシ−ベンゾフェノン、２− （２−ヒドロキシ−３
°、５’−シー ｔ−）−Ｆ−ルーフェニル）５−クロ
ロベンゾトリアゾールなどがある。
過酸化物の例としては、ベンゾイルペルオキシド、１．
３−ビス（ｔ−ブチルペルオキシイソプロビル）ベンゼ
ン、２．５−ジメチル−２，５−ジ（ｔ−ブチルペルオ
キシ）ヘキサンなどがある。
架橋助剤の例としては、トリアリルイソシアヌレート、
トリアリルシアヌレート、シアリル（イソ）シアヌレー
トなどがある。
分散剤、中和剤としては、ステアリン酸のカルシウム、
マグネシウム、ナトリウム等の塩などが挙げられる。
本発明組成物の製造は、パウダー状あるいはペレット状
のポリオレフィンに上記必須成分のほか、必要により他
の成分を添加し、ロール、ブラベンダープラストグラフ
、押出機等の混練機で溶融混練してなされる。
一般にはパウダー状のポリオレフィンに各成分を添加し
、ミキサー等の適当な混合装置にて混合後、押出機にて
溶融混練してペレット化し、このペレットを射出成形等
の成形に供するのが実際的である。各成分を混合して直
接成形しても差し支えない。
成形例としては他に圧縮成形、ブロー成形。
フィルム成形、押出しシート並びに真空成形、紡糸など
が好例である。
［作用および効果］
本発明のポリオレフィン組成物は、特定の酸化防止剤と
ヒンダードアミン型安定剤とに加えて特殊のフェニルエ
ーテル型化合物をポリオレフィンに配合したことにより
、放射線に対してすぐれた耐性を有するものである。ま
た、これらの添加剤の配合によって、ポリオレフィン自
体のＨａｚｅや色調は損なわれない、また、γ線の照射
によって生ずる分子量の低下の度合が少なく、衝撃強度
の低下も見られない。
本発明の効果の発現については、いろいろ考えることが
出来る。即ち、前記したように、化合物（Ａ） 、 （
Ｂ）の中の特定の化合物の組合わせについては、ある程
度の耐放射線効果があることは知られている。また、化
合物（Ｃ）については、それ自身に耐放射線性があるこ
とが知られている。しかしながら、これら３成分を組合
わせることにより本発明の著しく優れた耐放射線性のポ
リオレフィン組成物を得ることが出来ることは意外なこ
とである。
本発明の組成物が耐性を示す放射線としては、Ｘ線、α
線、β線、γ線のいずれもがその対象となる。
本発明組成物は、耐放射線性を有しているので、シリン
ジ、輸液、輸血セット、採血器具さらには又ｍ維製品、
衣料品、理化実験用具等への応用が可能である。また原
子力施設内のケーブル、配線材、絶縁材、パツキン、さ
らにはまた、放射能汚染された所で使用される車、ロボ
ット等の部品に利用でき、また、食品包装用にフィルム
や容器等への応用も可能である。
［実施例］
以下の実施例および比較例において用いられた添加剤は
次のものである。
化合物（Ａ）
（Ｃ）ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタ
エリスリトール−ジホスファイト
（ｄ） １，１．３−トリス（２−メチル−４−ジー
トリデシルホスファイト−５−ｔ−ブチルフェニル）ブ
タン化合物（Ｂ）
（ｉ）ポリ（（８−（１，１，３，３−テトラメチルブ
チル）イミノ−１，３，５−）リアジン−２，４−ジイ
ル）（（２゜２．８．８−テトラメチル−４−ピペリジ
ル）イミノ）へキサメチレン（（２，２，８，６−テト
ラメチル−４−ピペリジル）イミノ）】
既存化学物質Ｎｏ、（７）−２１７０
（Ｄコハク酸ジメチル−１−（２−ヒドロキシエチル）
−４−ヒドロキシ−２，２，８，１３−テトラメチルピ
ペ１ノジン重縮合物
（鵬）ビス−（２，２，８，８−テトラメチル−４−ピ
ペリジル）セバケート
化合物（Ｃ）
のＲの炭素数が１８のもの（松材石油研究所製、モレス
コノ−イラツド Ｒｉ−ｔｔｓ）その他の添加剤
Ｃａ５Ｔ ： ステアリン酸カルシウムＩＲＩＯＩＯ：
テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオネートコメタン
ＧＡＩ’ｌＤ：１，３，２．４−ジーＰ−／Ｉチルヘン
シリプアー’）ｋビトール
実施例１〜６、比較例１〜５
メルトフローレイト（ＭＦＲ） ５ ｇ／１０分、エチ
レン含量３重量２のプロピレン・エチレンランダム共重
合体１００重量部に上記化合物を第１表に記載さ−また
添加量で配合し、ヘンシェルミキサーにて攬１混合した
後、押出機（２３０℃設定）にて溶融混練し、ペレット
化した。このペレットを射出成形機にかけ（２４０℃設
定）２■■厚のシートを作成した。
二のシートをコバルト−８０線源にて、平均２．８ Ｍ
ｒ】ｄのγ線を当てた。得られた試片につき、カラーマ
シンにより ｂ値を、メルトインデクサ−（２３０℃２
．１１３ｋｇ加重）にて、ＭＦＲを測定し、８０℃オー
ブンに １週間入れた後のブリードを目視にて判定した
。また、フラットダート衝撃試験機にて破壊時の衝撃吸
収エネルギーを測定した（ＦＤＩＴ）、また、照射前の
試片については、ヘイズメータにてヘイズを測定した。
さらに、試片を１２０℃オーブンに入れて脆化時間を測
定した。 （ＢＰ）比較例についても同様な方法にて試
験をした。
配合を第１表、結果を第２表に示す。
これら実験例により、本特許のポリオレフィン組成物か
ら得られた製品は、ポリオレフィンの透明性に影響を与
えることもなく、γ線照射後の色相１分子量、衝撃強度
等の改良効果が認められることが明白である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a polyolefin composition, and particularly to a radiation-resistant polyolefin composition that is less likely to deteriorate when exposed to radiation such as gamma rays. (Prior art) When molded products of polyolefins such as polypropylene are used as medical devices, γ is used for the purpose of sterilization.
You may be exposed to radiation, etc. The molecular chains of polyolefins themselves are easily cleaved by radiation, and in this case, the molded products are degraded by γ rays, which causes problems such as cracking and yellowing, which poses practical problems. As a method for preventing such deterioration of polyolefins due to γ-ray irradiation, there is an example of using hindered amine as an additive as shown in JP-A-55-19199. In addition, in the specifications of JP-A-58-49737 and JP-A-5B-185855, a hindered amine having a specific structure and a phenol compound, etc. are used in combination. It has been disclosed that a certain degree of gamma ray resistance can be obtained by this. Problem to be Solved by the Invention 1 The present invention provides a polyolefin composition that is resistant to γ-ray irradiation by blending a special compound in addition to a phosphorous antioxidant and a hindered amine stabilizer into a polyolefin. This is what we are trying to provide. [Means for solving the problem] As a result of intensive study on this problem, the inventors have found that a polyolefin composition obtained by blending a specific compound with a specific antioxidant is resistant to γ-ray irradiation. The present invention was completed after discovering that it is effective in preventing deterioration over time and that there is little deterioration in coloring, physical properties, etc. That is, in the present invention, the following (A
This is a radiation-resistant polyolefin composition characterized by blending the compounds shown in ) to (C). (A) 0.01 to 0.5 parts by weight of at least one selected from aromatic phosphite-based antioxidants and aromatic phosphonite-based antioxidants (B) 0.01-0.01 parts by weight of a hindered amine type stabilizer 0.5 parts by weight, (C) 0.5 parts by weight of a phenyl ether compound having the following structure.
03-15 parts by weight. However, here a is an integer of 1-4, layer is 0 or 1, n
is an integer of 0 to 2, and R represents an alkyl group or cycloalkyl group having 3 to 4 carbon atoms. Polyolefins that can be used in the present invention include:
Ethylene, propylene, butene, pentene, hexene,
Single or copolymers of α-olefins such as 4-methylpentene, heptene, and octene; majority of these α-olefins and vinyl esters such as vinyl acetate, unsaturated organic compounds such as acrylic acid, maleic anhydride, and methyl methacrylate. Random combinations with acids (including salts, amides, and amines), vinylsilanes such as vinyltrimethoxysilane, etc. Examples include block or graft copolymers; or modified versions of these polymers such as chlorination, sulfonation, and oxidation. Specifically, for example, low, medium or high density polyethylene, polypropylene, polybutene, ethylene/propylene random or block copolymer, ethylene φ propylene/butene copolymer, ethylene/butene copolymer, ethylene/4-methylpentene. These include copolymers, propylene/hexene copolymers, propylene/hexene φ-butene copolymers, etc. Among these polymers, propylene polymers such as polypropylene, propylene/ethylene random or block copolymers, and propylene/ethylene/butene copolymers are particularly effective in the present invention. Examples of the compound (A) used in the present invention include (a)
) Lis-(mixed-mono and di-nonylphenyl)-phosphite (b) Tris-(2,4-di-t-butylphenyl)phosphite (C) Bis(2,4-di-t-butyl phenyl) pentaerythritol-diphosphite (d) 1,1,3-tris(2-methyl-4-di
Tridecyl phosphite-5-t-butylphenyl)butane (e) 4.4”-butylidene-bis(3-methyl-6-butylphenyl-di-tridecyl) phosphite (f) bis(2,6 -di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite (g)tetrakis(2,4-di-t-butylphenyl)
Examples include, but are not limited to, 4°4-biphenylene di-phosphonite. Examples of the compound (B) used in the present invention include (h)
2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,8
, $-pentamethyl-4-piperidyl) (i) Poly((8-(1,1,3,3-tetramethylbutyl)imino-1,3,5-)riazine-2,4-diyl)((2゜2.8.8-Tetramethyl-4-piperidyl)imino)hexamethylene ((2,2,6,El-tetramethyl-4-piperidyl)imino)1 Existing chemical substance No. (7)-2170 (D Dimethyl-1-(2- and droxyethyl) succinate
-4-Hydroxy-2,2,8,8-tetramethylpiperidine polycondensate (k) Tetrakis (2,2,8,8-tetramethyl-4
-piperidyl)-1,2,3,4-butanetetracarboxylate (1) Tris(2,2,8,8-tetramethyl-4-piperidyl)-tridecyl-1,2,3,4-butanetetracarboxylate Rate (ffi) bis-(2,2,8,B-tetramethyl-4
-piperidyl) sebacate (n) tris(1,2,2,8,6-bentamethyl-4
-piperidyl)-tridecyl-1,2,3,4-butanetetracarboxylate (o) N,N'-bis(2,2,8,1ll-tetramethyl-4piperidyl)hexamethylenediamine and 1.
Condensate with 2-di-bromoethane (p) Poly-[2-N,N'-di(2,2,8,8-tetramethyl-4-piperidyl)hexanediamine-4-
(tomorphilino)simtriazine] and the like are good examples, but those with a molecular weight of 500 or more are preferred. Examples of the phenyl ether compound (C) used in the present invention include (9) αo, :, o10rocfo, and the like. Here, R is a furkyl group, and has a carbon number of 12.13
．． 1B and 18.22 are good examples. As these compounds, those commercially available as radiation-resistant lubricating oils under the trade name of Moresco Hyrad series from Matsuzawa Petroleum Research Institute can be used. The compounding amounts of these compounds (A), (B) and (C) are as follows: (A) is 0.00 parts by weight per 100 parts by weight of the polyolefin.
01 to 0.5 parts by weight, preferably 0.03 to 0.3 parts by weight, and 0.01 to 0.5 parts by weight, preferably 0.01 to 0.5 parts by weight of (B).
and (C) in an amount of 0.03 to 15 parts by weight, preferably 0.05 to 10 parts by weight. If the amount of each compounded is less than the above range, sufficient effect will not be exhibited,
Exceeding the limit may cause bleeding and coloring problems.
Moreover, it is not practical in terms of cost. Other additional components can be added to the composition of the present invention as long as they do not impair the effects of the present invention. Additional components include commonly used anti-oxidizing agents, clarifying agents, core materials, ultraviolet absorbers, lubricants, antistatic agents, anti-blocking agents, anti-drop agents, pigments, peroxides, crosslinking aids,
Dispersant for metal soaps, etc. Neutralizing agents, etc. Examples of antioxidants include 3,5-di-t-butyl-4
-Hydroxy-toluene, tetrakis[methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
There are propionate comethane, etc., but since these cause yellowing during γ-ray irradiation, it is desirable to add a small amount. Further, distearyl-pentanylthritol-di-phosphite may be added without any problem, and even has the effect of improving yellowing. Other sulfur-based antioxidants include di-tetradecyl-3,3°-thio-dipropionate, distearyl-thio-dipropionate, lauryl-stearyl-thio-dipropionate, and tetrakis-(methylene-3-dodecylthiopropionate)methane. An agent may be added. Examples of clarifying agents and nucleating agents include 1,3,2,4-dibenzylidene sorbitol, which is a condensation product of sorbitol and benzaldehyde, and methyl, ethyl, n-butyl, t-butyl, etc. on the benzene ring of this compound. Some are substituted with an alkyl group or an alkoxy group such as methoxy, ethoxy, or propoxy. Further, there are aluminum-pt-butyl-benzoate, aromatic acidic phosphate ester derivatives, and the like. As ultraviolet absorbers, 2-hydroxy-4-n-octoxy-benzophenone, 2-(2-hydroxy-3
°, 5'-Ct-)-F-ruphenyl) 5-chlorobenzotriazole, and the like. Examples of peroxides include benzoyl peroxide, 1.
Examples include 3-bis(t-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane. Examples of crosslinking aids include triallylisocyanurate,
These include triallyl cyanurate and sialyl (iso) cyanurate. As dispersants and neutralizing agents, calcium stearate,
Examples include salts such as magnesium and sodium. The composition of the present invention is produced by adding the above-mentioned essential components to polyolefin in the form of powder or pellets, and other components as necessary, and melt-kneading the mixture with a kneading machine such as a roll, a Brabender plastograph, or an extruder. Ru. Generally, it is practical to add each component to powdered polyolefin, mix it in a suitable mixing device such as a mixer, melt and knead it in an extruder to form pellets, and then use the pellets for molding such as injection molding. It is. There is no problem even if each component is mixed and molded directly. Other molding examples include compression molding and blow molding. Film forming, extruded sheets as well as vacuum forming, spinning, etc. are good examples. [Functions and Effects] The polyolefin composition of the present invention has excellent resistance to radiation because it contains a special phenyl ether type compound in addition to a specific antioxidant and a hindered amine type stabilizer. It is something. Further, by incorporating these additives, the haze and color tone of the polyolefin itself are not impaired, and the degree of decrease in molecular weight caused by irradiation with gamma rays is small, and no decrease in impact strength is observed. Various considerations can be made regarding the manifestation of the effects of the present invention. That is, as described above, compound (A), (
It is known that certain combinations of compounds in B) have a certain degree of radiation resistance effect. Further, it is known that the compound (C) itself has radiation resistance. However, it is surprising that by combining these three components, it is possible to obtain the significantly superior radiation-resistant polyolefin composition of the present invention. The radiation to which the composition of the present invention exhibits resistance includes X-rays, α
This applies to both rays, β rays, and γ rays. Since the composition of the present invention has radiation resistance, it can be used in syringes, infusions, blood transfusion sets, blood sampling instruments, and even textile products.
It can be applied to clothing, physical and chemical experiment equipment, etc. It can also be used for cables, wiring materials, insulation materials, packing materials in nuclear facilities, as well as parts for cars, robots, etc. used in radioactively contaminated areas, and for films and containers for food packaging. It is also possible to apply [Example] The additives used in the following examples and comparative examples are as follows. Compound (A) (C) Bis(2,4-di-t-butylphenyl)pentaerythritol-diphosphite (d) 1,1,3-tris(2-methyl-4-di-
Tridecylphosphite-5-t-butylphenyl)butane compound (B) (i) Poly((8-(1,1,3,3-tetramethylbutyl)imino-1,3,5-)riazine-2 ,4-diyl)((2゜2.8.8-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,8,6-tetramethyl-4-piperidyl)imino)] Existing chemical substance No. , (7)-2170 (D dimethyl succinate-1-(2-hydroxyethyl)
-4-Hydroxy-2,2,8,13-tetramethylpipe-1-nodine polycondensate (Peng) bis-(2,2,8,8-tetramethyl-4-piperidyl)sebacate compound (C) Those with a carbon number of 18 (Matsuzai Oil Research Institute, Morescono-Irad Ri-tts) Other additives Ca5T: Calcium stearate IRIOIO:
Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane GAI'lD: 1,3,2,4-di-P-/Ichirhenshilipur')k Vitol Examples 1 to 6, Comparative Examples 1 to 5 The above compounds were added to 100 parts by weight of a propylene/ethylene random copolymer with a melt flow rate (MFR) of 5 g/10 min and an ethylene content of 3 weight 2. -Also, they were blended in the added amounts, mixed once in a Henschel mixer, then melt-kneaded in an extruder (set at 230°C) and pelletized. The pellets were put into an injection molding machine (set at 240°C) to produce a sheet with a thickness of 2mm. The second sheet was exposed to cobalt-80 radiation source at an average of 2.8 M.
r】d gamma rays were applied. For the obtained specimen, the b value was determined using a color machine and a melt indexer (230℃2
．． The MFR was measured under a load of 113 kg), and the bleed was visually determined after being placed in an 80°C oven for one week. In addition, the impact absorption energy at the time of fracture was measured using a flat dart impact tester (FDIT), and the haze of the sample before irradiation was measured using a haze meter. Furthermore, the specimen was placed in a 120°C oven and the embrittlement time was measured. (BP) Comparative examples were also tested in the same manner. The formulations are shown in Table 1, and the results are shown in Table 2. These experimental examples have shown that products obtained from the polyolefin composition of this patent do not affect the transparency of the polyolefin, and show improvements in hue, molecular weight, impact strength, etc. after γ-ray irradiation. It's obvious.
Claims (1)
）にて示される化合物を配合してなることを特徴とする
耐放射線性ポリオレフィン組成物。 （Ａ）芳香族亜リン酸エステル系酸化防止剤および芳香
族ホスフォナイト系酸化防止剤から選ばれた少なくとも
１種を０．０１〜０．５重量部 （Ｂ）ヒンダードアミン型安定剤を０．０１〜０．５重
量部 （Ｃ）下記構造を有するフェニルエーテル化合物を０．
０３〜１５重量部 ▲数式、化学式、表等があります▼ （ここでｌは１〜４の整数、ｍは０または１、ｎは０〜
２の整数、Ｒは炭素数３〜４０のアルキル基またはシク
ロアルキル基を示す）(1) The following (A) to (C) are added to 100 parts by weight of polyolefin.
1. A radiation-resistant polyolefin composition comprising a compound represented by: (A) 0.01 to 0.5 parts by weight of at least one selected from aromatic phosphite antioxidants and aromatic phosphonite antioxidants (B) 0.01 to 0.5 parts by weight of hindered amine type stabilizers 0.5 parts by weight (C) 0.5 parts by weight of a phenyl ether compound having the following structure.
03-15 parts by weight ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (Here l is an integer from 1 to 4, m is 0 or 1, n is 0 to
(an integer of 2, R represents an alkyl group or cycloalkyl group having 3 to 40 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20624886A JPS6361038A (en) | 1986-09-02 | 1986-09-02 | Radiation-resistant polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20624886A JPS6361038A (en) | 1986-09-02 | 1986-09-02 | Radiation-resistant polyolefin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6361038A true JPS6361038A (en) | 1988-03-17 |
Family
ID=16520188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20624886A Pending JPS6361038A (en) | 1986-09-02 | 1986-09-02 | Radiation-resistant polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6361038A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6395245A (en) * | 1986-10-09 | 1988-04-26 | Tokuyama Soda Co Ltd | Polypropylene composition |
| JPH02153953A (en) * | 1988-12-06 | 1990-06-13 | Tonen Sekiyukagaku Kk | Radiation-resistant polyolefin composition |
| JPH03259940A (en) * | 1990-03-09 | 1991-11-20 | Ube Ind Ltd | Polypropylene composition for food container |
| US5281378A (en) * | 1990-02-05 | 1994-01-25 | Hercules Incorporated | Process of making high thermal bonding fiber |
| KR19990039402A (en) * | 1997-11-12 | 1999-06-05 | 남창우 | Modification of Linear Low Density Polyethylene Resin by Electron Beam Irradiation |
| US9920274B2 (en) | 2015-02-09 | 2018-03-20 | Moresco Corporation | Lubricant composition, use thereof and aliphatic ether compound |
| CN114044967A (en) * | 2021-10-22 | 2022-02-15 | 金发科技股份有限公司 | Gamma irradiation resistant transparent polypropylene composition and preparation method and application thereof |
-
1986
- 1986-09-02 JP JP20624886A patent/JPS6361038A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6395245A (en) * | 1986-10-09 | 1988-04-26 | Tokuyama Soda Co Ltd | Polypropylene composition |
| JPH02153953A (en) * | 1988-12-06 | 1990-06-13 | Tonen Sekiyukagaku Kk | Radiation-resistant polyolefin composition |
| US5281378A (en) * | 1990-02-05 | 1994-01-25 | Hercules Incorporated | Process of making high thermal bonding fiber |
| JPH03259940A (en) * | 1990-03-09 | 1991-11-20 | Ube Ind Ltd | Polypropylene composition for food container |
| KR19990039402A (en) * | 1997-11-12 | 1999-06-05 | 남창우 | Modification of Linear Low Density Polyethylene Resin by Electron Beam Irradiation |
| US9920274B2 (en) | 2015-02-09 | 2018-03-20 | Moresco Corporation | Lubricant composition, use thereof and aliphatic ether compound |
| CN114044967A (en) * | 2021-10-22 | 2022-02-15 | 金发科技股份有限公司 | Gamma irradiation resistant transparent polypropylene composition and preparation method and application thereof |
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