JPH0123520B2 - - Google Patents
Info
- Publication number
- JPH0123520B2 JPH0123520B2 JP54040059A JP4005979A JPH0123520B2 JP H0123520 B2 JPH0123520 B2 JP H0123520B2 JP 54040059 A JP54040059 A JP 54040059A JP 4005979 A JP4005979 A JP 4005979A JP H0123520 B2 JPH0123520 B2 JP H0123520B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- low molecular
- polyisoprene rubber
- modified
- sealant
- 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.)
- Expired
Links
- 239000000565 sealant Substances 0.000 claims description 40
- 229920001971 elastomer Polymers 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 37
- 229920001195 polyisoprene Polymers 0.000 claims description 37
- 239000005060 rubber Substances 0.000 claims description 37
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 11
- 239000003566 sealing material Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- -1 maleic acid ester Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010454 slate Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HYDXXVRYXZJACI-UHFFFAOYSA-N C(C)N.C1(\C=C/C(=O)O1)=O Chemical compound C(C)N.C1(\C=C/C(=O)O1)=O HYDXXVRYXZJACI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 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
- DWPDSISGRAWLLV-JHZYRPMRSA-L calcium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Ca+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O DWPDSISGRAWLLV-JHZYRPMRSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- MXODCLTZTIFYDV-UHFFFAOYSA-L zinc;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O.C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O MXODCLTZTIFYDV-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
Description
本発明は、低分子量ポリイソプレンゴムを主成
分とするすぐれた弾性伸び性状と接着性を有する
シーリング材に関する。
近来、工程の簡素化、生産性向上、要求性能の
向上に伴なつて建築部門や土木部門、自動車工業
部門や工業用品部門等でのシーリング材の使用が
増大してきている。それも従来の溶剤を使用する
ものから溶剤をほとんど使用しないものへと大巾
に変りつつある。溶剤を使用しない方式になる
と、当然のことながら液状ないしは半固体状の低
分子量の重合体が用いられ、そのなかでも低分子
量のジエン系重合体が感温性が小さいこと、従来
通りのゴム加硫方法が適用できることなどの特徴
により、シーリング材のための有用な材料となつ
てきている。しかしながら、ジエン系重合体は金
属、ガラス、陶磁器、スレート等との親和性が本
質的に悪いためにそれらとの接着性を向上させる
には何らかの手段を講じる必要があり、シーリン
グ材に粘着付与樹脂を添加する方法がとられる場
合が多いが、それは用途によつてかならずしも充
分満足のできる接着性能を得ることができない
し、粘着付与樹脂がシーリング材の耐熱性や耐候
性を低下させるなどの不都合を生じるものであつ
た。さらに近年その需要が著しく増加しつつあ
る、建築分野や土木分野でのシーリング材として
は、基材への接着性のみならずすぐれた弾性伸び
が要求される。ここで弾性伸びとは、シーリング
材を一定速度で伸長した場合の破断時の伸び率を
意味し、多くの場合具体的に200％以上の伸び率
が要求される。
本発明者等はジエン系重合体が本来有している
すぐれた性質を損なわず、かつ金属、ガラス、陶
磁器、スレート等との接着性能にすぐれたシーリ
ング材用ジエン系重合体を求めて鋭意検討を重ね
た結果、特定の変性された低分子量ポリイソプレ
ンゴムを限定された条件下で用いることにより、
作業場での安全、衛生の面で安全で、作業性がよ
く、また弾性伸び性状にすぐれ、さらには金属、
カラス、陶磁器、スレート等との接着性の著しく
すぐれたシーリング材を見出し、本発明を完成す
るに至つた。すなわち、分子量が18000〜150000
であり、シス―１，４結合量が75％以上である低
分子量ポリイソプレンゴムに無水マレイン酸また
はその誘導体をイソプレン単量体単位に対して
0.5〜12モル％付加した変性低分子量ポリイソプ
レンゴムとその架橋剤および該変性低分子量ポリ
イソプレンゴム100重量部に対して250重量部以下
の充填剤を含有してなるシーリング材組成物によ
つて、接着性能そして弾性伸び性状共にすぐれた
シーリング材を得ることができることを見出した
ものである。
本発明の低分子量ポリイソプレンゴムはシーリ
ング材の主成分として用いる場合、その粘度が高
過ぎるとガンで打ち込んだり、ヘラで塗り込んだ
りする際の作業性で問題を生ずるし、また低過ぎ
るとシーリング材そのものが短時間で流動してし
まい、シーリング材としての機能を発現しなくな
るので、特定の分子量を有する必要がある。すな
わち、この低分子量ポリイソプレンゴムを用いた
シーリング材が適切なる作業性を有するためには
低分子量ポリイソプレンゴムの分子量が150000以
下、より好ましくは77000以下、特に好ましくは
60000以下でなければならない。またシーリング
材として架橋されてシーリング材として十分なる
弾性伸びを有するためには分子量が18000以上、
より好ましくは20000以上でなければならない。
なお、本発明でいう分子量とは粘度平均分子量
（Mv）を意味し、固有粘度（〔η〕）から次式よ
り算出されるものである（例えば日本化学会編
「実験化学講座８、高分子化学」（1964年、丸善発
行）参照）。
〔η〕＝1.21×10-4M0.77
さらに本発明の低分子量ポリイソプレンゴムの
シス―１，４結合量は75％以上、より好ましくは
80％以上でなければならない。シス―１，４結合
量が少ないと、最終的に得られるシーリング材の
弾性伸びが小さくなり、本発明の目的を達成しな
い。なお、本発明でシス―１，４結合量は、赤外
吸収スペクトル法にて評価されるものである。
このような特定の分子量およびミクロ構造を有
する、無水マレイン酸またはその誘導体を付加す
る前の未変性の低分子量ポリイソプレンゴムはア
ニオン重合法、配位アニオン重合法等によつて得
ることが可能であり、また天然ゴムや、チーグラ
ー重合またはアニオン重合法によつて得られた固
形の合成シス―１，４―ポリイソプレンゴムを高
温度（例えば180〜300℃）で熱分解することによ
つても得られる。しかしながら、熱分解法で得ら
れる低分子量ポリイソプレンゴムは熱分解の際に
副生する物質により臭気がはなはだしく強いし、
着色も大きく、また品質の均一化が難しいので好
ましいものではない。従つて本発明に用いる低分
子量ポリイソプレンゴムとしては重合の際にゲル
を生じることのなく、かつシス―１，４結合量の
多いもののできるリチウム系触媒によるアニオン
重合法による低分子量ポリイソプレンゴムが最も
好ましい。ここでそのアニオン重合法について説
明する。触媒としては金属リチウム、またはメチ
ルリチウム、プロピルリチウム、ブチルリチウ
ム、ジスチレニルリチウム等の有機リチウムを用
い、溶媒の存在下または非存在下にイソプレン単
量体を重合する。公知の如くその分子量はイソプ
レン単量体と触媒の使用比率で容易に制御でき
る。重合溶媒は使用した方が重合の制御が容易で
あり、一般的には使用する方が適切ではある。な
お、本発明の低分子量ポリイソプレンには、イソ
プレン単量体以外の、例えば、ブタジエンとかス
チレン単量体が、少量ならば共重合されていても
よい。本発明で最も肝要な点は無水マレイン酸ま
たはその誘導体で変性した低分子量ポリイソプレ
ンゴムを用いることである。しかも、無水マレイ
ン酸またはその誘導体の低分子量ポリイソプレン
ゴムへの該重合体の単量体あたりの付加量（以
下、単に付加量と記す。）は0.5〜12モル％の範囲
でなければならないということである。これらの
極性基の付加量は本発明の目的とする接着性能に
直接的に影響を与えるものであり、その付加量が
低過ぎると充分なる接着力が得られない。一方付
加量が多ければ接着力の点で有利ではあるが、多
過ぎると最終的に得られるシーリング材の弾性伸
びが小さくなり、本発明の目的にかなわない。し
たがつて極性基の付加量は0.5〜12モル％、より
好ましくは1.0〜7.0モル％にある必要がある。
本発明で使用される変性低分子量ポリイソプレ
ンゴムは低分子量ポリイソプレンゴムと無水マレ
イン酸および／または（マレイン酸、マレイン酸
エステル、マレインアミドあるいはマレインイミ
ド等の）無水マレイン酸誘導体とを反応して得ら
れる無水マレイン酸（誘導体）付加物のほか、低
分子量ポリイソプレンゴムに導入された無水マレ
イン酸基に例えば、必要に応じてｐ―トルエンス
ルフオン酸のような触媒の存在下または非存在下
にメタノール、エタノール、ｎ―プロパノール等
のアルコールまたはアンモニア、ｎ―プロピルア
ミン、ｎ―ブチルアミン等のアミン類を反応させ
て無水マレイン酸に基づくカルボキシル基の一方
あるいは両方をエステルの形にしたもの、または
アミド化したものさらにはイミド化したもの等を
意味する。中でも変性低分子量ポリイソプレンゴ
ムを長期保存した場合の粘度安定性の点からいえ
ば無水マレイン酸を付加した変性低分子量ポリイ
ソプレンゴムよりも該変性低分子量ポリイソプレ
ンゴムをアルコール誘導体またはアミン化合物誘
導体とした変性低分子量ポリイソプレンゴムが好
ましい。
低分子量ポリイソプレンゴムへの無水マレイン
酸またはその誘導体の付加反応は、例えば所定の
分子量を有する低分子量ポリイソプレンゴム中に
無水マレイン酸またはその誘導体を加えて、溶剤
の存在下または非存在下に、ラジカル触媒の存在
下または非存在下に加熱反応させることにより容
易に行なうことができる。ここで使用される溶剤
としては一般には炭化水素、ハロゲン化炭化水素
等が挙げられるが、ｎ―ブタン、ｎ―ヘキサン、
ｎ―ヘプタン、シクロヘキサン、ベンゼン、トル
エン、キシレン等の不活性溶剤がより好ましい。
また、本発明において使用されるもうひとつの
重要な構成成分である変性低分子量ポリイソプレ
ンゴムの架橋剤としては金属系架橋剤、アミン系
架橋剤、エポキシ系架橋剤、グリコール系架橋剤
そしてイソシアネート系架橋剤から選ばれた１種
または２種以上のものが用いられる。金属系架橋
剤とは周期律表第１族、第２族および第４族に属
する金属の化合物であつて、例えば酢酸カリウ
ム、水酸化ナトリウム、炭酸ナトリウム、酸化亜
鉛（亜鉛華）、酸化マグネシウム、酸化鉛、塩化
カルシウム、水酸化カルシウム、酢酸亜鉛、酢酸
カルシウム、樹脂酸亜鉛、樹脂酸ナトリウム、樹
脂酸カルシウム等である。アミン系の架橋剤の例
としてはジエチレントリアミン、トリエチレンテ
トラミン、ジアミノジフエニルメタン、ポリエチ
レンイミン、アジリデイニル化合物、ポリアミド
樹脂等が挙げられる。エポキシ系架橋剤の代表的
な例としてはビスフエノールＡやビスフエノール
Ｆとエピクロルヒドリンより結合によつて得られ
るエポキシ樹脂が挙げられ、そのエポキシ当量と
しては150〜700程度のものが好適である。グリコ
ール系架橋剤の例としてはポリオキシエチレング
リコール、ポリオキシプロピレングリコールおよ
びそれらのエステル化物が挙げられる。イソシア
ネート系架橋剤とはトリレンジイソシアネート、
フエニレンジイソシアネート、ジフエニルメタン
ジイソシアネート等の分子内に２個以上のイソシ
アネート基を有する化合物である。これらの架橋
剤の使用量はその種類、使用温度等により異な
り、一概には規定出来ないが、一般には変性低分
子量ポリイソプレンが含有する無水マレイン酸
（またはその誘導体）に対して0.5当量以上で用い
られる。なお、上記架橋剤の中でエポキシ系架橋
剤に関しては、エポキシ樹脂が架橋剤としての機
能を果すだけではなく、それ自身が硬化してシー
リング材組成物を硬くして弾性伸びを小さくする
ので、その使用量は変性低分子量ポリイソプレン
ゴム100重量部に対して20重量部以下、より好ま
しくは10重量部以下が適切である。
本発明のシーリング材組成物において今ひとつ
重要な点はシーリング材組成物に含有される充填
剤の量である。一般にシーリング材には未硬化状
態でチクソトロピー性を与えるために、または硬
化後のシーリング材に適度な硬さを付与するため
に、さらには組成物の配合コストを下げるために
充填剤が使用される。
本発明のシーリング材組成物において、この充
填剤の量は変性低分子量ポリイソプレンゴム100
重量部に対して250重量部以下、より好ましくは
175重量部以下でなければならない。ここで充填
剤の一例として炭酸カルシウム、クレー、シリ
カ、タルク、ガラス粉末、硫酸アルミニウム、雲
母粉、カーボンブラツク、アスベスト等の無機充
填剤およびエボナイト粉末、セラツク、セルロー
ス粉末、コルク粉末等の有機充填剤等が挙げられ
る。
本発明のシーリング材組成物には、変性低分子
量ポリイソプレンゴムおよびその架橋剤そして充
填剤の他に、必要に応じて例えばラノリン、植物
油、鉱物油、ジオクチルフタレート、液状ポリブ
テン等の可塑剤、増粘剤、発泡剤、オゾン劣化防
止剤、老化防止剤、また場合によつては適量の熱
可塑性樹脂や粘着付与樹脂が用いられる。また接
着性能を低下せしめない範囲内において未変性の
低分子量ジエン系重合体（ポリイソプレン、ポリ
ブタジエン）等が用いられてもよい。原則として
一般の固形ゴムを用いるとシーリング材の粘度が
高くなり、作業性が著しく低下するので好ましく
ないが、作業性の許される少量の割合で用いられ
るのはよい。
本発明のシーリング材組成物には原則としては
溶剤はほとんど含まれないが、粘度調整のために
ヘキサン、トルエン、酢酸エチル、メチルエチル
ケトン、メチルアルコール、イソプロピルアルコ
ール等の溶剤が少量使用される場合もある。
本発明のシーリング材組成物はニーダー、バン
バリーミキサー、オープンロール等の一般ゴム用
混合機、ペイントロール、撹拌機付槽式混合機等
で製造される。
本発明のシーリング材組成物は極性物質に対し
てのすぐれた接着性能とすぐれた弾性伸び性状を
有しているので金属、ガラス、スレート、陶磁器
等の材料が関連する場合の建築用及び土木用シー
リング材として有用である。
以下、実施例によつて本発明を説明するが、そ
れら実施例は本発明を何ら限定するものではな
い。
実施例 １
アニオン重合法により、シス―１，４結合量が
84％であり、分子量53000の低分子量ポリイソプ
レンゴム（以下LIRと略記す）を得た。該LIRと
無水マレイン酸（以下MANと略記す）とをキシ
レン溶液状態で、150℃で加熱反応させることに
よりMANが0.08，1.0および15モル％付加した変
性LIRを得た。この変性LIRを用いて、表１に示
した配合でニーダーにかけてシーリング材組成物
を得た。この配合組成物を剥離紙上で約3m／ｍ
の厚みのシート状にして、室温で硬化させた。硬
化は３〜５日間でほぼ完了したが、そのまま室温
でさらに20日間置いた後、硬化シーリング材を矩
形に切り出し、インストロン引張り試験機にて５
cm／minの引張り速度で伸長し、破断時の伸び率
と強度を測定した（表１）。
The present invention relates to a sealing material containing low molecular weight polyisoprene rubber as a main component and having excellent elastic extensibility and adhesive properties. BACKGROUND OF THE INVENTION In recent years, the use of sealants has been increasing in the construction sector, civil engineering sector, automobile industry sector, industrial goods sector, etc. as processes have been simplified, productivity has improved, and required performance has improved. There is also a major shift from conventional methods that use solvents to those that use almost no solvents. Naturally, when using a method that does not use solvents, liquid or semi-solid low molecular weight polymers are used, and among these, low molecular weight diene polymers have low temperature sensitivity, and conventional rubber processing is difficult. Characteristics such as the applicability of the sulfur process have made it a useful material for sealants. However, diene polymers inherently have poor affinity with metals, glass, ceramics, slate, etc., so it is necessary to take some measures to improve their adhesion with them, and tackifying resins are used in the sealant. However, depending on the application, it may not always be possible to obtain a fully satisfactory adhesive performance, and the tackifying resin may reduce the heat resistance and weather resistance of the sealant. It was something that would happen. Furthermore, as a sealing material in the architectural and civil engineering fields, the demand for which has been increasing significantly in recent years, not only adhesion to the base material but also excellent elastic elongation is required. Here, elastic elongation refers to the elongation rate at break when the sealant is stretched at a constant speed, and in many cases, an elongation rate of 200% or more is specifically required. The present inventors have conducted extensive studies in search of a diene polymer for sealing materials that does not impair the excellent properties originally possessed by diene polymers and has excellent adhesion performance to metals, glass, ceramics, slate, etc. As a result of repeated efforts, by using a specific modified low molecular weight polyisoprene rubber under limited conditions,
It is safe in terms of safety and hygiene in the workplace, has good workability, and has excellent elastic elongation properties.
The present inventors have discovered a sealing material that has excellent adhesion to glass, ceramics, slate, etc., and have completed the present invention. That is, the molecular weight is 18000-150000
Maleic anhydride or its derivatives are added to the isoprene monomer unit to a low molecular weight polyisoprene rubber with a cis-1,4 bond content of 75% or more.
By a sealant composition comprising a modified low molecular weight polyisoprene rubber added with 0.5 to 12 mol%, its crosslinking agent, and a filler of 250 parts by weight or less per 100 parts by weight of the modified low molecular weight polyisoprene rubber. It was discovered that it is possible to obtain a sealing material with excellent adhesive performance and elastic elongation properties. When the low molecular weight polyisoprene rubber of the present invention is used as the main component of a sealant, if the viscosity is too high, problems will arise in workability when driving in with a gun or applying with a spatula; Since the material itself will flow in a short time and will no longer function as a sealing material, it needs to have a specific molecular weight. That is, in order for a sealing material using this low molecular weight polyisoprene rubber to have appropriate workability, the molecular weight of the low molecular weight polyisoprene rubber must be 150,000 or less, more preferably 77,000 or less, particularly preferably 77,000 or less.
Must be less than 60000. In addition, in order to be cross-linked as a sealant and have sufficient elastic elongation as a sealant, the molecular weight must be 18,000 or more.
More preferably, it should be 20,000 or more.
In addition, the molecular weight in the present invention means the viscosity average molecular weight (Mv), which is calculated from the intrinsic viscosity ([η]) using the following formula (for example, "Experimental Chemistry Course 8, Polymer (See ``Chemistry'' (1964, published by Maruzen)). [η] = 1.21×10 -4 M 0.77 Furthermore, the amount of cis-1,4 bonds in the low molecular weight polyisoprene rubber of the present invention is 75% or more, more preferably
Must be 80% or higher. If the amount of cis-1,4 bonds is small, the elastic elongation of the final sealing material obtained will be small, and the object of the present invention will not be achieved. In the present invention, the amount of cis-1,4 bonds is evaluated by infrared absorption spectroscopy. Unmodified low molecular weight polyisoprene rubber having such a specific molecular weight and microstructure before addition of maleic anhydride or its derivatives can be obtained by an anionic polymerization method, a coordination anionic polymerization method, etc. It can also be produced by thermally decomposing natural rubber or solid synthetic cis-1,4-polyisoprene rubber obtained by Ziegler polymerization or anionic polymerization at high temperatures (for example, 180 to 300°C). can get. However, low molecular weight polyisoprene rubber obtained by pyrolysis has a very strong odor due to the substances that are produced as by-products during pyrolysis.
It is not preferable because it is highly colored and it is difficult to make the quality uniform. Therefore, the low-molecular-weight polyisoprene rubber used in the present invention is a low-molecular-weight polyisoprene rubber produced by an anionic polymerization method using a lithium catalyst that does not produce gel during polymerization and has a large amount of cis-1,4 bonds. Most preferred. Here, the anionic polymerization method will be explained. Metallic lithium or organic lithium such as methyllithium, propyllithium, butyllithium, and distyrenyllithium is used as a catalyst, and isoprene monomers are polymerized in the presence or absence of a solvent. As is known, the molecular weight can be easily controlled by adjusting the ratio of isoprene monomer to catalyst. It is easier to control the polymerization by using a polymerization solvent, and it is generally more appropriate to use a polymerization solvent. In addition, the low molecular weight polyisoprene of the present invention may be copolymerized with a small amount of a monomer other than isoprene monomer, such as butadiene or styrene monomer. The most important point of the present invention is the use of low molecular weight polyisoprene rubber modified with maleic anhydride or its derivatives. Moreover, the amount of maleic anhydride or its derivative added per monomer of the polymer to the low molecular weight polyisoprene rubber (hereinafter simply referred to as the amount added) must be in the range of 0.5 to 12 mol%. That's true. The amount of these polar groups added directly affects the adhesive performance, which is the objective of the present invention, and if the amount added is too low, sufficient adhesive strength cannot be obtained. On the other hand, if the amount added is large, it is advantageous in terms of adhesive strength, but if it is too large, the elastic elongation of the final sealing material obtained becomes small, which does not meet the purpose of the present invention. Therefore, the amount of polar groups added needs to be 0.5 to 12 mol%, more preferably 1.0 to 7.0 mol%. The modified low molecular weight polyisoprene rubber used in the present invention is prepared by reacting a low molecular weight polyisoprene rubber with maleic anhydride and/or a maleic anhydride derivative (such as maleic acid, maleic acid ester, maleinamide or maleimide). In addition to the resulting maleic anhydride (derivative) adduct, the maleic anhydride group introduced into the low molecular weight polyisoprene rubber may be treated, for example, in the presence or absence of a catalyst such as p-toluenesulfonic acid as necessary. and alcohols such as methanol, ethanol, n-propanol, or amines such as ammonia, n-propylamine, n-butylamine, etc., to form one or both of the carboxyl groups based on maleic anhydride into an ester, or It means amidated products, imidized products, etc. Among them, from the viewpoint of viscosity stability when the modified low molecular weight polyisoprene rubber is stored for a long period of time, it is better to use modified low molecular weight polyisoprene rubber with alcohol derivatives or amine compound derivatives than with modified low molecular weight polyisoprene rubber with maleic anhydride added. Modified low molecular weight polyisoprene rubber is preferred. The addition reaction of maleic anhydride or its derivatives to low molecular weight polyisoprene rubber can be carried out, for example, by adding maleic anhydride or its derivatives to low molecular weight polyisoprene rubber having a predetermined molecular weight, and then adding the maleic anhydride or its derivatives to low molecular weight polyisoprene rubber in the presence or absence of a solvent. This can be easily carried out by heating the reaction in the presence or absence of a radical catalyst. Solvents used here generally include hydrocarbons, halogenated hydrocarbons, etc., but include n-butane, n-hexane,
Inert solvents such as n-heptane, cyclohexane, benzene, toluene, and xylene are more preferred. In addition, the crosslinking agents for the modified low molecular weight polyisoprene rubber, which is another important component used in the present invention, include metal crosslinking agents, amine crosslinking agents, epoxy crosslinking agents, glycol crosslinking agents, and isocyanate crosslinking agents. One or more selected crosslinking agents may be used. Metallic crosslinking agents are compounds of metals belonging to Groups 1, 2, and 4 of the periodic table, such as potassium acetate, sodium hydroxide, sodium carbonate, zinc oxide (zinc white), magnesium oxide, These include lead oxide, calcium chloride, calcium hydroxide, zinc acetate, calcium acetate, zinc resinate, sodium resinate, calcium resinate, and the like. Examples of amine-based crosslinking agents include diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, polyethyleneimine, aziridenyl compounds, and polyamide resins. A typical example of the epoxy crosslinking agent is an epoxy resin obtained by bonding bisphenol A or bisphenol F with epichlorohydrin, and its epoxy equivalent is preferably about 150 to 700. Examples of glycol-based crosslinking agents include polyoxyethylene glycol, polyoxypropylene glycol, and esterified products thereof. Isocyanate crosslinking agents include tolylene diisocyanate,
These are compounds having two or more isocyanate groups in the molecule, such as phenylene diisocyanate and diphenylmethane diisocyanate. The amount of these crosslinking agents to be used varies depending on the type, temperature of use, etc., and cannot be absolutely specified, but generally it is 0.5 equivalent or more based on the maleic anhydride (or its derivative) contained in the modified low molecular weight polyisoprene. used. Regarding the epoxy crosslinking agent among the above crosslinking agents, the epoxy resin not only functions as a crosslinking agent, but also hardens itself to harden the sealant composition and reduce elastic elongation. The appropriate amount to be used is 20 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the modified low molecular weight polyisoprene rubber. Another important point in the sealant composition of the present invention is the amount of filler contained in the sealant composition. Generally, fillers are used in sealants to impart thixotropy in the uncured state, to impart appropriate hardness to the sealant after curing, and to reduce the compounding cost of the composition. . In the sealant composition of the present invention, the amount of this filler is 100% of the modified low molecular weight polyisoprene rubber.
250 parts by weight or less, more preferably
Must not exceed 175 parts by weight. Examples of fillers include inorganic fillers such as calcium carbonate, clay, silica, talc, glass powder, aluminum sulfate, mica powder, carbon black, and asbestos, and organic fillers such as ebonite powder, shellac, cellulose powder, and cork powder. etc. In addition to the modified low molecular weight polyisoprene rubber, its crosslinking agent, and filler, the sealant composition of the present invention may optionally contain a plasticizer such as lanolin, vegetable oil, mineral oil, dioctyl phthalate, liquid polybutene, etc. A viscous agent, a blowing agent, an antiozonant, an antiaging agent, and in some cases, an appropriate amount of a thermoplastic resin or a tackifying resin are used. Further, unmodified low molecular weight diene polymers (polyisoprene, polybutadiene), etc. may be used within a range that does not deteriorate adhesive performance. In principle, it is not preferable to use ordinary solid rubber because it increases the viscosity of the sealant and significantly reduces workability, but it is better to use it in a small proportion that allows for workability. In principle, the sealant composition of the present invention contains almost no solvent, but a small amount of solvent such as hexane, toluene, ethyl acetate, methyl ethyl ketone, methyl alcohol, isopropyl alcohol, etc. may be used to adjust the viscosity. . The sealant composition of the present invention is manufactured using a kneader, a Banbury mixer, a general rubber mixer such as an open roll, a paint roll, a tank mixer with an agitator, or the like. The sealant composition of the present invention has excellent adhesion performance to polar substances and excellent elastic extensibility, so it can be used for construction and civil engineering when materials such as metal, glass, slate, and ceramics are involved. Useful as a sealant. EXAMPLES The present invention will be explained below with reference to Examples, but these Examples do not limit the present invention in any way. Example 1 The amount of cis-1,4 bonds was reduced by anionic polymerization method.
84%, and a low molecular weight polyisoprene rubber (hereinafter abbreviated as LIR) with a molecular weight of 53,000 was obtained. By heating the LIR and maleic anhydride (hereinafter abbreviated as MAN) in a xylene solution state at 150° C., modified LIRs with 0.08, 1.0, and 15 mol% of MAN added were obtained. Using this modified LIR, a sealant composition was obtained by kneading the composition shown in Table 1. This blended composition is spread on release paper at approximately 3 m/m.
It was made into a sheet with a thickness of The curing was almost completed in 3 to 5 days, but after leaving it at room temperature for another 20 days, the cured sealant was cut into rectangles and tested with an Instron tensile tester.
It was stretched at a tensile rate of cm/min, and the elongation rate and strength at break were measured (Table 1).
【表】
表１に示したように本発明で規定された変性
LIRを用いた配合No.２はすぐれた弾性伸び性状を
有しているが、MAN付加量が低過ぎる変性LIR
および高過ぎる変性LIRを用いたシーリング材の
伸びは不充分である。一方未硬化のシーリング材
配合物をガラス板上で硬化させて、硬化物を手の
指で引つかいてその接着性をみた。配合No.１はガ
ラスとの接着力が低く容易にはがれたが、配合No.
２の接着力は高くてはがれにくかつた。
実施例 ２
アニオン重合法により得た、シス―１，４結合
量が各々81％、82％そして85％であり、分子量が
12000，38000そして185000であるLIRを用いて実
施例１と同様な手法でMAN付加反応を実施した
後メチルアルコールを添加することにより、マレ
イン酸モノメチルエステルが3.1モル％付加した
変性LIRを得た。該変性LIRを用いて表２に示し
たシーリング材配合物をプロペラ型撹拌機付混合
槽にて作製した。しかし分子量185000の変性LIR
を用いた場合は撹拌が極端に悪くて均一なシーリ
ング材組成物は得ることはできなかつた。配合No.
４，５，７について厚み３ｍ／ｍのシート状に成
形し、120℃で20分間熱処理することにより硬化
シーリング材組成物を作製し、引張り試験を実施
した。一方鋼板上に未硬化のシーリング配合物を
塗布して上と同様の熱処理を施した。[Table] Modifications defined in the present invention as shown in Table 1
Formulation No. 2 using LIR has excellent elastic elongation properties, but the modified LIR has an excessively low amount of MAN added.
Also, the elongation of sealants using modified LIR that is too high is insufficient. On the other hand, an uncured sealant compound was cured on a glass plate, and the cured product was checked with fingers to check its adhesiveness. Formulation No. 1 had low adhesion to glass and peeled off easily, but Formulation No.
The adhesive strength of No. 2 was high and it was difficult to peel off. Example 2 Obtained by anionic polymerization method, the amounts of cis-1,4 bonds are 81%, 82%, and 85%, respectively, and the molecular weight is
A MAN addition reaction was performed in the same manner as in Example 1 using LIRs of 12,000, 38,000, and 185,000, and then methyl alcohol was added to obtain a modified LIR with 3.1 mol% of maleic acid monomethyl ester added. Using the modified LIR, the sealant composition shown in Table 2 was prepared in a mixing tank equipped with a propeller-type stirrer. However, a modified LIR with a molecular weight of 185,000
When using this method, stirring was extremely poor and a uniform sealant composition could not be obtained. Formulation No.
Samples No. 4, 5, and 7 were molded into a sheet with a thickness of 3 m/m, heat treated at 120° C. for 20 minutes to prepare a cured sealant composition, and a tensile test was conducted. On the other hand, an uncured sealing compound was applied onto the steel plate and subjected to the same heat treatment as above.
【表】
表２に示したごとく、本発明に基づくシーリン
グ材（配合No.５）は破断伸び率も大きいし、鋼板
への接着力もすぐれていた。
実施例 ３
実施例１のMAN付加量が1.0モル％の変性LIR
を用いて、ニーダーにて表３に示したシーリング
材配合物を作製した。実施例１と同様の手順で硬
化シーリング材の引張り試験を実施した。その結
果を表３に示した。表３から判るように充填剤量
の使用量が125重量部のシーリング材はすぐれた
伸び性状を示したが、充填剤の使用量が350重量
部のものは伸びが小さく、本発明の目的にかなつ
ていない。またガラス板上で硬化させたところ配
合No.８のシーリング材組成物はガラスに対してす
ぐれた接着性を有していた。[Table] As shown in Table 2, the sealant based on the present invention (formulation No. 5) had a high elongation at break and had excellent adhesive strength to steel plates. Example 3 Modified LIR with 1.0 mol% MAN addition amount of Example 1
The sealant compositions shown in Table 3 were prepared using a kneader. A tensile test of the cured sealant was conducted in the same manner as in Example 1. The results are shown in Table 3. As can be seen from Table 3, the sealant containing 125 parts by weight of filler showed excellent elongation properties, but the sealant containing 350 parts by weight showed low elongation, which is not suitable for the purpose of the present invention. It hasn't come close. Furthermore, when cured on a glass plate, the sealant composition of formulation No. 8 had excellent adhesion to glass.
【表】
実施例 ４
アニオン重合法により得たシス―１，４結合量
が85％であり、分子量が45000のLIRを用いて、
トルエン中で180℃でMAN付加反応を実施した
後エチルアルコールを添加し、無水マレイン酸モ
ノエチルエステルが3.7モル％付加した変性LIR
を得た。該変性LIRを用いて表４のシーリング材
配合物をプロペラ撹拌機付混合槽にて作製した。
この混合物をテフロン上で150℃で30分間加熱し
てシート状に硬化成形した。一方鋼板上にも配合
物を塗布して同じく150℃で30分間加熱硬化した
充填剤量が本発明の範囲内にある配合No.10および
11のシーリング材は200％以上の伸長率を有して
いるが、充填剤量が本発明の範囲外にある配合No.
12および13のシーリング材の伸び率は小さい。ま
たNo.10および11の鋼板上での硬化物と鋼板との接
着性もすぐれていた。[Table] Example 4 Using LIR with a cis-1,4 bond amount of 85% and a molecular weight of 45,000 obtained by an anionic polymerization method,
Modified LIR with 3.7 mol% maleic anhydride monoethyl ester added by performing MAN addition reaction in toluene at 180°C and then adding ethyl alcohol.
I got it. Using the modified LIR, the sealant formulations shown in Table 4 were prepared in a mixing tank equipped with a propeller agitator.
This mixture was heated on Teflon at 150° C. for 30 minutes to harden and mold it into a sheet. On the other hand, the mixture was applied on a steel plate and cured by heating at 150°C for 30 minutes, and the filler amount was within the range of the present invention.
Sealant No. 11 has an elongation rate of 200% or more, but Formulation No. 1 has a filler amount outside the range of the present invention.
The elongation rate of sealants 12 and 13 is small. Furthermore, the adhesion between the cured product and the steel plates on Nos. 10 and 11 was also excellent.
【表】
比較例 １
エーテル化合物の存在下に、アニオン重合をす
ることにより得たシス―１，４結合量が40％であ
り、分子量が39000の低分子量ポリイソプレンゴ
ムを用いて、MAN付加反応を実施することによ
り、MANが1.5モル％付加した変性LIRを得た。
該変性LIRを用いて実施例１と同様の手法でシー
リング材を作製し、引張り試験を実施したとこ
ろ、その破断伸びは95％であり、本発明の目的に
かなわないものであつた。
比較例 ２
実施例１で得られたLIRを変性することなく、
表５に示す配合でニーダーにかけてシーリング材
組成物を得た。この配合組成物を脱脂した鉄板に
５ｍ／ｍの厚みで塗り付け、室温で１週間かけて
硬化させた後、90剥離強度を測定した。結果を表
５に示す。実施例３で得られたNo.８の配合組成物
について90剥離強度を測定したところ、接着力は
3.5Kg／cmであつた。[Table] Comparative Example 1 Using a low molecular weight polyisoprene rubber with a cis-1,4 bond content of 40% and a molecular weight of 39,000 obtained by anionic polymerization in the presence of an ether compound, a MAN addition reaction was carried out. By performing this, a modified LIR with 1.5 mol% of MAN added was obtained.
When a sealing material was prepared using the modified LIR in the same manner as in Example 1 and a tensile test was performed, the elongation at break was 95%, which did not meet the purpose of the present invention. Comparative Example 2 Without modifying the LIR obtained in Example 1,
A sealant composition was obtained by kneading with the formulation shown in Table 5. This blended composition was applied to a degreased iron plate at a thickness of 5 m/m, and after curing at room temperature for one week, the 90 peel strength was measured. The results are shown in Table 5. When the 90 peel strength was measured for the blended composition No. 8 obtained in Example 3, the adhesive strength was
It was 3.5Kg/cm.
【表】【table】
【表】
実施例 ５
実施例４で用いたLIRを用い、トルエン中で
180℃でMAn付加反応を実施した後モノエチルア
ミンを添加し、無水マレイン酸モノエチルアミド
が2.9モル％付加した変性LIR(A)を得た。さらに、
得られた変性LIRを150℃に加熱することにより、
無水マレイン酸モノエチルアミド基が脱水環化し
マレイミド基となつた変性LIR(B)を得た。これら
の変性LIRを用いて表５のシーリング材配合物を
プロペラ撹拌機付混合槽にて作成した。この配合
物をテフロン上で150℃で40分間加熱してシート
状に硬化成型した。一方鋼板上にも配合物を塗布
して同じく150℃で40分間加熱し硬化成型した。
こうして得られた硬化物を用い、実施例１と同
様にして引張り試験を行ない、破断時の伸びと強
度を測定した。[Table] Example 5 Using the LIR used in Example 4, in toluene
After carrying out the MAn addition reaction at 180°C, monoethylamine was added to obtain a modified LIR (A) with 2.9 mol% of maleic anhydride monoethylamide added. moreover,
By heating the obtained modified LIR to 150℃,
A modified LIR (B) in which the maleic anhydride monoethylamide group was dehydrated and cyclized to become a maleimide group was obtained. Using these modified LIRs, the sealant formulations shown in Table 5 were prepared in a mixing tank equipped with a propeller agitator. This mixture was heated on Teflon at 150° C. for 40 minutes to cure and mold into a sheet. On the other hand, the mixture was also applied onto a steel plate and heated at 150°C for 40 minutes to harden and mold. Using the thus obtained cured product, a tensile test was conducted in the same manner as in Example 1, and the elongation at break and strength were measured.
【表】
表５に示すとおり、硬化物は十分な強度と伸度
を有していた。また、鋼板との接着力は十分であ
り、指でははがすことはできなかつた。[Table] As shown in Table 5, the cured product had sufficient strength and elongation. In addition, the adhesive force with the steel plate was sufficient and it was impossible to peel it off with fingers.
Claims (1)
４結合量が75％以上である低分子量ポリイソプレ
ンゴムに無水マレイン酸またはその誘導体をイソ
プレン単量体単位に対して0.5〜12モル％付加し
た変性低分子量ポリイソプレンゴムとその架橋剤
および該変性低分子量ポリイソプレンゴム100重
量部に対して250重量部以下の充填剤を含有して
なり、かつその硬化物の破断伸びが200％以上で
あるシーリング材組成物。1 The molecular weight is 18,000 to 150,000, and the cis-1,
Modified low molecular weight polyisoprene rubber in which 0.5 to 12 mol% of maleic anhydride or a derivative thereof is added to the isoprene monomer unit to a low molecular weight polyisoprene rubber having a bond content of 75% or more, its crosslinking agent, and the modification A sealing material composition containing 250 parts by weight or less of a filler based on 100 parts by weight of low molecular weight polyisoprene rubber, and having an elongation at break of a cured product of the sealant composition of 200% or more.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4005979A JPS55133473A (en) | 1979-04-02 | 1979-04-02 | Sealing material composition |
| DE19792935846 DE2935846C2 (en) | 1978-09-07 | 1979-09-05 | Use of a compound based on modified polyisoprene as a sealing compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4005979A JPS55133473A (en) | 1979-04-02 | 1979-04-02 | Sealing material composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55133473A JPS55133473A (en) | 1980-10-17 |
| JPH0123520B2 true JPH0123520B2 (en) | 1989-05-02 |
Family
ID=12570342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4005979A Granted JPS55133473A (en) | 1978-09-07 | 1979-04-02 | Sealing material composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55133473A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3214149A4 (en) | 2014-10-28 | 2018-07-25 | Kuraray Co., Ltd. | Sealant composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5125544A (en) * | 1974-08-28 | 1976-03-02 | Kuraray Co | NENDOANTEISEINOSUGURETA MIKARYUGOMUHAIGOBUTSU NO SEIZOHO |
| JPS5125545A (en) * | 1974-08-28 | 1976-03-02 | Kuraray Co | Tomeiseiryokona karyugomuseihin |
-
1979
- 1979-04-02 JP JP4005979A patent/JPS55133473A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5125544A (en) * | 1974-08-28 | 1976-03-02 | Kuraray Co | NENDOANTEISEINOSUGURETA MIKARYUGOMUHAIGOBUTSU NO SEIZOHO |
| JPS5125545A (en) * | 1974-08-28 | 1976-03-02 | Kuraray Co | Tomeiseiryokona karyugomuseihin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55133473A (en) | 1980-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU684836B2 (en) | Dissimilar arm asymmetric radial or star block copolymers for adhesives and sealants | |
| AU676232B2 (en) | Randomly epoxidized small star polymers | |
| US3932327A (en) | Adhesive compositions | |
| US4100137A (en) | Crosslinking of hydroxyl-containing polymers with polyaldehyde compounds | |
| US5356994A (en) | Adhesive/sealant composition comprising a rubber component | |
| JPH06506004A (en) | adhesive rubber composition | |
| US4138378A (en) | Liquid polyalkene in thermoplastic elastomer sealant formulation | |
| JP5629320B2 (en) | Rubber composition having high elasticity | |
| EP0617728A1 (en) | Compositions which can be cross-linked at room temperature, method of preparing them and their use | |
| JP3113049B2 (en) | Hydrogenated block copolymers containing epoxy groups and their preparation | |
| EP0755415A1 (en) | Epoxidized low viscosity rubber toughening modifiers for epoxy resins | |
| US20050209412A1 (en) | Modified polymer and coating material | |
| US4113914A (en) | Process for applying sealant composition | |
| JPH0123520B2 (en) | ||
| GB2280188A (en) | Coreactive conjugated diene polymer compositions which phase seperate when cured | |
| JP4849209B2 (en) | Adhesive composition and adhesive tape using the same | |
| US3842023A (en) | Polymeric solder composition | |
| WO2021153455A1 (en) | Thermosetting composition containing styrene-butadiene-styrene block polymer, and method for curing same | |
| US4409056A (en) | Curable sealing composition | |
| JPH0345101B2 (en) | ||
| JPH0269545A (en) | Rubber composition improved in adhesiveness | |
| JPS634561B2 (en) | ||
| KR950703608A (en) | SINGLE-COMPONENT THERMOSETTING MASSES, STORAGE STABLE ATROOM TEMPERATURE, MADE OF ANHYDRIDE GROUP-CONTAINING POLYMERS AND POWDERY CROSSLINKING AGENTS, PROCESS FOR PRODUCING THE SAME AND THEIR USE) | |
| JPH0412904B2 (en) | ||
| JPS649335B2 (en) |