JP6792646B2 - マイクロ高密度シール、組成物、およびこれらを作製する方法 - Google Patents
マイクロ高密度シール、組成物、およびこれらを作製する方法 Download PDFInfo
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- JP6792646B2 JP6792646B2 JP2018563438A JP2018563438A JP6792646B2 JP 6792646 B2 JP6792646 B2 JP 6792646B2 JP 2018563438 A JP2018563438 A JP 2018563438A JP 2018563438 A JP2018563438 A JP 2018563438A JP 6792646 B2 JP6792646 B2 JP 6792646B2
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- silane
- polyolefin
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- 239000000203 mixture Substances 0.000 title claims description 190
- 238000000034 method Methods 0.000 title claims description 65
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 291
- 229910000077 silane Inorganic materials 0.000 claims description 284
- 229920000098 polyolefin Polymers 0.000 claims description 203
- 238000007789 sealing Methods 0.000 claims description 141
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 115
- -1 polypropylene Polymers 0.000 claims description 57
- 229920001112 grafted polyolefin Polymers 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 49
- 239000004088 foaming agent Substances 0.000 claims description 48
- 238000009833 condensation Methods 0.000 claims description 41
- 230000005494 condensation Effects 0.000 claims description 41
- 239000004711 α-olefin Substances 0.000 claims description 38
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 28
- 238000004132 cross linking Methods 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 18
- 229920001155 polypropylene Polymers 0.000 claims description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 16
- 238000007906 compression Methods 0.000 claims description 13
- 230000006835 compression Effects 0.000 claims description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 9
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- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000463 material Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 33
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- 230000008569 process Effects 0.000 description 30
- 229920002943 EPDM rubber Polymers 0.000 description 26
- 239000003981 vehicle Substances 0.000 description 26
- 150000001336 alkenes Chemical class 0.000 description 19
- 239000000945 filler Substances 0.000 description 19
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
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- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 229920001187 thermosetting polymer Polymers 0.000 description 10
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- 239000011521 glass Substances 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
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- 150000002978 peroxides Chemical class 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000004156 Azodicarbonamide Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001343 alkyl silanes Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- 235000019399 azodicarbonamide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
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- 239000012815 thermoplastic material Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 2
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- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- IXQIQBXABDUOAW-UHFFFAOYSA-N n'-(trimethoxysilylmethyl)hexane-1,6-diamine Chemical compound CO[Si](OC)(OC)CNCCCCCCN IXQIQBXABDUOAW-UHFFFAOYSA-N 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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Description
[0039]第1のポリオレフィンは、オレフィンブロックコポリマー、エチレン/α−オレフィンコポリマー、プロピレン/α−オレフィンコポリマー、EPDM、EPM、またはこれらの材料のいずれかの2つ以上のものの混合物を含めた、ポリオレフィンエラストマーでよい。例示的なブロックコポリマーは、商品名INFUSE(商標)で販売されているもの、オレフィンブロックコポリマー(Dow Chemical Company)およびSEPTON(商標)V−SERIES、スチレン−エチレン−ブチレン−スチレンブロックコポリマー(株式会社クラレ)を含む。例示的なエチレン/α−オレフィンコポリマーは、商品名TAFMER(商標)(例えば、TAFMER DF710)(三井化学株式会社)、およびENGAGE(商標)(例えば、ENGAGE8150)(Dow Chemical Company)として販売されているものを含む。例示的なプロピレン/α−オレフィンコポリマーは、商品名VISTAMAXX6102グレード(Exxon Mobil Chemical Company)、TAFMER(商標)XM(三井化学)、およびVersify(Dow Chemical Company)として販売されているものを含む。EPDMは、約0.5〜約10重量%のジエン含量を有し得る。EPMは、45重量%〜75重量%のエチレン含量を有し得る。
[0050]第2のポリオレフィンは、オレフィンブロックコポリマー、エチレン/α−オレフィンコポリマー、プロピレン/α−オレフィンコポリマー、EPDM、EPM、またはこれらの材料のいずれかの2つ以上のものの混合物を含めた、ポリオレフィンエラストマーでよい。例示的なブロックコポリマーは、商品名INFUSE(商標)(Dow Chemical Company)およびSEPTON(商標)V−SERIES(Kuraray Co.、LTD.)として販売されているものを含む。例示的なエチレン/α−オレフィンコポリマーは、商品名TAFMER(商標)(例えば、TAFMER DF710)(三井化学株式会社)およびENGAGE(商標)(例えば、ENGAGE8150)(Dow Chemical Company)として販売されているものを含む。例示的なプロピレン/α−オレフィンコポリマーは、商品名TAFMER(商標)XMグレード(三井化学)およびVISTAMAXX(商標)(例えば、VISTAMAXX6102)(Exxon Mobil Chemical Company)として販売されているものを含む。EPDMは、約0.5〜約10重量%のジエン含量を有し得る。EPMは、45重量%〜75重量%のエチレン含量を有し得る。
[0062]グラフト化開始剤(本開示において「ラジカル開始剤」とまた称される)は、それぞれのポリオレフィンと反応して、シラン架橋剤分子と反応し、かつ/またはカップリングすることができる反応種を形成することによって、少なくとも第1および第2のポリオレフィンのグラフトプロセスにおいて利用することができる。グラフト化開始剤は、ハロゲン分子、アゾ化合物(例えば、アゾビスイソブチル)、カルボキシルペルオキシ酸(carboxylic peroxyacids)、ペルオキシ酸エステル、ペルオキシケタール、ならびにペルオキシド(例えば、アルキルヒドロペルオキシド、ジアルキルペルオキシド、およびジアシルペルオキシド)を含むことができる。一部の実施形態では、グラフト化開始剤は、ジ−t−ブチルペルオキシド、t−ブチルクミルペルオキシド、ジクミルペルオキシド、2,5−ジメチル−2,5−ジ(t−ブチル−ペルオキシ)ヘキシン−3,1,3−ビス(t−ブチル−ペルオキシ−イソプロピル)ベンゼン、n−ブチル−4,4−ビス(t−ブチル−ペルオキシ)バレレート、ベンゾイルペルオキシド、t−ブチルペルオキシベンゾエート、t−ブチルペルオキシイソプロピルカーボネート、およびt−ブチルペルベンゾエート、ならびにビス(2−メチルベンゾイル)ペルオキシド、ビス(4−メチルベンゾイル)ペルオキシド、t−ブチルペルオクトエート、クメンヒドロペルオキシド、メチルエチルケトンペルオキシド、ラウリルペルオキシド、tert−ブチルペルアセテート、ジ−t−アミルペルオキシド、t−アミルペルオキシベンゾエート、1,1−ビス(t−ブチルペルオキシ)−3,3,5−トリメチルシクロヘキサン、α,α’−ビス(t−ブチルペルオキシ)−1,3−ジイソプロピルベンゼン、α,α’−ビス(t−ブチルペルオキシ(butylpexoxy))−1,4−ジイソプロピルベンゼン、2,5−ビス(t−ブチルペルオキシ)−2,5−ジメチルヘキサン、および2,5−ビス(t−ブチルペルオキシ)−2,5−ジメチル−3−ヘキシンおよび2,4−ジクロロベンゾイルペルオキシドから選択される有機過酸化物である。例示的なペルオキシドは、商品名LUPEROX(商標)として販売されているもの(Arkema、Inc.から入手可能)を含む。
[0065]シラン架橋剤を使用して、第1および第2のポリオレフィン上へシラン部分を共有結合的にグラフトすることができ、シラン架橋剤は、アルコキシシラン、シラザン、シロキサン、またはこれらの組合せを含み得る。様々な潜在的なシラン架橋剤またはシラン架橋剤分子のグラフトおよび/またはカップリングは、それぞれのシラン架橋剤と反応するグラフト化開始剤によって形成される反応種によって促進される。
[0074]縮合触媒は、シラングラフト化ポリオレフィンエラストマー上のシラングラフトの加水分解およびそれに続く縮合の両方を促進し、架橋を形成することができる。一部の態様では、架橋は、電子ビーム線の使用によって助長することができる。一部の態様では、縮合触媒は、例えば、有機塩基、カルボン酸、ならびに有機金属化合物(例えば、有機チタネート、ならびに鉛、コバルト、鉄、ニッケル、亜鉛、およびスズの錯体またはカルボン酸塩)を含むことができる。他の態様では、縮合触媒は、脂肪酸および金属錯体化合物、例えば、金属炭酸塩;アルミニウムトリアセチルアセトネート、鉄トリアセチルアセトネート、マンガンテトラアセチルアセトネート、ニッケルテトラアセチルアセトネート、クロムヘキサアセチルアセトネート、チタンテトラアセチルアセトネートおよびコバルトテトラアセチルアセトネート;金属アルコキシド、例えば、アルミニウムエトキシド、アルミニウムプロポキシド、アルミニウムブトキシド、チタンエトキシド、チタンプロポキシドおよびチタンブトキシド;金属塩化合物、例えば、酢酸ナトリウム、オクチル酸スズ、オクチル酸鉛、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸カルシウム、ナフテン酸鉛、ナフテン酸コバルト、ジブチルスズジオクトエート、ジブチルスズジラウレート、ジブチルスズマレエートおよびジブチルスズジ(2−エチルヘキサノエート);酸性化合物、例えば、ギ酸、酢酸、プロピオン酸、p−トルエンスルホン酸、トリクロロ酢酸、リン酸、モノアルキルリン酸、ジアルキルリン酸、p−ヒドロキシエチル(メタ)アクリレートのリン酸エステル、モノアルキル亜リン酸およびジアルキル亜リン酸;酸、例えば、p−トルエンスルホン酸、無水フタル酸、安息香酸、ベンゼンスルホン酸、ドデシルベンゼンスルホン酸、ギ酸、酢酸、イタコン酸、シュウ酸およびマレイン酸、これらの酸のアンモニウム塩、低級アミン塩または多価金属の塩、水酸化ナトリウム、塩化リチウム;有機金属化合物、例えば、ジエチル亜鉛およびテトラ(n−ブトキシ)チタン;およびアミン、例えば、ジシクロヘキシルアミン、トリエチルアミン、N,N−ジメチルベンジルアミン、N,N,N’,N’−テトラメチル−1,3−ブタンジアミン、ジエタノールアミン、トリエタノールアミンおよびシクロヘキシルエチルアミンを含むことができる。さらに他の態様では、縮合触媒は、ジブチルスズジラウレート(ibutyltindilaurate)、ジオクチルスズマレエート、ジブチルスズジアセテート、ジブチルスズジオクトエート、酢酸第一スズ、オクタン酸第一スズ、ナフテン酸鉛、カプリル酸亜鉛、およびナフテン酸コバルトを含むことができる。シラン架橋ポリオレフィンエラストマーまたはブレンドの所望の最終材料特性によって、単一の縮合触媒または縮合触媒の混合物を利用し得る。縮合触媒(複数可)は、シラングラフト化ポリオレフィンエラストマー/ブレンド組成物の全重量に基づいて、約0.25重量%〜約8重量%を含めて、約0.01重量%〜約1.0重量%の量で存在し得る。
[0076]発泡剤は、押出および/または成形プロセスの間に、シラングラフト化ポリオレフィンエラストマーおよび縮合触媒ブレンドに加えられ、発泡したシラン架橋ポリオレフィンエラストマーを生成する、化学的発泡剤(例えば、有機もしくは無機発泡剤)および/または物理的発泡剤(例えば、気体および揮発性低重量分子)でよい。
[0082]シラン架橋ポリオレフィンエラストマーは、1種もしくは複数の充填剤を任意選択で含み得る。充填剤(複数可)は、シラングラフト化ポリオレフィンと共に押し出し得、一部の態様では、20%超、30%超、40%超、または50%超の結晶化度を有するさらなるポリオレフィンを含み得る。一部の態様では、充填剤(複数可)は、金属酸化物、金属水酸化物、金属炭酸塩、金属硫酸塩、金属ケイ酸塩、粘土、タルク、カーボンブラック、およびシリカを含み得る。用途および/または所望の特性によって、これらの材料は、煙霧を出す(fumed)か、またはか焼し得る。
[0090]マイクロ高密度シラン架橋ポリオレフィンエラストマーの合成/生成は、それぞれの構成要素を、押出の前にゴム化合物を混合および輸送するさらなるステップの必要性を除去する、単一ステップのMonosilプロセスを使用して1つの押出機において、または2ステップのSioplasプロセスを使用して2つの押出機において合わせることによって行い得る。
[00115]「熱可塑性物質」は、本明細書で使用する場合、熱に曝露されたときに軟化し、室温に冷却したときその当初の状態に戻るポリマーを意味すると定義される。「熱硬化性物質」は、本明細書で使用する場合、硬化したときに凝固し、不可逆的に「固化」または「架橋」するポリマーを意味すると定義される。上記のMonosilまたはSioplasプロセスのいずれかにおいて、最終熱硬化性マイクロ高密度シラン架橋ポリオレフィンエラストマーまたはマイクロ高密度シーリングメンバーを生成するために使用される様々な異なる材料の熱可塑性および熱硬化性の特性の慎重なバランスを理解することは重要である。反応二軸スクリュー押出機、反応単軸スクリュー押出機、および/または反応単軸スクリュー押出機を使用して混合され、反応する中間ポリマー材料のそれぞれは熱硬化性物質である。したがって、シラングラフト化ポリオレフィンブレンドおよび発泡したシラン架橋性ポリオレフィンブレンドは熱可塑性物質であり、それぞれの材料が流動することができるように加熱によって軟化することができる。発泡したシラン架橋性ポリオレフィンブレンドが未硬化のシーリングエレメントまたは他のそれぞれの物品へと押し出され、成形され、プレスされ、かつ/または形づくられると、発泡したシラン架橋性ポリオレフィンブレンドは、周囲温度および周囲湿度にて架橋または硬化し始め、マイクロ高密度シーリングメンバーおよびマイクロ高密度シラン架橋ポリオレフィンブレンドを形成することができる。
[00125]全ての化学物質、前駆体および他の構成物は、商業的なサプライヤーから得て、それ以上精製することなく提供されたまま使用した。
[00126]実施例1(Ex.1)またはED76−4Aは、82.55重量%のENGAGE8842および14.45重量%のMOSTEN TB003を3.0重量%のSILAN RHS14/032またはSILFIN29と一緒に押し出すことによって生成し、シラングラフト化ポリオレフィンエラストマーを形成させた。次いで、実施例1のシラングラフト化ポリオレフィンエラストマーを、2.0重量%のMBF−AC170EVAマイクロカプセル化された起泡剤、3重量%のAmbicat LE4472縮合触媒、および0.7重量%のAD−2プロセス助剤(process aide)と共に押し出し、発泡したシラン架橋性ポリオレフィンエラストマーを形成させ、次いで、これを未硬化のマイクロ高密度シーリングメンバーの形態へと押し出した。次いで、未硬化のマイクロ高密度シーリングメンバーの実施例1の発泡したシラン架橋性ポリオレフィンエラストマーを周囲温度および湿度にて硬化させて、本開示のエラストマーと一致する発泡したシラン架橋ポリオレフィンエラストマーを形成させた。実施例1の組成物は下記の表1に提供し、その発泡したシラン架橋ポリオレフィンブレンドと関連する材料特性を下記の表2に提供する。
[00127]実施例2(Ex.2)またはED76−4Eは、19.00重量%のENGAGE8150、58.00重量%のENGAGE8842、および20.00重量%のMOSTEN TB003を3.0重量%のSILAN RHS14/032またはSILFIN29と一緒に押し出すことによって生成し、シラングラフト化ポリオレフィンエラストマーを形成させた。次いで、実施例2のシラングラフト化ポリオレフィンエラストマーを、2.0重量%のMBF−AC170EVAマイクロカプセル化された起泡剤、3重量%のAmbicat LE4472縮合触媒、および0.7重量%のAD−2プロセス助剤(process aide)と共に押し出し、発泡したシラン架橋性ポリオレフィンエラストマーを形成させ、次いで、これを未硬化のマイクロ高密度シーリングメンバーへと押し出した。次いで、未硬化のマイクロ高密度シーリングメンバーの実施例2の発泡したシラン架橋性ポリオレフィンエラストマーを、周囲温度および湿度にて硬化させて、本開示のエラストマーと一致する発泡したシラン架橋ポリオレフィンエラストマーを形成させた。実施例2の組成物は下記の表1に提供し、その発泡したシラン架橋ポリオレフィンブレンドと関連する材料特性を、下記の表2に提供する。
[00128]実施例3(Ex.3)またはED76−5は、19.00重量%のENGAGE8150、53.00重量%のENGAGE8842、および25.00重量%のMOSTEN TB003を3.0重量%のSILAN RHS14/032またはSILFIN29と一緒に押し出すことによって生成し、シラングラフト化ポリオレフィンエラストマーを形成させた。次いで、実施例3のシラングラフト化ポリオレフィンエラストマーを2.0重量%のMBF−AC170EVAマイクロカプセル化された起泡剤、3重量%のAmbicat LE4472縮合触媒、および0.7重量%のAD−2プロセス助剤(process aide)と共に押し出し、発泡したシラン架橋性ポリオレフィンエラストマーを形成させ、これを次いで、未硬化のマイクロ高密度シーリングメンバーへと押し出した。次いで、未硬化のマイクロ高密度シーリングメンバーの実施例3の発泡したシラン架橋性ポリオレフィンエラストマーを、周囲温度および湿度にて硬化させて、本開示のエラストマーと一致する発泡したシラン架橋ポリオレフィンエラストマーを形成させた。実施例3の組成物は下記の表1に提供し、その発泡したシラン架橋ポリオレフィンブレンドと関連する材料特性を、下記の表2に提供する。
[00129]実施例4(Ex.4)またはED76−6は、16.36重量%のENGAGE8150、45.64重量%のENGAGE8842、および35.00重量%のMOSTEN TB003を3.0重量%のSILAN RHS14/032またはSILFIN29と一緒に押し出すことによって生成し、シラングラフト化ポリオレフィンエラストマーを形成させた。次いで、実施例4のシラングラフト化ポリオレフィンエラストマーを、2.0重量%のMBF−AC170EVAマイクロカプセル化された起泡剤、3重量%のAmbicat LE4472縮合触媒、および0.7重量%のAD−2プロセス助剤(process aide)と共に押し出し、発泡したシラン架橋性ポリオレフィンエラストマーを形成させ、次いで、これを未硬化のマイクロ高密度シーリングメンバーへと押し出した。次いで、未硬化のマイクロ高密度シーリングメンバーの実施例4の発泡したシラン架橋性ポリオレフィンエラストマーを、周囲温度および湿度にて硬化させて、本開示のエラストマーと一致する発泡したシラン架橋ポリオレフィンエラストマーを形成させた。実施例4の組成物は下記の表1に提供し、その発泡したシラン架橋ポリオレフィンブレンドと関連する材料特性を、下記の表2に提供する。
[00134]実施形態Aは、0.70g/cm3未満の密度を有する発泡したシラン架橋ポリオレフィンエラストマーを含む組成物を含むマイクロ高密度シーリングメンバーであって、マイクロ高密度シーリングメンバーは、ASTM D395(22時間@70℃)によって測定すると、約40.0%〜約78.0%の圧縮永久ひずみを示す、マイクロ高密度シーリングメンバーである。
本発明は以下の実施態様を含む。
(1)0.70g/cm 3 未満の密度、ASTM D412に従って測定される5.0〜8.7MPaの範囲の引張強度、ASTM D412に従って測定される60〜87の範囲のショアA硬度、及び約5%〜約20%の結晶化度を有する発泡したシラン架橋ポリオレフィンエラストマーブレンドを含む組成物を含む、マイクロ高密度シーリングメンバーであって、
約1重量%〜約35重量%の発泡したシラン架橋ポリオレフィンエラストマーブレンドが40%超の結晶化度を有するポリプロピレン充填剤であり、
マイクロ高密度シーリングメンバーがASTM D395(22時間@70℃)によって測定すると、約40.0%〜約78.0%の圧縮永久ひずみを示し、
発泡したシラン架橋ポリオレフィンエラストマーブレンドが、0.86g/cm 3 未満の密度を有する第1のポリオレフィン、ここで第1のポリオレフィンはエチレン/α−オレフィンコポリマーである;40%未満の結晶化度を有する第2のポリオレフィン、ここで第2のポリオレフィンはエチレン/α−オレフィンコポリマー、プロピレン/α−オレフィンコポリマー、又はプロピレン/α−オレフィンコポリマーとエチレン/α−オレフィンコポリマーの混合物である;及びポリプロピレン充填剤を、シラン架橋剤及びグラフト化開始剤を用いてシラングラフト化して、シラングラフト化ポリオレフィンブレンドを形成し、シラングラフト化ポリオレフィンブレンドを縮合触媒、およびマイクロカプセル化された発泡剤を用いて発泡、架橋してなる、マイクロ高密度シーリングメンバー。
(2)発泡したシラン架橋ポリオレフィンエラストマーブレンドが約3重量%〜約10重量%のポリプロピレン充填剤を含み、約0.60g/cm 3 〜約0.69g/cm 3 の密度を有する、(1)に記載のマイクロ高密度シーリングメンバー。
(3)前記発泡したシラン架橋ポリオレフィンエラストマーブレンドが、約5%〜約10%の結晶化度を示す、(1)又は(2)に記載のマイクロ高密度シーリングメンバー。
(4)前記発泡したシラン架橋ポリオレフィンエラストマーブレンドが、約−75℃〜約−25℃のガラス転移温度を示す、(1)から(3)のいずれかに記載のマイクロ高密度シーリングメンバー。
(5)ASTM D2244によって測定すると、約0.25△E〜約2.0△Eの風化による色の差異を示す、(1)から(4)のいずれかに記載のマイクロ高密度シーリングメンバー。
(6)着色剤をさらに含む、(1)から(5)のいずれかに記載のマイクロ高密度シーリングメンバー。
(7)マイクロ高密度シーリングメンバーを作製するための方法であって、
0.86g/cm 3 未満の密度を有する第1のポリオレフィン、40%未満の結晶化度を有する第2のポリオレフィン、40%超の結晶化度を有するポリプロピレン充填剤、シラン架橋剤、およびグラフト化開始剤を一緒に押し出して、シラングラフト化ポリオレフィンブレンドを形成させるステップと、ここで、シラングラフト化ポリオレフィンブレンドは約1重量%〜約35重量%のポリプロピレン充填剤を含む;
前記シラングラフト化ポリオレフィンブレンド、縮合触媒、およびマイクロカプセル化された発泡剤を一緒に押し出して、発泡したシラン架橋可能なポリオレフィンブレンドを形成させるステップと;
前記発泡したシラン架橋可能なポリオレフィンブレンドを未硬化のマイクロ高密度シーリングエレメントへと成形するステップと;
前記未硬化のマイクロ高密度シーリングエレメントの前記発泡したシラン架橋可能なポリオレフィンブレンドを周囲温度および周囲湿度にて架橋させて、前記エレメントを、約0.60g/cm 3 〜約0.69g/cm 3 の密度を有し、かつ発泡したシラン架橋されたポリオレフィンブレンドを含むマイクロ高密度シーリングメンバーへと形成させるステップと
を含み、
第1のポリオレフィンはエチレン/α−オレフィンコポリマーであり、第2のポリオレフィンはエチレン/α−オレフィンコポリマー、プロピレン/α−オレフィンコポリマー、又はプロピレン/α−オレフィンコポリマーとエチレン/α−オレフィンコポリマーの混合物であり、
前記マイクロ高密度シーリングメンバーは、ASTM D395(22時間@70℃)によって測定すると、約40.0%〜約78.0%の圧縮永久ひずみを示し、
マイクロ高密度シーリングメンバーが、ASTM D412に従って測定される5.0〜8.7MPaの範囲の引張強度を示し、
マイクロ高密度シーリングメンバーが、ASTM D412に従って測定される60〜87の範囲のショアA硬度を示し、
発泡したシラン架橋されたポリオレフィンブレンドが約5%〜約20%の結晶化度を示し、
発泡したシラン架橋可能なポリオレフィンブレンドが熱可塑性の特性を示す、方法。
(8)発泡したシラン架橋されたポリオレフィンブレンドが約5%〜約10%の結晶化度を示す、(7)に記載の方法。
(9)ポリプロピレン充填剤の量が約3重量%〜約10重量%の範囲である(7)に記載の方法。
Claims (8)
- 0.70g/cm3未満の密度、ASTM D412に従って測定される5.0〜8.7MPaの範囲の引張強度、ASTM D412に従って測定される60〜87の範囲のショアA硬度、及び5%〜20%の結晶化度を有する発泡したシラン架橋ポリオレフィンエラストマーブレンドからなるマイクロ高密度シーリングメンバーであって、
1重量%〜35重量%の発泡したシラン架橋ポリオレフィンエラストマーブレンドがポリプロピレンであり、
マイクロ高密度シーリングメンバーがASTM D395(22時間@70℃)によって測定すると、40.0%〜78.0%の圧縮永久ひずみを示し、
発泡したシラン架橋ポリオレフィンエラストマーブレンドが、0.86g/cm3未満の密度を有する第1のポリオレフィン、ここで第1のポリオレフィンはエチレン/α−オレフィンコポリマーである;40%未満の結晶化度を有する第2のポリオレフィン、ここで第2のポリオレフィンはエチレン/α−オレフィンコポリマー、プロピレン/α−オレフィンコポリマー、又はプロピレン/α−オレフィンコポリマーとエチレン/α−オレフィンコポリマーの混合物である;及び40%超の結晶化度を有するポリプロピレンを、シラン架橋剤及びグラフト化開始剤を用いてシラングラフト化して、シラングラフト化ポリオレフィンブレンドを形成し、シラングラフト化ポリオレフィンブレンドを縮合触媒、およびマイクロカプセル化された発泡剤を用いて発泡、架橋してなり、
シラン架橋剤がビニルトリメトキシシラン及び/又はビニルトリエトキシシランである、マイクロ高密度シーリングメンバー。 - 発泡したシラン架橋ポリオレフィンエラストマーブレンドが3重量%〜10重量%のポリプロピレンを含み、0.60g/cm3 〜0.69g/cm3の密度を有する、請求項1に記載のマイクロ高密度シーリングメンバー。
- 前記発泡したシラン架橋ポリオレフィンエラストマーブレンドが、5%〜10%の結晶化度を示す、請求項1又は2に記載のマイクロ高密度シーリングメンバー。
- 前記発泡したシラン架橋ポリオレフィンエラストマーブレンドが、−75℃〜−25℃のガラス転移温度を示す、請求項1から3のいずれか一項に記載のマイクロ高密度シーリングメンバー。
- 着色剤をさらに含む、請求項1から4のいずれか一項に記載のマイクロ高密度シーリングメンバー。
- マイクロ高密度シーリングメンバーを作製するための方法であって、
0.86g/cm3未満の密度を有する第1のポリオレフィン、40%未満の結晶化度を有する第2のポリオレフィン、40%超の結晶化度を有するポリプロピレン、シラン架橋剤、およびグラフト化開始剤を一緒に押し出して、シラングラフト化ポリオレフィンブレンドを形成させるステップと、ここで、シラングラフト化ポリオレフィンブレンドは1重量%〜35重量%のポリプロピレンを含む;
前記シラングラフト化ポリオレフィンブレンド、縮合触媒、およびマイクロカプセル化された発泡剤を一緒に押し出して、発泡したシラン架橋可能なポリオレフィンブレンドを形成させるステップと;
前記発泡したシラン架橋可能なポリオレフィンブレンドを未硬化のマイクロ高密度シーリングエレメントへと成形するステップと;
前記未硬化のマイクロ高密度シーリングエレメントの前記発泡したシラン架橋可能なポリオレフィンブレンドを周囲温度および周囲湿度にて架橋させて、前記エレメントを、0.60g/cm3 〜0.69g/cm3の密度を有し、かつ発泡したシラン架橋されたポリオレフィンブレンドからなるマイクロ高密度シーリングメンバーへと形成させるステップと
を含み、
第1のポリオレフィンはエチレン/α−オレフィンコポリマーであり、第2のポリオレフィンはエチレン/α−オレフィンコポリマー、プロピレン/α−オレフィンコポリマー、又はプロピレン/α−オレフィンコポリマーとエチレン/α−オレフィンコポリマーの混合物であり、
前記マイクロ高密度シーリングメンバーは、ASTM D395(22時間@70℃)によって測定すると、40.0%〜78.0%の圧縮永久ひずみを示し、
マイクロ高密度シーリングメンバーが、ASTM D412に従って測定される5.0〜8.7MPaの範囲の引張強度を示し、
マイクロ高密度シーリングメンバーが、ASTM D412に従って測定される60〜87の範囲のショアA硬度を示し、
発泡したシラン架橋されたポリオレフィンブレンドが5%〜20%の結晶化度を示し、
発泡したシラン架橋可能なポリオレフィンブレンドが熱可塑性の特性を示し、
シラン架橋剤がビニルトリメトキシシラン及び/又はビニルトリエトキシシランである、方法。 - 発泡したシラン架橋されたポリオレフィンブレンドが5%〜10%の結晶化度を示す、請求項6に記載の方法。
- 発泡したシラン架橋されたポリオレフィンブレンドの重量を基準としたポリプロピレンの量が3重量%〜10重量%の範囲である請求項6に記載の方法。
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2017
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- 2017-12-08 KR KR1020197020034A patent/KR20190097118A/ko not_active Withdrawn
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