JPS62295939A - Flame-retardant ethylene/ethyl acrylate resin composition - Google Patents
Flame-retardant ethylene/ethyl acrylate resin compositionInfo
- Publication number
- JPS62295939A JPS62295939A JP13831686A JP13831686A JPS62295939A JP S62295939 A JPS62295939 A JP S62295939A JP 13831686 A JP13831686 A JP 13831686A JP 13831686 A JP13831686 A JP 13831686A JP S62295939 A JPS62295939 A JP S62295939A
- Authority
- JP
- Japan
- Prior art keywords
- ethyl acrylate
- silane
- group
- flame
- ethylene
- 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
- 239000004925 Acrylic resin Substances 0.000 title claims abstract 4
- 239000000203 mixture Substances 0.000 title claims description 28
- 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 title claims description 27
- 239000003063 flame retardant Substances 0.000 title claims description 27
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 title abstract 3
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 17
- 239000000194 fatty acid Substances 0.000 claims abstract description 17
- 229930195729 fatty acid Natural products 0.000 claims abstract description 17
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 17
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000000977 initiatory effect Effects 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 44
- 229910000077 silane Inorganic materials 0.000 claims description 44
- 150000002736 metal compounds Chemical class 0.000 claims description 39
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 claims description 17
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 17
- 239000005042 ethylene-ethyl acrylate Substances 0.000 claims description 17
- 239000011342 resin composition Substances 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 21
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 229920000578 graft copolymer Polymers 0.000 abstract description 6
- 150000001282 organosilanes Chemical class 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 125000005372 silanol group Chemical group 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 8
- 239000000347 magnesium hydroxide Substances 0.000 description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- -1 aluminum hydroxide Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000007665 sagging Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003818 cinder Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000004711 α-olefin Chemical group 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000010062 adhesion mechanism Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical group CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate 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
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000004718 silane crosslinked polyethylene Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（産業上の利用分野〕
本発明は、高温時の形状保持性に優れ、燃焼時のドリッ
プ防止、また機械物性として折り曲げ白化性、摩耗性改
善にも効果がみられるばかりでなく、火災発生による燃
焼によってもハロゲン系の有害性、腐蝕性ガスを全く発
生しない押出し成形加工性に優れた難燃性エチレン−エ
チルアクリレート系樹脂組成物に関するものである。[Detailed Description of the Invention] 3. Detailed Description of the Invention (Field of Industrial Application) The present invention has excellent shape retention at high temperatures, prevention of dripping during combustion, and mechanical properties such as bending whitening resistance and abrasion resistance. A flame-retardant ethylene-ethyl acrylate resin composition that is not only effective in improvement but also has excellent extrusion processability and does not emit any harmful halogen-based or corrosive gases even when burned in a fire. It is.
従来、電線、ケーブルをはじめ電器製品の絶縁材料とし
て多用されているポリオレフィン組成物に難燃性を付与
するためには、ポリオレフィンにハロゲン化合物と三酸
化アンチモンを添加することにより達成されていた。し
かるにこれらの組成物はハロゲン組成物であり燃焼時に
ハロゲン化ガスを発生するので人体に有害であり、かつ
金属が腐蝕されるので好ましくなかった。また発煙量が
多く、視界が悪いため火災時の人の避難および消化活動
は著しく制限されていた。Conventionally, flame retardancy has been achieved in polyolefin compositions, which are often used as insulating materials for electric wires, cables, and other electrical appliances, by adding halogen compounds and antimony trioxide to polyolefins. However, these compositions are halogen compositions and generate halogenated gas when burned, which is harmful to the human body and corrodes metals, which is not desirable. In addition, large amounts of smoke and poor visibility severely limited human evacuation and firefighting efforts in the event of a fire.
一方、従来の難燃性組成物にあって、難燃１生の他に併
せて耐熱成形も向上させるためには化学架橋、電子線架
橋等の大小りな架橋装置を必要とし、設備自体コスト、
その後の運用、保守管理費などが嵩み、延いて（ユ組酸
物のコスト上昇を招いていた。また特開昭６０−１０１
１２９号公報にみられるように、シラングラフト化ポリ
オレフィン樹脂を用いて最終的に架橋したことを特徴と
する難燃性架橋組成物では架橋反応を促進させるために
は触媒を添ｈ［１するなどの方法が行なわれるが、混練
はシラングラフトポリマー同士のシロキリン架橋を目的
とするものである。On the other hand, with conventional flame-retardant compositions, in order to improve not only flame retardancy but also heat-resistant molding, large and small cross-linking equipment such as chemical cross-linking and electron beam cross-linking are required, and the equipment itself is expensive and
After that, operation and maintenance costs increased, which led to an increase in the cost of the acid products.
As seen in Publication No. 129, in a flame-retardant crosslinked composition that is finally crosslinked using a silane-grafted polyolefin resin, a catalyst may be added to promote the crosslinking reaction. The purpose of kneading is to crosslink the silane-grafted polymers with each other.
更に特開昭６０−１４７４６３号公報にみられるように
、あらかじめシラングラフトさせたオレフィン系樹脂を
ベースにした難燃ポリオレフィン組成物を作る場合、ひ
とつには、水酸化マグネシウムを使用しているが、これ
は脱水温度が水酸化アルミニウム等の水和全屈化合物よ
り高く、水架（６が進行しにくい点をあげているばかり
でなく、延いては水架橋を恐れる余り、水酸化マグネシ
ウムを非架橋のポリオレフィン樹脂に一度練り込んだ高
濃度のマスターバッチを別に用意し、成形時に、混合し
て押出成形等を行なうもので、あくまでシラングラフト
マー同士のシロキサン架橋を最終的に目的とするもので
ある。Furthermore, as seen in JP-A-60-147463, when making a flame-retardant polyolefin composition based on an olefin resin to which silane has been grafted in advance, magnesium hydroxide is used. This is because the dehydration temperature is higher than that of hydrated total bending compounds such as aluminum hydroxide, which not only makes it difficult for water crosslinking (6) to proceed, but also because of the fear of water crosslinking, magnesium hydroxide is not crosslinked. A high-concentration masterbatch that has been kneaded into the polyolefin resin is prepared separately and mixed during molding to perform extrusion molding, etc., and the ultimate purpose is to crosslink siloxane between silane graftomers. .
即ら、これらシラングラフトマーのシロキサン架橋は、
シラン例えば、ビニルアルコキシシランなどを過酸化物
等のラジカル発生剤のもとて、ポリオレフィン樹脂にグ
ラフト化させたもので、これはオレフィン鎖に加水分解
可能なシラノール基を有する枝を多数形成しており、水
分く温水、蒸気）と錫系触媒のもとに置き、加水分解に
よる、シラングラフトマーのシロキサン同士（”）Ｓｉ
−０−＞の強固な結合を生じさせる、いわば水分子を
媒介とするシラノール基の縮合反応である。That is, the siloxane crosslinking of these silane graftomers is
Silanes, such as vinyl alkoxysilanes, are grafted onto polyolefin resins using radical generators such as peroxides, which form many branches with hydrolyzable silanol groups on the olefin chain. The siloxane of the silane graftomer (Si
-0-> is a so-called condensation reaction of silanol groups mediated by water molecules, which produces a strong bond.
上）小の反応は、難燃組成物の混練加工時に生じると、
最終製品の成形加工時、著しく加工が悪化し、外観も悪
く、場合によっては押出成形不可の状態が起こる場合が
あるため、特に水分を含む添加剤からなる、難燃組成物
の場合は、脱水開始温度の高い水和物を用いたり、難燃
組成物をシラングラフトマーを含む系、水和物を含む系
との二つに分け、最終成形加工時に、マスターバッチの
形でブレンド成形するなど慢カシラングラフトマーと水
和物との接触を避ける方法がとられてきた。Above) When a small reaction occurs during the kneading process of a flame retardant composition,
During the molding process of the final product, the process may deteriorate significantly, the appearance may be poor, and in some cases, extrusion may become impossible. For example, using a hydrate with a high starting temperature, dividing the flame retardant composition into a system containing a silane graftomer and a system containing a hydrate, and blending and molding in the form of a masterbatch during the final molding process. Efforts have been made to avoid contact between the Kashiran graftomer and the hydrate.
これに対し本発明は特公昭５７−２４３７３号公報、特
公昭５７−２６６２Ｏ号公報に示されるようにシラノー
ル基を分子鎖内に無数に有するシラングラフトマーのシ
ラノール基（−）Ｓｉ−ＯＨ）が、水和金属化合物およ
び無機質充填剤等の表面の僅かな水分により、混練加工
時の摩擦熱によって加水分解し、無機質表面のヒドロキ
シル基と縮合反応し、強固なシロキサン結合を生じるも
ので、その反応機構は、前記特許で示されるような触媒
を促進剤として温水又は蒸気で樹脂間のシラングラフト
マーを水架橋せしめる樹脂組成物とは全く異なるもので
ある。On the other hand, the present invention discloses that the silanol group (-)Si-OH) of a silane graftomer having countless silanol groups in its molecular chain is disclosed in Japanese Patent Publications No. 57-24373 and 57-2662O. A small amount of water on the surface of hydrated metal compounds and inorganic fillers causes hydrolysis due to frictional heat during kneading, and condensation reaction with hydroxyl groups on the surface of the inorganic material to form strong siloxane bonds. The mechanism is completely different from the resin composition shown in the above-mentioned patent, in which the silane graftomer between resins is water-crosslinked using hot water or steam using a catalyst as a promoter.
一方、従来の難燃性組成物にあっては、難燃性は水和金
属化合物でノンハロゲン化を達成できるものの、ベース
になる樹脂については、特公昭５７−１０８９８号公報
にみられるように結晶状オレフィン重合体樹脂の他にポ
リスチレン、ＡＢＳ、ナイロン等の熱可塑性樹脂をあげ
ている。が、これら樹脂の燃焼した場合のスチレン系、
アミド系が発生するガスはノンハロゲンではあるが、相
当量の有害ガスが発生するものであった。On the other hand, in conventional flame retardant compositions, flame retardancy can be achieved by non-halogenation with hydrated metal compounds, but the base resin is crystallized as seen in Japanese Patent Publication No. 57-10898. In addition to olefin polymer resins, thermoplastic resins such as polystyrene, ABS, and nylon are mentioned. However, when these resins burn, styrene,
Although the gas generated by the amide system was non-halogen, a considerable amount of harmful gas was generated.
また更に上記特公昭５７−１０８９８号公報にみられる
ように熱可塑性樹脂、水酸化マグネシウムおよび炭素粉
末の三者による難燃向上を主体とした自消性樹脂組成物
は用途によっては、特に通信線の絶縁線およびジャケッ
トなどは、多色、例えば８色などのカラー表示が限定さ
れており、炭素粉末による難燃性向上を目的とした組成
物は、全く実際にそぐわない組成物であった。Furthermore, as seen in the above-mentioned Japanese Patent Publication No. 57-10898, self-extinguishing resin compositions mainly consisting of a thermoplastic resin, magnesium hydroxide, and carbon powder to improve flame retardancy may be used depending on the application, especially for communication lines. Insulated wires, jackets, etc., are limited to multiple colors, for example, eight colors, and a composition intended to improve flame retardance using carbon powder was completely unsuitable for actual use.
また特公昭５９−３８２６０号公報は、ポリオレフィン
は極性がなく、充填剤との親和性がないことから、充填
剤にカップリング剤等を表面処理する変わりに、樹脂自
身にシラングラフト化することによって極性をもたせ、
充填剤との親和性改善を施し、充填剤による補強効果を
更に向上させ、材料の機械的な特性および表面硬度の向
上を目的としているにすぎず、難燃性に関する言及が仝
くみられず、本発明のように最初からエチレン鎖にアク
リル酸エチルの極性を含む難燃樹脂組成物とは全く樹脂
設計に対する考え方が異なるものである。Furthermore, Japanese Patent Publication No. 59-38260 discloses that since polyolefins are non-polar and have no affinity with fillers, instead of surface-treating the fillers with a coupling agent, etc., the resin itself is grafted with silane. Give polarity,
The purpose is simply to improve the affinity with the filler, further improve the reinforcing effect of the filler, and improve the mechanical properties and surface hardness of the material, and there is no mention of flame retardancy. The approach to resin design is completely different from that of the flame-retardant resin composition, which includes the polarity of ethyl acrylate in the ethylene chain from the beginning, as in the present invention.
また単に、極性による充填剤との親和性改善というだけ
で、その詳細な密着機構については何ら触れられておら
ず、極性ということに終止している。Moreover, it merely mentions that the affinity with the filler is improved by polarity, but there is no mention of the detailed adhesion mechanism, and the explanation is limited to polarity.
また、特公昭５７−２４３７３号公報の思想は本発明と
同じものの、ハロゲン系の難燃剤を含むこと、シラング
ラフトマーのシラノール基の枝が無機質充填剤をとらえ
る、強力な捕捉効果を上げているが、その詳細な密着機
構については、推論の域を脱しておらず、金属水和物を
用いることによるシロキリン架橋構造とその結果である
ゲル分率の残査については具体的に明記されていない。Furthermore, although the concept of Japanese Patent Publication No. 57-24373 is the same as the present invention, it contains a halogen-based flame retardant, and the silanol group branches of the silane graftomer capture inorganic fillers, creating a strong trapping effect. However, the detailed adhesion mechanism is still beyond the realm of speculation, and the cross-linked structure of siloquiline due to the use of metal hydrates and the resulting residual gel fraction have not been specifically specified. .
また上記特許のなかで無機質充填剤の使用範囲が１０重
四部〜１５０重母部と狭いことは、本発明の水和金属化
合物の高充填による高度の難燃化と物性バランスとは、
異なる領域の難燃組成物である。In addition, the use range of the inorganic filler in the above patent is narrow from 10 to 150 parts by weight, which means that the high degree of flame retardancy and physical property balance achieved by the high filling of the hydrated metal compound of the present invention is
There are different areas of flame retardant compositions.
本発明は、前記の事情を考慮してなされたもので、その
目的とするところは、火災発生時の人体への安全性を高
く周囲の金属等を腐蝕させることもない、無公害化を達
成したものである。架橋設備を備えることなく、低コス
トで高温時の形状保持性、燃焼時のドリップ防止低発煙
性を確実にして、機械物性として、抗張力、揚傷性、折
り曲げ白化性、摩耗性、低温特性および耐薬品性等の改
善など物性バランスのとれた加工性の良好な組成物を提
供するにある。The present invention has been made in consideration of the above-mentioned circumstances, and its purpose is to achieve high safety for the human body in the event of a fire, do not corrode surrounding metals, etc., and achieve non-pollution. This is what I did. Without the need for crosslinking equipment, we ensure shape retention at high temperatures, low smoke generation during combustion, and excellent mechanical properties such as tensile strength, puncture resistance, whitening resistance on bending, abrasion resistance, low-temperature properties, and It is an object of the present invention to provide a composition with good processability and well-balanced physical properties such as improved chemical resistance.
（発明の構成〕
本発明の難燃性樹脂組成物は、いずれもハロゲン元素を
一切含まず、燃焼しても有害なガスを全く発生せず、シ
ラングラフトマーを含む樹脂と水和金属化合物との強固
な結合を生じさせる反応機構を対象とし、土台とするも
のである。(Structure of the Invention) The flame-retardant resin composition of the present invention does not contain any halogen elements, does not generate any harmful gases even when burned, and is composed of a resin containing a silane graftomer and a hydrated metal compound. It is based on the reaction mechanism that causes the strong bonding of .
即ち本発明は、シラングラフトマーを含めたエチレン−
エチルアクリレート樹脂で、特に極性のないオレフィン
樹脂に比べ、Ｅ Ｅ Ａ 、Ｆ−Ｊ脂は水和金属化合物
との密着力が自ずと強く、またアクリル酸の酸性とアル
カリ性を示す水和金属化合物の中和化による反応性も起
こり難燃特性については非常に優れていることを見出し
た。また、低結晶性でエラストマーに匹敵するほどの柔
軟性を有し、水和金属化合物を高充填でき更に難燃度を
向上させることができる。That is, the present invention provides ethylene-containing silane graftomers.
Ethyl acrylate resins, especially compared to non-polar olefin resins, EEA and F-J resins naturally have stronger adhesion to hydrated metal compounds. It has been found that reactivity occurs due to oxidation, and the flame retardant properties are very good. In addition, it has low crystallinity and flexibility comparable to elastomers, and can be highly filled with hydrated metal compounds and further improve flame retardancy.
更にシラングラフトマーと水和金属化合物について言え
ば、シラングラフトマーは周知のように水架橋樹脂と言
われ、架橋促進剤である触媒を含むシラングラフトマー
が周囲の水分と熱のある一定以上の環境条件にあかれる
ことにより、シラングラフトマー同士が、シロキサン結
合を形成し、最終的にはシラン架橋ポリエチレンが形成
される。Furthermore, regarding silane graftomers and hydrated metal compounds, silane graftomers are known as water-crosslinked resins, and silane graftomers containing catalysts as crosslinking promoters are exposed to ambient moisture and heat above a certain level. When exposed to environmental conditions, the silane graftomers form siloxane bonds with each other, ultimately forming silane crosslinked polyethylene.
この場合ジブチル錫ジラウレートを代表とする有機金属
化合物の触媒が必ず促進剤として必要となる。In this case, an organometallic compound catalyst typified by dibutyltin dilaurate is always required as a promoter.
しかしここて難燃剤としての水和金属化合物をシラング
ラフトマーと同時に混練した場合、架橋促進の触媒の助
けを全く必要とぜず、水和金属化”合物の表面のヒドロ
キシル基（ＯＨ基）とシラングラフトマーのシラノール
基（−）Ｓｉ−ＯＨ）が、水和金属化合物表面の僅かな
水分と有機金属化合物の触媒に類した金属化合物との影
響で、混錬時に発生する摩隙熱の環境下で加水分解によ
る縮合反応が生じ強固なシロキサン結合（−３ｉ −０
−Ｍｍｏｎ：Ｍ金属）を形成する。この時触媒等を全く
必要としないのである。However, when a hydrated metal compound as a flame retardant is kneaded together with a silane graftomer, no help from a catalyst to promote crosslinking is required, and the hydroxyl groups (OH groups) on the surface of the hydrated metal compound are mixed. The silanol group (-)Si-OH) of the silane graftomer and the silanol group (-) Si-OH) suppress the friction heat generated during kneading due to the influence of the slight moisture on the surface of the hydrated metal compound and the metal compound similar to the catalyst of the organometallic compound. A condensation reaction due to hydrolysis occurs in the environment, forming a strong siloxane bond (-3i -0
-Mmon: M metal) is formed. At this time, no catalyst or the like is required at all.
このため燃焼時、発生する熱が、水和金属化合物が分解
して脱水した水の気化熱によって吸収される冷却効果と
、本発明の特徴であるアクリル酸の極性基と水和金属化
合物の密着力に加えてシラングラフトマーと水和金属化
合物間の強固な結合によって燃焼による分解を抑制する
働きにより、燃焼時タレ防止効果を発揮し、かつ固い燃
え殻を形成するため延焼防止効果を同時に発揮するもの
である。更に強固な結合は発煙量を著しく抑制する効果
も発揮することを発見した。For this reason, the heat generated during combustion is absorbed by the heat of vaporization of water dehydrated when the hydrated metal compound decomposes, and the cooling effect is absorbed, and the characteristic of the present invention is that the polar group of acrylic acid and the hydrated metal compound adhere to each other. In addition to the strong bond between the silane graft tomer and the hydrated metal compound, the strong bond between the silane graft tomer and the hydrated metal compound suppresses decomposition due to combustion, thereby preventing sagging during combustion, and forming a hard cinder to prevent the spread of fire. It is something. Furthermore, it was discovered that strong bonding also has the effect of significantly suppressing the amount of smoke generated.
従って炭素粉末による燃焼抑制効果とは全く異なるもの
である。しかし本願は用途に応じて顔料としてのカーボ
ンブラックをはじめとする種々の着色剤を添加してもそ
の燃焼防止効果が発揮されるため自由自在に着色でき広
範囲の用途に適用でき優れた発明である。また要求され
る難燃レベルに応じて、水和金属化合物およびシラング
ラフトマーの量をコントロールすることにより変成でき
る。Therefore, this effect is completely different from the combustion suppressing effect of carbon powder. However, the present invention is an excellent invention that can be freely colored and applied to a wide range of uses, since even if various colorants such as carbon black are added as pigments depending on the purpose, the combustion prevention effect is exhibited. . Furthermore, modification can be performed by controlling the amounts of the hydrated metal compound and silane graftomer depending on the required level of flame retardancy.
更に水和金属化合物に表面処理剤を使用することによっ
て柔軟性、成形加工性等を改善できるばかりでなく、水
和金属化合物をより高充填できるものである。Furthermore, by using a surface treatment agent for the hydrated metal compound, not only the flexibility and moldability can be improved, but also the hydrated metal compound can be filled more highly.
（１）エチレン−アクリル酸エチル（ＥＥＡ）樹脂とは
エチレンとアクリル酸エチルとを共重合させた重合体で
ある。低結晶性でありアクリル酸エチル（ＥＡ）の含有
量が５Ｗ％で密度０．９１０と非常に低く、水和金属化
合物を高充填できるとともに、側鎖としてアクリル酸エ
ステルであるアクリル酸エチルの極性基をもつところか
ら充填剤との結びつきが強いため難燃性のレベルは無極
性のポリオレフィンより、非常によいことを発見した。(1) Ethylene-ethyl acrylate (EEA) resin is a copolymer of ethylene and ethyl acrylate. It has low crystallinity and has a very low density of 0.910 with an ethyl acrylate (EA) content of 5W%, allowing for high loading of hydrated metal compounds, and the polarity of ethyl acrylate, which is an acrylic ester, as a side chain. It was discovered that because it has a group, it has a strong bond with the filler, so the level of flame retardancy is much better than that of non-polar polyolefin.
更にこれにＦＥＡシラングラフトマー樹脂を加えると、
密度が驚くほど向上し、燃焼性、機械物性等の諸物性が
箸しく向上するものでおる。特にアクリル酸エチルの含
有量は３〜５０ｗ％の範囲で有効であり特に１０〜２Ｏ
％のちのが最もよい。また、あらかじめシラングラフト
させたシラングラフトポリマーとは、即ち、シラングラ
フトマーが一般式ＲＲ’Ｓｉ Ｙ２ （Ｒは１価のオ
レフィン不飽和炭化水素基又はヒドロカルボキシ基、Ｙ
は加水分解しうる帽しル、Ｒ゛は脂肪族不飽和炭化水素
以外の１価の炭化水素基あるいは、Ｙ、と同じもの）で
表わされる有機シランを遊離ラジカル生成化合物のもと
で反応させて得られたシラングラフト変成樹脂であり、
これは、前記特公昭５７−２４３７３号公報および特公
昭４８−１７１１号公報、特開昭５０−２４３４２号公
報等に示されている公知の方法を用いるもので、具体的
に例えばポリオレフィン系樹脂をベースにビニルトリメ
トキシシランなどをＤＣＰ （ジクミルパーオキサイド
〉等の重合開始剤作用の強い有機過酸化物を併用するこ
とによって得られる。Furthermore, when FEA silane graftomer resin is added to this,
The density is surprisingly improved, and various physical properties such as combustibility and mechanical properties are significantly improved. In particular, the content of ethyl acrylate is effective in the range of 3 to 50 w%, especially 10 to 2 O
% later is best. In addition, the silane graft polymer that has been grafted with silane in advance means that the silane graft polymer has the general formula RR'Si Y2 (R is a monovalent olefinically unsaturated hydrocarbon group or a hydrocarboxy group, Y
is a hydrolyzable cap, R is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon, or the same as Y) is reacted in the presence of a free radical-generating compound. It is a silane graft modified resin obtained by
This method uses the known method disclosed in the aforementioned Japanese Patent Publication No. 57-24373, Japanese Patent Publication No. 48-1711, Japanese Patent Application Laid-open No. 50-24342, etc. Specifically, for example, polyolefin resin is It can be obtained by using vinyltrimethoxysilane or the like as a base together with an organic peroxide having a strong polymerization initiator effect such as DCP (dicumyl peroxide).
シラングラフトマーの量として２重量％以下では高温時
の形状保持性、燃焼時のタレ防止に効果がないため、２
重量％以上が好ましい。またシラングラフトマーの架橋
度としてキシレン不溶残留分としてゲル分率という尺度
で言えば、ゲル分率２Ｏ重量％〜８０重量％が好ましい
。ゲル分率２Ｏ重量％以下では、高温時の形状保持性燃
焼時のタレ防止効果がうずく、ゲル分率８０重量％以上
では成形加工性が悪くなる。エチレンとアクリル酸エチ
ルとの重合体およびそのシラングラフトマーの組み合わ
せは、樹脂混合物の表面高度、耐寒性、耐ストレスクラ
ッキング、接着性向上などの諸々の要求により組み合わ
せが可能であり、いずれの組み合わせも容易に混練溶融
される。If the amount of silane graftomer is less than 2% by weight, it will not be effective in maintaining shape at high temperatures or preventing sagging during combustion.
It is preferably at least % by weight. Further, as the degree of crosslinking of the silane graftomer, the gel fraction is preferably 20% by weight to 80% by weight in terms of gel fraction as xylene-insoluble residue. If the gel fraction is less than 20% by weight, the shape retention at high temperatures and the effect of preventing sagging during combustion will be impaired, and if the gel fraction is more than 80% by weight, moldability will deteriorate. The combination of a polymer of ethylene and ethyl acrylate and its silane graftomer can be combined depending on various requirements such as surface height, cold resistance, stress cracking resistance, and improved adhesion of the resin mixture. Easily kneaded and melted.
（２）本発明において使用される水和金属化合物として
は、水和金属化合物が、分解開始温度が１５０〜４５０
′Ｃの範囲にあって一般弐Ｍ−Ｏｎ−Ｘ）−１２Ｏ（こ
こにＭは金属、ｍ、ｎは金属の原子価によって定まる１
以上の整数、Ｘは含有結合水素を示す数で表わされる化
合物又は該化合物を含む複塩であり具体的には、例えば
水酸化アルミニウム（１！ ２ ｏ３・３Ｈ；２Ｏ；又
はＡｉ（ＯＨ）３）、水酸化マグネシウム（Ｍ（］ ０
・ト１□０；又はＭＵ（ＯＨ）２、水酸化カルシウム（
ＣａＯ−町Ｏ又はＣａ （ＯＨ＞２ ）、水酸化バリ
ウム（Ｂａ Ｏ・＋１．２Ｏ又はＢａ Ｏ”９１−１２
Ｏ＞ 、ｍ化ジルコニウム水和物（ＺｒＯ−ｎＨ２Ｏ）
、酸化錫水和物（Ｓｎ Ｏ・Ｈ２Ｃ）、塩基性炭酸マグ
ネシウム（３Ｍ（］ ＣＯ３・ Ｍ（］ （ＯＨ
）２ ・ ３Ｈ２Ｏ） 、ハイドロタルサイト（
６Ｍａ ０−Ａｉ２Ｏ３ ・町０）、ドウツナイト（Ｎ
ａ ＣＯ３−Ａｌ２Ｏ２・ ｎＨ２Ｏ）、硼砂（Ｎａ
２Ｏ ” Ｂ２Ｏ５ ・５８２Ｏ）ホウ酸亜Ｋｉ （Ｚ
ｎ Ｂ４０７ ・２Ｚｎ Ｏ）等である。(2) As the hydrated metal compound used in the present invention, the hydrated metal compound has a decomposition initiation temperature of 150 to 450°C.
'C range and general 2M-On-X)-12O (where M is a metal, m and n are determined by the valence of the metal 1
The above integer, X is a compound represented by a number indicating the contained bonded hydrogen or a double salt containing the compound, and specifically, for example, aluminum hydroxide (1!2 o3.3H; 2O; or Ai(OH)3 ), magnesium hydroxide (M(] 0
・To1□0; or MU(OH)2, calcium hydroxide (
CaO-choO or Ca (OH>2), barium hydroxide (BaO・+1.2O or BaO"91-12
O>, m-zirconium hydrate (ZrO-nH2O)
, tin oxide hydrate (Sn O・H2C), basic magnesium carbonate (3M(] CO3・M(] (OH
)2 ・3H2O), hydrotalcite (
6Ma 0-Ai2O3 ・Town 0), Doutsunite (N
a CO3-Al2O2・nH2O), borax (Na
2O ” B2O5 ・582O) Boric acid Substituent Ki (Z
n B407 ・2Zn O), etc.
上記水和金属化合物を５０重量部から３００重量部配合
した場合、水和金属化合物の表面の僅かな水分により、
混練加工時の摩擦熱によってシラングラフトマーのシラ
ノール基（−）Ｓｉ−ＯＨ＞が、加水分解し無機質表面
のヒドロキシル基と縮合反応し強固なシロキリン結合を
生じ、高温時の形状保持性、燃焼時のドリップ防止を達
成し、機械物性として抗張力、信性、折り曲げ白化性、
摩耗性、薬品性、低温特性等の改善と物性バランスのと
れた加工性の良好な組成物を形成するものである。When 50 to 300 parts by weight of the above hydrated metal compound is blended, due to the slight moisture on the surface of the hydrated metal compound,
Due to the frictional heat during the kneading process, the silanol group (-)Si-OH> of the silane graftomer is hydrolyzed and undergoes a condensation reaction with the hydroxyl group on the inorganic surface to form a strong siloquiline bond, which improves shape retention at high temperatures and during combustion. Achieved drip prevention, mechanical properties such as tensile strength, reliability, bending whitening resistance,
It forms a composition that has improved abrasion resistance, chemical properties, low-temperature properties, etc., and has well-balanced physical properties and good processability.
５０重量部以下では、所望の難燃効果は（ｑにくく、ま
た３００重量部以上では抗張力等の機械物性が低下し、
また押出し加工性が悪くなる。If it is less than 50 parts by weight, the desired flame retardant effect will not be achieved (q), and if it is more than 300 parts by weight, mechanical properties such as tensile strength will decrease,
Moreover, extrusion processability deteriorates.
（３）本発明において使用されろ水和金属化合物は、表
面処理なしのものも、もちろん良いが、特に水和金属化
合物が１種以上のシランカップリング剤、シリコーン誘
導体又は脂肪酸、脂肪酸金属塩で表面処理されたものは
、機械特性および加工性が向上する。(3) The hydrated metal compound used in the present invention may of course be one without surface treatment, but in particular, the hydrated metal compound may be one or more silane coupling agents, silicone derivatives, fatty acids, or fatty acid metal salts. Surface-treated products have improved mechanical properties and processability.
（ｉ）シランカップリング剤としては一般式ＲＲ’５ｉ
Ｙ２で表わされ、Ｒは有機官能基、Ｙは加水分解しうる
有機基、Ｒｏは脂肪族不飽和炭化水素以外の一価の炭化
水素基あるいはＹと同じものであること、具体的には分
子内の一方の末端に無機質と反応する反応基（メトキシ
基、カルボキシル基、セロソルブ基など〉であり、これ
は一般的に三官能基を有する場合が多いが、三官能、−
官能を有する場合でも、もらろんよい。またもう一方の
末端には、有機材料である樹脂側と化学結合する反応基
（ビニル基、エポキシ基、メタクリル基、アミノ基、メ
ルカプト基など）を有するもので主鎖がアルコキシオリ
ゴマーを骨格とするものである。特に反応基としてメタ
クリル基、アクリル基が最も効果的な結合を引き起こす
。(i) As a silane coupling agent, general formula RR'5i
Represented by Y2, R is an organic functional group, Y is a hydrolyzable organic group, Ro is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon, or the same as Y, specifically, It is a reactive group (methoxy group, carboxyl group, cellosolve group, etc.) that reacts with inorganic substances at one end of the molecule, and it generally has a trifunctional group, but trifunctional, -
Even if you have sensuality, it's okay. The other end has a reactive group (vinyl group, epoxy group, methacrylic group, amino group, mercapto group, etc.) that chemically bonds with the resin side of the organic material, and the main chain has an alkoxy oligomer skeleton. It is something. In particular, as reactive groups, methacrylic groups and acrylic groups cause the most effective bonding.
（ｉｉ）シリコーン誘導体としては、シリコーン誘導体
がジメチルポリシロキサンの一部を官能基、加水分解基
等と置換してなるオリガノポリシロキリン変性物である
ジメチルポリシロキサンのメチル基の一部を各種の有機
基で置換したタイプで、各種の変性有機基としては、α
−メチルスチレン基、α−オレフィン基、ポリエーテル
、アルコール基、フルオロアルキル基なとの相溶性、親
水性、潤滑成形、撥水性などを改良することを目的とす
る変性基、アミン基、メルカプト基、エポキシ基、カル
ボキシル基などの反応性、吸着性を目的とした変成基、
高扱脂肪酸、カルバナ、アミドを置換した８１【型、つ
や出しを目的とした変性基、メタアクリロキシプロピル
基を有する反応性に富んだ変性型、末端にＯＨ基、ＮＨ
２基を有する反応型など、多種多様の変性基誘導体があ
げられる。(ii) As silicone derivatives, various silicone derivatives include a portion of the methyl group of dimethylpolysiloxane, which is a modified organopolysiloxane obtained by substituting a portion of dimethylpolysiloxane with a functional group, a hydrolyzable group, etc. This type is substituted with an organic group, and various modified organic groups include α
- Modifying groups, amine groups, mercapto groups for the purpose of improving compatibility with methylstyrene groups, α-olefin groups, polyethers, alcohol groups, fluoroalkyl groups, hydrophilicity, lubricious molding, water repellency, etc. , modified groups for the purpose of reactivity and adsorption such as epoxy groups and carboxyl groups,
Highly reactive fatty acid, carbana, amide-substituted 81 [type, modified group for polishing purposes, highly reactive modified type with methacryloxypropyl group, OH group at the end, NH
There are a wide variety of modified group derivatives, including reactive types having two groups.
（ｉ目）脂肪酸としては、脂肪酸がカルボキシ基（ＣＯ
ＯＨ＞を１個もつカルボン酸ＲＣＯＯト１のＲがＣ３〜
Ｃ４０の飽和および不飽和の鎖式構造をもつもので具体
的には、ステアリン酸などの飽和脂肪酸、オレイン酸な
どの不飽和脂肪酸等の汎用脂肪酸で充分効果が認められ
る。脂肪酸は、疎水性なので、例えば水酸化マグネシウ
ムのようにスラリー状での生成と同時に表面処理を施こ
したい場合、脂肪酸を乳化させる界面活性剤を同時に併
用して、エマルジョン化させて水中の水酸化マグネシウ
ムを表面処理して後に乾燥してもよい。その界面活性剤
は物性に影響を及ぼさない範囲で併用してもかまわない
。(I) As fatty acids, fatty acids have carboxy groups (CO
Carboxylic acid RCOO with one OH> R of 1 is C3~
Those having C40 saturated and unsaturated chain structures, specifically general-purpose fatty acids such as saturated fatty acids such as stearic acid and unsaturated fatty acids such as oleic acid, are sufficiently effective. Fatty acids are hydrophobic, so if you want to perform surface treatment at the same time as forming a slurry, such as magnesium hydroxide, use a surfactant that emulsifies the fatty acids at the same time to form an emulsion and reduce hydroxylation in water. Magnesium may be surface treated and then dried. The surfactant may be used in combination as long as it does not affect the physical properties.
（ｉｖ）脂肪酸金属塩としては、前記の脂肪酸とアルカ
リ金属との塩である（ＲＣＯＯＭ：Ｍはアルカリ金属原
子）もので、具体例としては、ステアリン酸ソーダ、ス
テアリン酸カリ、オレイン酸ソーダ、オレイン酸カリな
どがあげられる。もちろん脂肪酸としては直鎖飽和型、
不飽和型を問わず側鎖部分が金属と結合したものも、も
ちろん有効である。(iv) Fatty acid metal salts include salts of the aforementioned fatty acids and alkali metals (RCOOM: M is an alkali metal atom); specific examples include sodium stearate, potassium stearate, sodium oleate, Examples include acid potassium. Of course, as a fatty acid, it is a straight chain saturated type.
Regardless of the unsaturated type, those in which the side chain moiety is bonded to a metal are of course effective.
（４）その他の添加物
本発明の難燃性組成物は所望により、通常使用される添
加物例えば酸化防止剤、中和剤、紫外線吸収剤、帯電防
止剤、顔料、分散剤、滑剤、増粘剤、発泡剤、金属劣化
防ＩＥ剤、流動調整剤など、またリンおよびホスフィン
誘導体の難燃剤、その他の無機質充填剤、架橋剤、架橋
助剤等を含有させることもできる。又は電子線照射架橋
ざぜることも可能である。(4) Other additives If desired, the flame retardant composition of the present invention may contain commonly used additives such as antioxidants, neutralizers, ultraviolet absorbers, antistatic agents, pigments, dispersants, lubricants, and additives. It is also possible to contain a viscosity agent, a foaming agent, a metal deterioration prevention agent, a fluidity regulator, etc., a flame retardant such as phosphorus and phosphine derivatives, other inorganic fillers, a crosslinking agent, a crosslinking aid, etc. Alternatively, crosslinking by electron beam irradiation is also possible.
更に所望により強度向上、衝撃強度向上、成形加工性改
良としてα−オレフィン単独重合体又は共重合体および
α−オレフィンを主体とした酢酸ビニル、無水マレイン
酸、アクリル酸等の極性上ツマ−との共重合体（グラフ
ト共重合体含む）およびこれらの混合物、またそれらの
少なくとも１種以上のあらかじめシラングラフトさせた
シラングラフトマーを、特許請求範囲である、難燃性エ
チレン−エチルアクリレート樹脂組成物に添加しても何
ら差しつかえない。特に同レベルの低結晶性樹脂として
超低密度ポリエチレン（ＶＬＤＰＥ）、リニヤ−低密度
ポリエチレン（ＬＬＤＰＥ）が特に有効である。Furthermore, if desired, to improve strength, impact strength, and moldability, α-olefin homopolymers or copolymers and α-olefin-based polar polymers such as vinyl acetate, maleic anhydride, and acrylic acid may be added. Copolymers (including graft copolymers), mixtures thereof, and at least one silane-grafted silane graft tomer thereof are added to the claimed flame-retardant ethylene-ethyl acrylate resin composition. There is no harm in adding it. In particular, very low density polyethylene (VLDPE) and linear low density polyethylene (LLDPE) are particularly effective as low-crystalline resins of the same level.
（５）水和金属化合物の表面処理方法
処理方法は、ヘンシェルミキサー、ブレンダー等の攪拌
機械で充分であり、機種によっては、処理の攪拌時間の
長短の差はあるものの、特別の装置を必要としない。(5) Surface treatment method for hydrated metal compounds A stirring machine such as a Henschel mixer or blender is sufficient for the treatment method. Depending on the model, the length of stirring time for treatment may vary, but special equipment is not required. do not.
添加の方法は、滴下式、一括投入方式など、処理剤の使
用方法について使い分ける必要がある。It is necessary to use a different method of addition depending on how the processing agent is used, such as a dripping method or a bulk addition method.
また処理剤の性質については、水又はアルコール、溶剤
などで、希釈しても良いし、界面活性剤等でエマルジョ
ン化したものを用いてもよい。例えば水酸化マグネシウ
ムの生産ライン工程での処理もできる。これは生産ライ
ン工程で水酸化マグネシウムはスラリー状で上がり、こ
のとき表面処理剤を一括投入し充分に攪拌処理を行ない
、乾燥工程を行なうこともできる。また乾燥工程終了後
、上記のもので表面処理してももちろんよい。Regarding the properties of the processing agent, it may be diluted with water, alcohol, a solvent, etc., or it may be emulsified with a surfactant or the like. For example, it can be processed in a production line process for magnesium hydroxide. Magnesium hydroxide is produced in the form of a slurry during the production line process, and at this time, the surface treatment agent can be added all at once, sufficiently stirred, and then a drying process can be performed. Furthermore, after the drying process is completed, the surface may be treated with the above-mentioned materials.
（６）混合、混練方法
これらの各成分はそれぞれ計量混合され、従来のゴムプ
ラスチックのための装置と方法が利用でき特別の装置を
必要としない。すなわちリボンブレンダー、ヘンシェル
ミキサー等の混合攪拌機を用いて各成分を充分混合分散
させたのち、パンバリロール、押出機等の溶融混練機で
混練し目的物を得る。(6) Mixing and kneading method These components are individually measured and mixed, and conventional equipment and methods for rubber plastics can be used, and no special equipment is required. That is, each component is sufficiently mixed and dispersed using a mixer such as a ribbon blender or a Henschel mixer, and then kneaded using a melt kneader such as a panburi roll or an extruder to obtain the desired product.
（７）押出成形
押出成形は（６）で得たペレットをチューブ状、テープ
状など任意の形状のダイスを用いて押出せる。この場合
、シラングラフト物を架橋せしめるために錫系などの架
橋促進触媒を用いる必要もなく、また成形後、温水処理
や蒸気加圧を施して、架橋促進をうながす必要は全くな
い。(7) Extrusion molding In extrusion molding, the pellets obtained in (6) can be extruded using a die of any shape such as a tube shape or a tape shape. In this case, there is no need to use a crosslinking promoting catalyst such as a tin-based catalyst to crosslink the silane grafted product, and there is no need to promote crosslinking by hot water treatment or steam pressurization after molding.
その理由については特公昭５７−２６６２Ｏ号公報にも
触れているがシラングラフトマーのシラノール基と親和
性の良好な充填剤とが強固に結合するためで、グラフト
マー同士の架橋反応は必要はないためである。The reason for this is mentioned in Japanese Patent Publication No. 57-2662O, but it is because the silanol groups of the silane graftomer and the filler with good affinity are strongly bonded, and there is no need for a crosslinking reaction between the graftomers. It is.
従って、材料としてのシラングラフトマーは、吸水によ
る早期架橋を防ぐためにシラングラフトマーをアルミ内
装の袋へ保管することを強いられたが、（６）の方法等
で一度混練されたものは、吸水性の心配はなく、大気中
に３日間放置した場合でも、又乾燥容器内に密封した場
合３ケ月を経過しても押出加工性に支障のないことを確
認している。Therefore, silane graft tomer as a material was forced to be stored in aluminum-lined bags to prevent early crosslinking due to water absorption, but once kneaded using method (6) etc. It has been confirmed that there is no problem with extrusion processability even if the product is left in the air for 3 days or sealed in a dry container for 3 months.
本発明は、
（１）火災発生による燃焼によってもハロゲン系の有害
ガスおよび腐蝕性ガスを一斉発生しない、無公害化を達
成した難燃性樹脂組成物である。The present invention is: (1) A flame-retardant resin composition that does not generate any harmful halogen gas or corrosive gas even when burned due to a fire, and is pollution-free.
（２）従来使用した架橋設備を利用せずに演むだけでな
く、架橋設備自体のコスト、稼動、保守管理などが不要
となり材料の低コスト化を図ることが可能であり経済性
にも優れる。(2) Not only can it be performed without using conventional cross-linking equipment, but it also eliminates the cost, operation, maintenance, etc. of the cross-linking equipment itself, making it possible to reduce the cost of materials and being highly economical. .
（３）以上の特長は樹脂配合組成物上、充填剤の中でも
水和金属化合物に限定し、シラングラフトマーとのシラ
ノール基（）Ｓｉ−ＯＨ＞が水和金属化合物の表面のヒ
ドロキシル基（０ト１基）と水和金属化合物表面の僅か
な水分と有機金属化合物の触媒に類した金属化合物との
影響で、混練時に発生する摩擦前の環境下で加水分解に
よる縮合反応が生じ強固なシロキサン結合（Ｓｉ Ｏ
ＭｍＯｎ：Ｍ金属）を形成する。この時、触媒温水架橋
処理等を全く必要としない。(3) The above features are limited to the hydrated metal compound among the fillers in the resin blend composition, and the silanol group ()Si-OH> of the silane graftomer is the hydroxyl group (0) on the surface of the hydrated metal compound. Due to the influence of a small amount of moisture on the surface of the hydrated metal compound and a metal compound similar to the catalyst of an organometallic compound, a condensation reaction by hydrolysis occurs in the environment before friction that occurs during kneading, forming a strong siloxane. Bond (SiO
MmOn: M metal) is formed. At this time, there is no need for catalyst hot water crosslinking treatment or the like.
（４）このため燃焼時、発生する熱が水和金属化合物が
分解して脱水した水の気化熱によって吸収される冷却効
果と、本発明の特徴であるシラングラフトマーと水和金
属化合物間の強固な結合によって燃焼による分解を抑制
する働きにより、燃焼時タレ防止効果を発揮し、かつ固
い燃え殻を形成するため延焼防止効果を同時に発揮する
ものである。(4) Therefore, the heat generated during combustion is absorbed by the heat of vaporization of dehydrated water as the hydrated metal compound decomposes, and the cooling effect between the silane graftomer and the hydrated metal compound, which is a feature of the present invention, is achieved. The strong bond suppresses decomposition due to combustion, which prevents sagging during combustion, and forms a hard cinder, which simultaneously prevents the spread of fire.
更に強固な結合は発煙量を著しく抑制する効果も発揮す
る。Furthermore, strong bonding also exhibits the effect of significantly suppressing the amount of smoke generated.
（５）樹脂をエチレン−アクリル酸エチルを選ぶことに
よって、樹脂中の極性基と水和金属化合物との密着力が
向上すること、また、水和金属化合物はもとよりアルカ
リ金属を主成分とする為、燃焼時、離脱した水分により
アルカリ性を強く示し、酸性を示すアクリル酸との中和
化が起こりやすいため、難燃性に対しては更に著しい効
果を発揮する。また、エチレン−アクリル酸エチルは低
結晶性なのでエラストマーに匹敵するほどの柔軟性を有
し水和金属化合物を高充填化できるものである。(5) By choosing ethylene-ethyl acrylate as the resin, the adhesion between the polar groups in the resin and the hydrated metal compound is improved, and since the hydrated metal compound is mainly composed of alkali metals, During combustion, it exhibits strong alkalinity due to the water released, and neutralization with acrylic acid, which is acidic, is likely to occur, so it exhibits an even more remarkable effect on flame retardancy. Furthermore, since ethylene-ethyl acrylate has low crystallinity, it has flexibility comparable to that of elastomers, and can be highly filled with hydrated metal compounds.
（６）表面処理剤を使用することによって更に柔軟性、
成形加工性等を改善できる。(6) Further flexibility by using a surface treatment agent.
Molding processability etc. can be improved.
（７）また従来技術と比べ、前記の炭素粉末による燃焼
抑制効果とは全く別の燃焼抑制効果であり、目的に応じ
て識別を容易にするため、着色剤として、カーボンブラ
ックを始めとする種々の顔料の添加にかかわらずその燃
焼抑制効果があるため用途に応じて自由自在にカラーリ
ングが可能である。(7) In addition, compared to the conventional technology, the combustion suppressing effect is completely different from the combustion suppressing effect of the carbon powder described above, and in order to facilitate identification depending on the purpose, various coloring agents such as carbon black are used. Regardless of the addition of pigments, it has a combustion suppressing effect, so it is possible to freely color it depending on the application.
以下実施例をあげて説明する。 This will be explained below by giving examples.
実施例■
先ず、最初にエチレンとアクリル酸エチルとの共重合体
樹脂でおるエチレン−エチルアクリレート（ＥＥＡ）樹
脂２種類を第−表に示す配合で以下の手順に従って調整
した。Example (2) First, two types of ethylene-ethyl acrylate (EEA) resins, which are copolymer resins of ethylene and ethyl acrylate, were prepared according to the following procedure with the formulations shown in Table 1.
ビニルメトキシシランにジグミルパーオキサイド（ＤＣ
Ｐ＞を溶解させ、低結晶性ポリエチレン三種類（１）（
２）（３）を用い、表１の通り混合攪拌し、これを単軸
の５０ｍｍφ押出機を用いて押出温度１５０〜２Ｏ０℃
で押出し、ペレット状のシラングラフトマー樹脂Ａ、Ｂ
を得た。樹脂Ａ、Ｂは各々アルミラミネート袋内に密閉
封入し、外部の水分を遮断した状態で保存し必要に応じ
て小出して使用した。digmyl peroxide (DC) to vinylmethoxysilane
Three types of low-crystalline polyethylene (1) (
2) Using (3), mix and stir as shown in Table 1, and extrude this using a single-screw 50 mmφ extruder at an extrusion temperature of 150 to 200°C.
extruded into pelleted silane graftomer resins A and B.
I got it. Resins A and B were each hermetically sealed in an aluminum laminate bag, stored in a state where external moisture was blocked, and dispensed as needed for use.
（＊１）日本石油化学（体製レクスロンＥＥＡＥＡ含有
率５％ ＭＦＲ１，０
（＊２）日本石油化学（１１製レクスロンＥＥＡＥＡ含
有率１５％ ＭＦＲ３，０
次に表２に示すように各種成分を容器内に一括混合し、
パンバリロールで混練し、造粒した。(*1) Nippon Petrochemical (manufactured by Taiyo Co., Ltd. Rexron EEAEA content 5% MFR 1,0 (*2) Nippon Petrochemical (manufactured by 11 Rexron EEAEA content 15% MFR 3,0 Mix all at once in
The mixture was kneaded using a panbari roll and granulated.
得られた組成物を再度ロールプレスし各種の測定用試験
片を作製した。シラングラフトマーと水和金属化合物の
結合度としてはキシレン溶液残留分としてゲル分率を目
安とし、機械特性として抗張力、伸び、脆化温度、表面
特性として傷のつきにくさ、折り曲げ白化性、摩耗性、
熱特性として加熱変形率、耐熱性、その他の評価として
耐薬品性、酸素指数、発煙量、燃性特性としてドリップ
性、燃え殻の硬さ程度、延焼防止効果をそれぞれ判定し
た。また最終的に使用される場合の加工性チェックを５
０ｍφ押出機で確認した。更に材料としての総合判定を
行い表３に示した。The obtained composition was again roll-pressed to prepare various test pieces for measurement. The degree of bonding between the silane graftomer and the hydrated metal compound is based on the gel fraction as a residual amount in xylene solution, the mechanical properties are tensile strength, elongation, and embrittlement temperature, and the surface properties are scratch resistance, bending whitening, and abrasion. sex,
Thermal properties were determined by heating deformation rate and heat resistance, other evaluations were chemical resistance, oxygen index, and amount of smoke, and flammability properties were evaluated by dripping properties, cinder hardness, and fire spread prevention effect. In addition, check the workability in the case of final use.
Confirmed using a 0mφ extruder. Furthermore, a comprehensive evaluation of the materials was performed and shown in Table 3.
シラングラフトマーを組成物に含む難燃［１組酸物（実
施例１〜９）は全ての評価物性を満足し、組成物の色は
、原色灰、黄、黒でも燃焼特性は良好である。Flame-retardant compositions containing silane graftomers [1 set of acids (Examples 1 to 9) satisfied all evaluation physical properties, and the composition had good combustion characteristics even when the primary colors were gray, yellow, and black. .
また、シラングラフトマーを含まない組成物は比較例１
．２にみられるように表面特性が悪く、また熱特性およ
び燃焼特性が著しくあとる。In addition, a composition that does not contain silane graftomer is Comparative Example 1.
．． As seen in No. 2, the surface properties are poor, and the thermal properties and combustion properties are significantly inferior.
更に水酸化マグネシウムの添加範囲としては、比較例３
．４にみられるように３０手量部では、燃焼特性が悪く
、３５０重団部では、伸び、脆化温度および押出加工性
が著しく低下した。Furthermore, as for the addition range of magnesium hydroxide, Comparative Example 3
．． As seen in No. 4, at 30 parts by weight, the combustion characteristics were poor, and at 350 parts by weight, elongation, embrittlement temperature and extrusion processability were significantly reduced.
Claims (8)
チレン−エチルアクリレート樹脂とそれのあらかじめシ
ラングラフトさせたシラングラフトマーを混合させた樹
脂１００重量部に対して水和金属化合物５０〜３００重
量部を添加してなる難燃性エチレン−エチルアクリレー
ト系樹脂組成物。(1) 50 to 300 parts by weight of a hydrated metal compound per 100 parts by weight of a resin prepared by mixing ethylene-ethyl acrylate resin, which is a copolymer of ethylene and ethyl acrylate, with a silane graft tomer grafted with silane in advance. A flame-retardant ethylene-ethyl acrylate resin composition.
Ｒは１価のオレフィン不飽和炭化水素基又はヒドロカル
ボキシ基、Ｙは加水分解しうる有機基、Ｒ′は脂肪族不
飽和炭化水素以外の１価の炭化水素基あるいは、Ｙと同
じもの）で表わされる有機シランを遊離ラジカル生成化
合物のもとで反応させて得られたシラングラフト変性樹
脂である特許請求の範囲第１項記載の難燃性エチレン−
エチルアクリレート系樹脂組成物。(2) The silane graftomer has the general formula RR'SiY_2 (
R is a monovalent olefinically unsaturated hydrocarbon group or a hydrocarboxy group, Y is a hydrolyzable organic group, R' is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon, or the same as Y) The flame-retardant ethylene resin according to claim 1, which is a silane graft-modified resin obtained by reacting the represented organic silane in the presence of a free radical-forming compound.
Ethyl acrylate resin composition.
０℃の範囲にあって一般式ＭｍＯｎ・ＸＨ＿２Ｏ（ここ
にＭは金属、ｍ、ｎは金属の原子価によって定まる１以
上の整数、Ｘは含有結合水素を示す数で表わされる化合
物又は該化合物を含む複塩である特許請求の範囲第１項
記載の難燃性エチレン−エチルアクリレート系樹脂組成
物。(3) The hydrated metal compound has a decomposition initiation temperature of 150 to 45
A compound or a compound represented by the general formula MmOn.XH_2O (where M is a metal, m and n are integers of 1 or more determined by the valence of the metal, and The flame-retardant ethylene-ethyl acrylate resin composition according to claim 1, which is a double salt containing.
剤、シリコーン誘導体又は脂肪酸、脂肪酸金属塩で表面
処理された特許請求の範囲第３項記載の難燃性エチレン
−エチルアクリレート系樹脂組成物。(4) The flame-retardant ethylene-ethyl acrylate resin composition according to claim 3, wherein the hydrated metal compound is surface-treated with one or more silane coupling agents, silicone derivatives, fatty acids, or fatty acid metal salts. .
２で表わされ、Ｒは有機官能基、Ｙは加水分解しうる有
機基、Ｒ′は脂肪族不飽和炭化水素以外の一価の炭化水
素基あるいはＹと同じものである特許請求の範囲の第４
項記載の難燃性エチレン−エチルアクリレート系樹脂組
成物。(5) The silane coupling agent has the general formula RR'SiY_
2, R is an organic functional group, Y is a hydrolyzable organic group, and R' is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon or the same as Y. Fourth
The flame-retardant ethylene-ethyl acrylate resin composition described in 1.
部を官能基、加水分解基等と置換してなるオリガノポリ
シロキサン変性物である特許請求の範囲第４項記載の難
燃性エチレン−エチルアクリレート系樹脂組成物。(6) The flame-retardant ethylene-ethyl acrylate system according to claim 4, wherein the silicone derivative is a modified organopolysiloxane obtained by substituting a part of dimethylpolysiloxane with a functional group, a hydrolyzable group, etc. Resin composition.
カルボン酸ＲＣＯＯＨのＲがＣ３〜Ｃ４０の飽和および
不飽和の鎖式構造をもつものである特許請求の範囲の第
４項記載の難燃性エチレン−エチルアクリレート系樹脂
組成物。(7) Flame retardancy according to claim 4, wherein the fatty acid is a carboxylic acid RCOOH having one carboxyl group (COOH), and R has a C3 to C40 saturated and unsaturated chain structure. Ethylene-ethyl acrylate resin composition.
個もつカルボン酸ＲＣＯＯＨのＲがＣ３〜Ｃ４０の飽和
および不飽和の鎖式構造をもつ脂肪酸とアルカリ金属と
の塩である（ＲＣＯＯＭ：Ｍはアルカリ金属原子）特許
請求の範囲の第４項記載の難燃性エチレン−エチルアク
リレート系樹脂組成物。(8) Fatty acid metal salt has 1 carboxyl group (COOH)
R of the carboxylic acid RCOOH having 3 to 40 carbon atoms is a salt of a C3 to C40 fatty acid with a saturated and unsaturated chain structure and an alkali metal (RCOOM: M is an alkali metal atom) Flame-retardant ethylene-ethyl acrylate resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13831686A JPS62295939A (en) | 1986-06-16 | 1986-06-16 | Flame-retardant ethylene/ethyl acrylate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13831686A JPS62295939A (en) | 1986-06-16 | 1986-06-16 | Flame-retardant ethylene/ethyl acrylate resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62295939A true JPS62295939A (en) | 1987-12-23 |
Family
ID=15219044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13831686A Pending JPS62295939A (en) | 1986-06-16 | 1986-06-16 | Flame-retardant ethylene/ethyl acrylate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62295939A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009298831A (en) * | 2008-06-10 | 2009-12-24 | Hitachi Cable Ltd | Non-halogen flame-retardant thermoplastic elastomer resin composition, its manufacturing method and electric wire or cable using the same |
-
1986
- 1986-06-16 JP JP13831686A patent/JPS62295939A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009298831A (en) * | 2008-06-10 | 2009-12-24 | Hitachi Cable Ltd | Non-halogen flame-retardant thermoplastic elastomer resin composition, its manufacturing method and electric wire or cable using the same |
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