JPH04246462A - Rubber chip-containing curable composition - Google Patents
Rubber chip-containing curable compositionInfo
- Publication number
- JPH04246462A JPH04246462A JP3027637A JP2763791A JPH04246462A JP H04246462 A JPH04246462 A JP H04246462A JP 3027637 A JP3027637 A JP 3027637A JP 2763791 A JP2763791 A JP 2763791A JP H04246462 A JPH04246462 A JP H04246462A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyl group
- polymer
- composition
- curable composition
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 229920001971 elastomer Polymers 0.000 title claims abstract description 75
- 239000005060 rubber Substances 0.000 title claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 99
- 229920000642 polymer Polymers 0.000 claims abstract description 90
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 34
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 34
- 150000001993 dienes Chemical class 0.000 claims abstract description 24
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 91
- 150000004678 hydrides Chemical class 0.000 claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 13
- -1 azo compound Chemical class 0.000 description 41
- 239000000047 product Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 32
- 229920005862 polyol Polymers 0.000 description 31
- 239000002904 solvent Substances 0.000 description 27
- 238000002156 mixing Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229920001195 polyisoprene Polymers 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000004359 castor oil Substances 0.000 description 6
- 235000019438 castor oil Nutrition 0.000 description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 6
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004034 viscosity adjusting agent Substances 0.000 description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009408 flooring Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VGMQZCPHUDXGFR-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].[Li].C1=CC=CC2=CC=CC=C21 VGMQZCPHUDXGFR-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 150000002923 oximes Chemical class 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 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 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
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- 239000010457 zeolite Substances 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JIRKHEPVCOYRND-UHFFFAOYSA-N 1,4-dihydroxy-2-methyl-2-propan-2-ylpiperazine Chemical compound CC(C)C1(C)CN(O)CCN1O JIRKHEPVCOYRND-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
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- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ゴムチップ含有硬化性
組成物に関する。詳しくは、機械的強度に優れた硬化物
を得ることができるゴムチップ含有硬化性組成物に関す
る。FIELD OF THE INVENTION This invention relates to a curable composition containing rubber chips. Specifically, the present invention relates to a rubber chip-containing curable composition from which a cured product with excellent mechanical strength can be obtained.
【０００２】0002
【従来の技術および発明が解決しようとする課題】ゴム
チップ含有硬化性組成物としては、水酸基含有液状ジエ
ン系重合体，ポリイソシアネート化合物およびゴムチッ
プからなる組成物が知られており（特開昭６３−１８６
７４９号公報）、この組成物から道路舗装材，床材，緩
衝材などに有用な硬化物が得られる。[Prior Art and Problems to be Solved by the Invention] As a curable composition containing rubber chips, a composition consisting of a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a rubber chip is known (Japanese Unexamined Patent Application Publication No. 1983-1996-1). 186
No. 749), and from this composition a cured product useful for road paving materials, flooring materials, cushioning materials, etc. can be obtained.
【０００３】しかし、上記硬化物は滑りにくく、かつ種
々に着色することが可能であるという、通常の道路舗装
材や床材にはない長所を有するものの、変色しやすいと
いう欠点がある。特に、高温、高湿の環境下で光照射を
受けると、変色するので、使用分野に大きな制約を受け
る上、前記長所を長期間にわたって保持することが難し
い。近年、かかるゴムチップ含有硬化性組成物は屋内ば
かりでなく、ゴルフ施設などの野外にもその用途が拡大
しているため、ゴムチップ含有硬化性組成物の耐変色性
の一層の向上が望まれている。また、上記組成物はゴム
チップを結合するバインダーとして作用する水酸基含有
液状ジエン系重合体とポリイソシアネート化合物との硬
化物とゴムチップとの密着性や接着性がよくないため、
硬化物の機械的強度が不足する。そのため、より一層機
械的強度の優れた硬化物を与える組成物が望まれている
。[0003] However, although the above-mentioned cured product has advantages that ordinary road paving materials and flooring materials do not have in that it is hard to slip and can be colored in various ways, it has the disadvantage that it is easily discolored. In particular, when exposed to light in a high temperature and high humidity environment, the material changes color, which severely limits the field of use and makes it difficult to maintain the above advantages over a long period of time. In recent years, the use of such rubber chip-containing curable compositions has been expanding not only indoors but also outdoors such as golf facilities, so it is desired to further improve the discoloration resistance of rubber chip-containing curable compositions. . In addition, the above composition does not have good adhesion or adhesion between the rubber chip and the cured product of the hydroxyl group-containing liquid diene polymer and the polyisocyanate compound, which act as a binder for binding the rubber chip.
The mechanical strength of the cured product is insufficient. Therefore, a composition that provides a cured product with even better mechanical strength is desired.
【０００４】0004
【課題を解決するための手段】そこで、本発明者らは上
記欠点を解消した組成物を得るべく鋭意検討を重ねた結
果、特定の成分からなる液状重合体組成物をバインダー
として用いれば、耐変色性ならびに機械的強度のすぐれ
たゴムチップ含有硬化性を与える組成物が得られること
を見出し、本発明を完成した。[Means for Solving the Problems] The present inventors have made extensive studies to obtain a composition that eliminates the above-mentioned drawbacks, and have found that if a liquid polymer composition consisting of specific components is used as a binder, it will be resistant to The present invention was completed based on the discovery that a rubber chip-containing curable composition with excellent discoloration and mechanical strength can be obtained.
【０００５】すなわち、本発明は第１に（Ａ）水酸基含
有液状イソプレン系重合体の水素化物，（Ｂ）ポリイソ
シアネート化合物および（Ｃ）ゴムチップからなるゴム
チップ含有硬化性組成物を提供し、第２に（Ａ）水酸基
含有液状ジエン系重合体および／または水酸基含有液状
イソプレン系重合体の水素化物，（Ｂ）ポリイソシアネ
ート化合物，（Ｃ）ゴムチップおよび（Ｄ）有機過酸化
物からなるゴムチップ含有硬化性組成物を提供するもの
である。Specifically, the present invention firstly provides a rubber chip-containing curable composition comprising (A) a hydride of a liquid isoprene polymer containing hydroxyl groups, (B) a polyisocyanate compound, and (C) rubber chips; (A) a hydride of a hydroxyl group-containing liquid diene polymer and/or a hydroxyl group-containing liquid isoprene polymer, (B) a polyisocyanate compound, (C) a rubber chip and (D) a rubber chip-containing curable compound consisting of an organic peroxide. A composition is provided.
【０００６】本発明の第１の組成物では、バインダーと
して（Ａ）成分および（Ｂ）成分からなる液状重合体組
成物を用いることに特徴を有する。（Ａ）成分として用
いる水酸基含有液状イソプレン系重合体の水素化物は、
水酸基含有液状イソプレン系重合体を水素化して得られ
るものである。ここで、水酸基含有液状イソプレン系重
合体としては、既知のものを任意に使用でき、または公
知の方法により容易に製造することができるものである
。例えば、イソプレンモノマーを過酸化水素，水酸基を
有するアゾ化合物（例えば、２，２’−アゾビス〔２−
メチル−Ｎ−（２−ヒドロキシエチル）−プロピオンア
ミド〕等）または水酸基を有するパーオキシド（例えば
、シクロヘキサノンパーオキシド等）を重合開始剤とし
てラジカル重合することにより水酸基含有液状ポリイソ
プレンが得られる。ここで、重合開始剤の使用量は特に
制限はないが、通常はイソプレンモノマー１００ｇに対
して過酸化水素の場合は１．０〜５０ｇ、２，２’−ア
ゾビス〔２−メチル−Ｎ−（２−ヒドロキシエチル）プ
ロピオンアミド〕の場合は５．０〜５０ｇ、シクロヘキ
サノンパーオキシドの場合は５．０〜５０ｇが適当であ
る。重合は無溶媒で行うことも可能であるが、反応の制
御の容易さ等のため溶媒を用いるのが好ましい。溶媒と
してはエタノール，イソプロパノール，ｎ−ブタノール
等が通常用いられる。反応温度は８０〜１５０℃、反応
時間は０．５〜１５時間が適当である。The first composition of the present invention is characterized in that a liquid polymer composition comprising components (A) and (B) is used as a binder. The hydride of the hydroxyl group-containing liquid isoprene polymer used as component (A) is:
It is obtained by hydrogenating a hydroxyl group-containing liquid isoprene polymer. Here, as the hydroxyl group-containing liquid isoprene polymer, any known one can be used, or one that can be easily produced by a known method. For example, isoprene monomer is converted into hydrogen peroxide, an azo compound having a hydroxyl group (e.g., 2,2'-azobis[2-
Hydroxyl group-containing liquid polyisoprene can be obtained by radical polymerization using methyl-N-(2-hydroxyethyl)-propionamide] or a hydroxyl group-containing peroxide (for example, cyclohexanone peroxide, etc.) as a polymerization initiator. Here, the amount of polymerization initiator used is not particularly limited, but usually 1.0 to 50 g of hydrogen peroxide per 100 g of isoprene monomer, 2,2'-azobis[2-methyl-N-( In the case of [2-hydroxyethyl)propionamide], 5.0 to 50 g is appropriate, and in the case of cyclohexanone peroxide, 5.0 to 50 g is appropriate. Although polymerization can be carried out without a solvent, it is preferable to use a solvent for ease of controlling the reaction. Ethanol, isopropanol, n-butanol, etc. are usually used as the solvent. Suitable reaction temperature is 80 to 150°C and reaction time is 0.5 to 15 hours.
【０００７】また、上記の如き方法以外にも、例えばナ
フタレンジリチウム等の触媒を用い、イソプレンモノマ
ーをアニオン重合させてイソプレンリビングポリマーを
製造し、これに、さらにモノエポキシ化合物を反応させ
ることによっても目的とする水酸基含有液状ポリイソプ
レンを得ることができる。この場合の重合は、無溶媒下
で行うことも可能であるが、ラジカル重合の場合と同様
の理由から、溶媒を用いるのが好ましい。溶媒としては
ヘキサン，シクロヘキサン等の飽和炭化水素が用いられ
る。なお、反応温度は５０〜１００℃、反応時間１〜１
０時間が適当である。また、重合時にイソプレンに対し
５０ｍｏｌ％以下の割合の下記モノマーを添加すること
もできる。すなわち、炭素数２〜２２の付加重合性モノ
マー（ブテン，ペンテン，スチレン，α−メチルスチレ
ン，アクリロニトリル，アクリル酸またはそのエステル
，メタクリル酸またはそのエステル，塩化ビニル，酢酸
ビニル，アクリルアミド等）、炭素数４〜２２のジエン
モノマー（ブタジエン，クロロプレン，１，３−ペンタ
ジエン，シクロペンタジエン等）である。[0007] In addition to the above method, for example, isoprene monomer is anionically polymerized using a catalyst such as naphthalene dilithium to produce an isoprene living polymer, and then a monoepoxy compound is further reacted with the polymer. The desired hydroxyl group-containing liquid polyisoprene can be obtained. Although the polymerization in this case can be carried out without a solvent, it is preferable to use a solvent for the same reason as in the case of radical polymerization. Saturated hydrocarbons such as hexane and cyclohexane are used as the solvent. The reaction temperature was 50 to 100°C, and the reaction time was 1 to 1.
0 hours is appropriate. Further, during polymerization, the following monomers can be added in a proportion of 50 mol% or less based on isoprene. That is, addition polymerizable monomers having 2 to 22 carbon atoms (butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid or its ester, methacrylic acid or its ester, vinyl chloride, vinyl acetate, acrylamide, etc.), carbon number 4 to 22 diene monomers (butadiene, chloroprene, 1,3-pentadiene, cyclopentadiene, etc.).
【０００８】重合反応終了後に、溶液を減圧下で蒸留す
れば溶剤が除去され、水酸基含有液状イソプレン系重合
体が得られる。このようにして得られた水酸基含有液状
イソプレン系重合体の数平均分子量は３００〜２５００
０、好ましくは５００〜１００００であり、水酸基含有
量は０．１〜１０ｍｅｑ／ｇ、好ましくは０．３〜７ｍ
ｅｑ／ｇである。なお、水酸基は分子鎖末端あるいは分
子鎖内部のいずれにあってもよいが、分子鎖末端にある
ものが望ましい。また、本発明では二種以上の水酸基含
有液状イソプレン系重合体を組合せて使用することもで
きる。After the polymerization reaction is completed, the solution is distilled under reduced pressure to remove the solvent and obtain a hydroxyl group-containing liquid isoprene polymer. The number average molecular weight of the hydroxyl group-containing liquid isoprene polymer thus obtained is 300 to 2500.
0, preferably 500 to 10,000, and the hydroxyl group content is 0.1 to 10 meq/g, preferably 0.3 to 7 m
It is eq/g. Note that the hydroxyl group may be located either at the end of the molecular chain or inside the molecular chain, but it is preferably located at the end of the molecular chain. Furthermore, in the present invention, two or more types of hydroxyl group-containing liquid isoprene polymers can be used in combination.
【０００９】上記水酸基含有液状イソプレン系重合体を
均一系触媒，不均一系触媒等を用いる公知の方法により
水素化することにより、その水素化物とすることができ
る。均一系触媒を用いる場合、ヘキサン，シクロヘキサ
ン等の飽和炭化水素やベンゼン，トルエン，キシレン等
の芳香族炭化水素を溶媒とし、常温〜１５０℃の反応温
度で、常圧〜５０ｋｇ／ｃｍ２ Ｇの水素圧下で水素添
加反応が行われる。均一系触媒としては遷移金属ハライ
ドとアルミニウム，アルカリ土類金属もしくはアルカリ
金属などのアルキル化物との組合せによるチーグラー触
媒等を上記重合体の二重結合あたり０．０１〜０．１ｍ
ｅｑ％程度使用する。反応は通常１〜２４時間で終了す
る。不均一系触媒等を用いる場合、ヘキサン，シクロヘ
キサン等の飽和炭化水素やベンゼン，トルエン，キシレ
ン等の芳香族炭化水素、ジエチルエーテル，テトラヒド
ロフラン，ジオキサン等のエーテル類、エタノール，イ
ソプロパノール等のアルコール類等またはこれらの混合
系を溶媒とし、常温〜２００℃の反応温度で常圧〜１０
０ｋｇ／ｃｍ２ Ｇの水素圧下で水素添加反応が行われ
る。不均一系触媒としてはニッケル，コバルト，パラジ
ウム，白金，ロジウム，ルテニウム等の触媒を単独で、
またはシリカ，ケイソウ土，アルミナ，活性炭等の担体
に担持して用いる。その使用量は、重合体の重量に対し
０．０５〜１０重量％が適当である。これらの触媒は単
独で使用するほか二種以上を混合して用いてもよい。反
応は通常１〜４８時間で終了する。[0009] The hydroxyl group-containing liquid isoprene polymer can be hydrogenated by a known method using a homogeneous catalyst, a heterogeneous catalyst, etc. to obtain a hydrogenated product thereof. When using a homogeneous catalyst, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene is used as a solvent at a reaction temperature of room temperature to 150°C and under a hydrogen pressure of normal pressure to 50 kg/cm2 G. A hydrogenation reaction takes place. As a homogeneous catalyst, a Ziegler catalyst made of a combination of a transition metal halide and an alkylated product of aluminum, an alkaline earth metal, or an alkali metal is used at a rate of 0.01 to 0.1 m per double bond of the above polymer.
Use about eq%. The reaction usually completes in 1 to 24 hours. When using a heterogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, alcohols such as ethanol and isopropanol, etc. Using a mixed system of these as a solvent, the reaction temperature ranges from room temperature to 200°C and the pressure ranges from normal pressure to 10°C.
The hydrogenation reaction is carried out under a hydrogen pressure of 0 kg/cm2G. Heterogeneous catalysts include nickel, cobalt, palladium, platinum, rhodium, ruthenium, etc. alone.
Alternatively, it is used by being supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon. The amount used is suitably 0.05 to 10% by weight based on the weight of the polymer. These catalysts may be used alone or in combination of two or more. The reaction usually completes in 1 to 48 hours.
【００１０】反応終了後に触媒をろ別して、溶液を減圧
下で蒸留すれば溶剤が除去され、水酸基含有液状イソプ
レン系重合体の水素化物が得られる。この水酸基含有液
状イソプレン系重合体の水素化物は数平均分子量が３０
０〜２５０００、好ましくは５００〜１００００であり
、水酸基含有量は０．１〜１０ｍｅｑ／ｇであるものが
望ましい。After the reaction is completed, the catalyst is filtered off and the solution is distilled under reduced pressure to remove the solvent and obtain a hydrogenated liquid isoprene polymer containing hydroxyl groups. The hydride of this hydroxyl group-containing liquid isoprene polymer has a number average molecular weight of 30
0 to 25,000, preferably 500 to 10,000, and the hydroxyl group content is preferably 0.1 to 10 meq/g.
【００１１】水素化反応後における重合体中の不飽和二
重結合の水素化の割合（水素化率）は下式で表される。The hydrogenation rate (hydrogenation rate) of unsaturated double bonds in the polymer after the hydrogenation reaction is expressed by the following formula.
【００１２】0012
【数１】[Math 1]
【００１３】Ａ：水素化前の重合体の臭素価Ｂ：水素化
後の重合体の臭素価A: Bromine number of the polymer before hydrogenation B: Bromine number of the polymer after hydrogenation
【００１４】上記水素化物の水素化率は５０％以上、好
ましくは７０％以上である。本発明においては、二種以
上の水酸基含有液状イソプレン系重合体の水素化物を混
合して用いてもよい。また、本発明の効果を損なわない
範囲で水酸基含有液状イソプレン系重合体とその水素化
物の混合物を用いてもよい。The hydrogenation rate of the above hydride is 50% or more, preferably 70% or more. In the present invention, a mixture of two or more hydrides of hydroxyl group-containing liquid isoprene polymers may be used. Further, a mixture of a hydroxyl group-containing liquid isoprene polymer and its hydride may be used within a range that does not impair the effects of the present invention.
【００１５】本発明の第１の組成物において（Ｂ）成分
として用いるポリイソシアネート化合物とは、１分子中
に２個またはそれ以上のイソシアネート基を有する有機
化合物であって、前記した水酸基含有液状イソプレン系
重合体の水酸基に対する反応性イソシアネート基を有す
るものである。このポリイソシアネート化合物の例とし
ては、通常の芳香族，脂肪族および脂環族のものを挙げ
ることができ、例えばトリレンジイソシアネート（ＴＤ
Ｉ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、
カルボジイミド変性ジフェニルメタンジイソシアネート
、ポリメチレンポリフェニルイソシアネート、フェニレ
ンジイソシアネート、ナフタリン−１，５−ジイソシア
ネート、ο−トルイジンジイソシアネート、トリフェニ
ルメタントリイソシアネート、トリス（イソシアネート
フェニル）チオホスフェート、イソプロピルベンゼン−
２，４−ジイソシアネート等の芳香族ポリイソシアネー
ト；キシリレンジイソシアネート（ＸＤＩ）、テトラメ
チルキシリレンジイソシアネート（ＴＭＸＤＩ）等の脂
肪族−芳香族ポリイソシアネート（イソシアネート基が
脂肪族炭化水素基を介して芳香族環基と結合したポリイ
ソシアネート、すなわち分子中に芳香族環と直接結合し
たイソシアネート基を有さないポリイソシアネートのこ
と）；ヘキサメチレンジイソシアネート、ドデカンジイ
ソシアネート、リジンジイソシアネート、リジンエステ
ルトリイソシアネート、１，６，１１−ウンデカントリ
イソシアネート、１，８−ジイソシアネート−４−イソ
シアネートメチルオクタン、１，３，６−ヘキサメチレ
ントリイソシアネート、トリメチルヘキサメチレンジイ
ソシアネート等の脂肪族ポリイソシアネート；トランス
シクロヘキサン−１，４−ジイソシアネート、ビシクロ
ヘプタントリイソシアネート、イソホロンジイソシアネ
ート（ＩＰＤＩ）、水素添加ジフェニルメタンジイソシ
アネート、水素添加キシリレンジイソシアネート、水素
添加テトラメチルキシリレンジイソシアネート等の脂環
族ポリイソシアネート；前記ポリイソシアネート化合物
の環化三量体（イソシアヌレート変性体）、ビューレッ
ト変性体やエチレングリコール、１，４−ブタンジオー
ル、プロピレングリコール、ジプロピレングリコール、
トリメチロールプロパン、ポリエーテルポリオール、ポ
リマーポリオール、ポリテトラメチレンエーテルグリコ
ール、ポリエステルポリオール、アクリルポリオール、
ポリアルカジエンポリオール、ポリアルカジエンポリオ
ールの水素化物、部分鹸化エチレン−酢酸ビニル共重合
体、ヒマシ油系ポリオール等のポリオール化合物と前記
ポリイソシアネート化合物との付加反応物等が用いられ
る。The polyisocyanate compound used as component (B) in the first composition of the present invention is an organic compound having two or more isocyanate groups in one molecule, and is a hydroxyl group-containing liquid isoprene compound as described above. It has an isocyanate group that is reactive with the hydroxyl group of the polymer. Examples of this polyisocyanate compound include the usual aromatic, aliphatic and cycloaliphatic compounds, such as tolylene diisocyanate (TD
I), diphenylmethane diisocyanate (MDI),
Carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl)thiophosphate, isopropylbenzene-
Aromatic polyisocyanates such as 2,4-diisocyanate; aliphatic-aromatic polyisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI) (isocyanate groups are aromatic via aliphatic hydrocarbon groups); Polyisocyanate bonded to a ring group, that is, a polyisocyanate that does not have an isocyanate group directly bonded to an aromatic ring in the molecule); hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6, Aliphatic polyisocyanates such as 11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate; transcyclohexane-1,4-diisocyanate, bicyclo Alicyclic polyisocyanates such as heptane triisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate; cyclized trimers of the above polyisocyanate compounds (isocyanurate-modified Biuret modified product, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol,
Trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol,
Addition reaction products of polyol compounds such as polyalkadiene polyols, hydrides of polyalkadiene polyols, partially saponified ethylene-vinyl acetate copolymers, and castor oil-based polyols with the above-mentioned polyisocyanate compounds are used.
【００１６】また、これらポリイソシアネート化合物は
二種以上を混合して用いることもでき、さらにこれらポ
リイソシアネート化合物のイソシアネート基をフェノー
ル類，オキシム類，イミド類，メルカプタン類，アルコ
ール類、ε−カプロラクタム，エチレンイミン，α−ピ
ロリドン，マロン酸ジエチル，亜硫酸水素ナトリウム，
ホウ酸等のブロック剤でブロックした、いわゆるブロッ
クイソシアネート化合物をも用いることができる。[0016] These polyisocyanate compounds can also be used as a mixture of two or more types, and furthermore, the isocyanate groups of these polyisocyanate compounds can be combined with phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, Ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite,
A so-called blocked isocyanate compound blocked with a blocking agent such as boric acid can also be used.
【００１７】本発明の第１の組成物において、（Ａ）成
分と（Ｂ）成分の配合割合については特に制限はないが
、通常（Ａ）成分の水酸基（ＯＨ）に対する（Ｂ）成分
のイソシアネート基（ＮＣＯ）の割合（ＮＣＯ／ＯＨ）
がモル比で０．３〜２５、好ましくは０．５〜１５とな
るように配合するのが好ましい。また、後述するポリオ
ール化合物，ポリアミン化合物等のイソシアネート基と
反応する水酸基やアミノ基を有する化合物を配合する場
合は、配合するすべての水酸基を有する化合物（水素化
物を含む）の水酸基（ＯＨ）と、すべてのアミノ基を有
する化合物のアミノ基（ＮＨ２ ）に対するイソシアネ
ート基の割合（ＮＣＯ／ＯＨ）またはＮＣＯ／（ＯＨ＋
ＮＨ２ ））がモル比で０．３〜２５、好ましくは０．
５〜１５となるように配合すべきである。In the first composition of the present invention, there is no particular restriction on the blending ratio of components (A) and (B), but usually the isocyanate of component (B) is relative to the hydroxyl group (OH) of component (A). Ratio of groups (NCO) (NCO/OH)
It is preferable to mix so that the molar ratio is 0.3 to 25, preferably 0.5 to 15. In addition, when compounding a compound having a hydroxyl group or an amino group that reacts with an isocyanate group such as a polyol compound or a polyamine compound described later, the hydroxyl group (OH) of all the compounds having a hydroxyl group (including hydrides) to be blended, The ratio of isocyanate groups to amino groups (NH2) in a compound having all amino groups (NCO/OH) or NCO/(OH+
NH2 )) in a molar ratio of 0.3 to 25, preferably 0.
It should be blended so that it becomes 5-15.
【００１８】本発明の第１の組成物では、上記（Ａ）成
分と（Ｂ）成分からなる液状重合体組成物をバインダー
として用い、これに（Ｃ）ゴムチップを加えてゴムチッ
プ含有硬化性組成物とする。バインダーとして用いる液
状重合体組成物は、上記（Ａ）成分および（Ｂ）成分を
必須成分とするが、所望によりポリオール化合物，ポリ
アミン化合物，無機充填材，有機充填材，触媒，粘度調
整剤，その他の添加剤を適宜配合することができる。In the first composition of the present invention, a liquid polymer composition consisting of the above components (A) and (B) is used as a binder, and (C) rubber chips are added thereto to form a rubber chip-containing curable composition. shall be. The liquid polymer composition used as a binder has the above-mentioned components (A) and (B) as essential components, but optionally contains a polyol compound, a polyamine compound, an inorganic filler, an organic filler, a catalyst, a viscosity modifier, and others. Additives may be appropriately blended.
【００１９】ここで、ポリオール化合物とは、１分子中
に２個またはそれ以上の水酸基を有する化合物であり、
次に示す低分子量ポリオール化合物，重合型ポリオール
化合物およびヒマシ油系ポリオール化合物が好適に用い
られる。低分子ポリオール化合物としては、一級ポリオ
ール，二級ポリオール，三級ポリオールのいずれを用い
てもよい。具体的には、例えば１，２−プロピレングリ
コール，ジプロピレングリコール，１，２−ブタンジオ
ール，１，３−ブタンジオール，２，３−ブタンジオー
ル，１，２−ペンタンジオール，２，３−ペンタンジオ
ール，２，５−ヘキサンジオール，２，４−ヘキサンジ
オール，２−エチル−１，３−ヘキサンジオール，シク
ロヘキサンジオール，グリセリン，Ｎ，Ｎ−ビス−２−
ヒドロキシプロピルアニリン，Ｎ，Ｎ’−ビスヒドロキ
シイソプロピル−２−メチルピペラジン，ビスフェノー
ルＡのプロピオンオキサイド付加物等の少なくとも１個
の二級炭素に結合した水素基を含有する低分子量ポリオ
ールが挙げられる。[0019] Here, the polyol compound is a compound having two or more hydroxyl groups in one molecule,
The following low molecular weight polyol compounds, polymerizable polyol compounds and castor oil polyol compounds are preferably used. As the low molecular weight polyol compound, any of primary polyol, secondary polyol, and tertiary polyol may be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentane Diol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N,N-bis-2-
Examples include low molecular weight polyols containing a hydrogen group bonded to at least one secondary carbon, such as hydroxypropylaniline, N,N'-bishydroxyisopropyl-2-methylpiperazine, and propion oxide adduct of bisphenol A.
【００２０】さらに、ポリオール化合物として、二級炭
素に結合した水酸基を含有しないエチレングリコール，
ジエチレングリコール，１，３−プロピレングリコール
，１，４−ブタンジオール，１，５−ペンタンジオール
，１，６−ヘキサンジオール，トリメチロールプロパン
，ペンタエリスリトール，ジペンタエリスリトール等を
用いることもできる。その分子量は通常５０〜５００の
範囲のものである。Furthermore, as a polyol compound, ethylene glycol, which does not contain a hydroxyl group bonded to a secondary carbon,
Diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. can also be used. Its molecular weight is usually in the range of 50-500.
【００２１】また、ポリウレタン原料として用いられる
重合型ポリオール化合物としては、例えばポリエーテル
ポリオール及びその変性体，ポリテトラエチレンエーテ
ルグリコール，テトラヒドロフラン／アルキレンオキサ
イド共重合ポリオール，エポキシ樹脂変性ポリオール，
ポリエステルポリオール，ポリジエン系ポリオール，部
分鹸化エチレン−酢酸ビニル共重合体等を挙げることが
できる。これらポリオール化合物の数平均分子量は通常
５００〜１０，０００である。Examples of polymerizable polyol compounds used as polyurethane raw materials include polyether polyols and modified products thereof, polytetraethylene ether glycol, tetrahydrofuran/alkylene oxide copolymer polyols, epoxy resin-modified polyols,
Examples include polyester polyols, polydiene polyols, partially saponified ethylene-vinyl acetate copolymers, and the like. The number average molecular weight of these polyol compounds is usually 500 to 10,000.
【００２２】さらに、ヒマシ油系ポリオール化合物とし
ては、ヒマシ油，水素化ヒマシ油、ヒマシ油エステル交
換物等を挙げることができる。これらポリオール化合物
は、二種類以上を混合して用いることもできる。使用可
能なポリアミン化合物は、１分子中に２個またはそれ以
上の活性水素を有するアミノ基を持つ化合物である。具
体的には、例えばヘキサメチレンジアミン，ポリオキシ
プロピレンポリアミン等の脂肪族ポリアミン、３，３’
−ジメチル−４，４’−ジアミノジシクロヘキシルメタ
ン等の脂環族ポリアミン、３，３’−ジクロロ−４，４
’−ジアミノジフェニルメタン，３，５’−ジエチルト
ルエン−２，４−ジアミン，３，５’−ジエチルトルエ
ン−２，６−ジアミン等の芳香族ポリアミン等を挙げる
ことができる。Further, examples of the castor oil polyol compound include castor oil, hydrogenated castor oil, and castor oil transesterified products. These polyol compounds can also be used in combination of two or more types. The polyamine compound that can be used is a compound having an amino group having two or more active hydrogens in one molecule. Specifically, aliphatic polyamines such as hexamethylene diamine and polyoxypropylene polyamine, 3,3'
-Alicyclic polyamines such as dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dichloro-4,4
Aromatic polyamines such as '-diaminodiphenylmethane, 3,5'-diethyltoluene-2,4-diamine, and 3,5'-diethyltoluene-2,6-diamine can be mentioned.
【００２３】上記の如きポリオール化合物またはポリア
ミン化合物は、通常は前記した（Ａ）成分の水酸基含有
液状イソプレン系重合体の水素化物１００重量部に対し
てポリオール化合物またはポリアミン化合物を１〜１，
０００重量部、好ましくは３〜２００重量部の割合で配
合することができる。The above-mentioned polyol compound or polyamine compound is usually used in an amount of 1 to 1% by weight per 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer as component (A).
000 parts by weight, preferably 3 to 200 parts by weight.
【００２４】次に、無機充填材としては、亜鉛，アスベ
スト，アルミナ，アルミニウム，カオリンクレー，ガラ
ス級ガラスフレーク，ガラス繊維，炭素（チャンネルブ
ラック，ファーネスブラック，アセチレンブラック，サ
ーマルブラック），炭素繊維，カスミ石，クリオライト
，グラファイト，シリカ，ケイ灰石，ケイソウ土，酸化
亜鉛，酸化マグネシウム，酸化ジルコニウム，酸化チタ
ン，酸化鉄，水酸化アルミニウム，水酸化マグネシウム
，スレート粉，ゼオライト，石英粉，炭酸カルシウム，
炭酸マグネシウム，タルク，チタン酸カリウム，窒化ホ
ウ素，長石粉，銅，ニッケル，二硫化モリブテン，硫酸
バリウム，ホワイティング，ロウ石クレー、マイカ，セ
ッコウ等を挙げることができる。Next, examples of inorganic fillers include zinc, asbestos, alumina, aluminum, kaolin clay, glass-grade glass flakes, glass fiber, carbon (channel black, furnace black, acetylene black, thermal black), carbon fiber, and kaolin clay. Stone, cryolite, graphite, silica, wollastonite, diatomaceous earth, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, aluminum hydroxide, magnesium hydroxide, slate powder, zeolite, quartz powder, calcium carbonate,
Magnesium carbonate, talc, potassium titanate, boron nitride, feldspar powder, copper, nickel, molybdenum disulfide, barium sulfate, whiting, waxite clay, mica, gypsum, etc. can be mentioned.
【００２５】また、有機充填材としては、セルロース，
リグニン，キチン質，皮革粉，ヤシガラ，木粉等をはじ
め、木綿，麻，羊毛，絹等の天然系繊維、ナイロン，ポ
リエステル，ビニロン，アセテート，アクリル等の合成
繊維、ポリエチレン，ポリプロピレン，ポリスチレン，
アクリル−ブタジエン−スチレン樹脂，ポリカーボネー
ト，ポリエチレンテレフタレート，ポリブチレンテレフ
タレート，ポリメチルメタクリレート，塩化ビニル樹脂
，エポキシ樹脂，フェノール樹脂等の合成樹脂粉末また
は顆粒等を挙げることができる。[0025] Further, as the organic filler, cellulose,
Lignin, chitin, leather powder, coconut shell, wood flour, etc., natural fibers such as cotton, linen, wool, silk, synthetic fibers such as nylon, polyester, vinylon, acetate, acrylic, polyethylene, polypropylene, polystyrene, etc.
Examples include synthetic resin powders or granules such as acrylic-butadiene-styrene resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, vinyl chloride resin, epoxy resin, and phenol resin.
【００２６】このような無機充填材あるいは有機充填材
は本発明の効果を損なわない範囲で適宜配合することが
できる。[0026] Such inorganic fillers or organic fillers can be appropriately blended within a range that does not impair the effects of the present invention.
【００２７】硬化反応を促進するためにトリエチレンジ
アミン，テトラメチルグアニジン，Ｎ，Ｎ，Ｎ’Ｎ’−
テトラメチルヘキサン−１，６−ジアミン，Ｎ，Ｎ，Ｎ
’Ｎ”Ｎ”−ペンタメチルジエチレントリアミン，ビス
（２−ジメチルアミノエチル）エーテル，１，２−ジメ
チルイミダゾール，Ｎ−メチル−Ｎ’−（２−ジメチル
アミノ）エチルピペラジン，ジアザビシクロウンデセン
等の三級アミン，スタナスオクトエート，ジブチルチン
ジアセテート，ジブチルチンジラウレート，ジブチルチ
ンチオカルボキシレート，ジブチルチンマーカプチド，
ジオクチルチンチオカルボキシレート，フェニル水銀プ
ロピオン酸塩，オクテン酸鉛等の有機金属化合物、前記
三級アミンのカルボン酸塩等の触媒を添加することがで
きる。これら触媒は、（Ａ）成分である水酸基含有液状
イソプレン系重合体の水素化物１００重量部に対して最
大１０重量部添加することができる。１０重量部を越え
ると、硬化促進硬化が限界となるばかりでなく、局部的
な異常反応生起（ゲル化）の危険性が大きくなるので好
ましくない。Triethylenediamine, tetramethylguanidine, N,N,N'N'-
Tetramethylhexane-1,6-diamine, N,N,N
'N''N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, 1,2-dimethylimidazole, N-methyl-N'-(2-dimethylamino)ethylpiperazine, diazabicycloundecene, etc. Tertiary amine, stannath octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, dibutyltin mercaptide,
Catalysts such as dioctyltinthiocarboxylate, phenylmercury propionate, organometallic compounds such as lead octenoate, and carboxylates of the above-mentioned tertiary amines can be added. A maximum of 10 parts by weight of these catalysts can be added to 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer as component (A). If the amount exceeds 10 parts by weight, not only will accelerated curing reach a limit, but also the risk of local abnormal reaction occurrence (gelation) will increase, which is not preferable.
【００２８】粘度調整剤としては、ジオクチルフタレー
ト等の可塑剤、パラフィン系，ナフテン系，アロマ系等
のプロセスオイル、オレフィンオリゴマー、アルキルベ
ンゼン、アルキルナフタレン、アルキルジフェニルエタ
ン、シリコーンオイル等を挙げることができる。この粘
度調整剤の配合量についても特に制限はないが、通常は
（Ａ）成分の水酸基含有液状イソプレン系重合体の水素
化物１００重量部に対し５００重量部以下、好ましくは
２００重量部以下である。本発明においては、所望によ
りさらに下記に示す他の添加剤を、反応中または反応後
に添加することもできる。Examples of the viscosity modifier include plasticizers such as dioctyl phthalate, paraffinic, naphthenic, and aromatic process oils, olefin oligomers, alkylbenzenes, alkylnaphthalenes, alkyldiphenylethanes, and silicone oils. There is no particular restriction on the amount of this viscosity modifier, but it is usually 500 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer as component (A). . In the present invention, other additives shown below may be added during or after the reaction, if desired.
【００２９】粘度低下のためにｎ−ヘキサン，シクロヘ
キサン，トルエン，キシレン等の炭化水素系溶剤、メチ
ルエチルケトン，シクロヘキサノン等のケトン系溶剤、
酢酸ブチル等のエステル系溶剤、テトラヒドロフラン等
のエーテル系溶剤、Ｎ，Ｎ−ジエチルホルムアミド，ジ
メチルスルホキシド等の溶剤を配合してもよい。この溶
剤の配合量についても特に制限はないが、通常は（Ａ）
成分である水酸基含有液状イソプレン系重合体の水素化
物１００重量部に対して２００重量部以下、好ましくは
１００重量部以下である。Hydrocarbon solvents such as n-hexane, cyclohexane, toluene and xylene, ketone solvents such as methyl ethyl ketone and cyclohexanone, etc. to reduce viscosity;
Ester solvents such as butyl acetate, ether solvents such as tetrahydrofuran, and solvents such as N,N-diethylformamide and dimethyl sulfoxide may be blended. There are no particular restrictions on the amount of this solvent, but usually (A)
The amount is 200 parts by weight or less, preferably 100 parts by weight or less, based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer.
【００３０】また、粘着力，接着力の調整のためにアル
キルフェノール樹脂，テルペン樹脂，テルペンフェノー
ル樹脂，キシレンホルムアルデヒド樹脂，ロジン，水添
ロジン，クマロン樹脂，脂肪族石油樹脂，脂環族石油樹
脂および芳香族石油樹脂等の粘着性付与剤を使用しても
よい。さらに、耐熱性，耐候性向上のためにヒンダード
フェノール系，ヒンダードアミン系，ヘンゾトリアゾー
ル系等の老化防止剤を加えたり、難燃剤として赤リン，
ヘキサブロモベンゼン等を加えたり、消泡剤としてシリ
コン化合物等を加えたり、発泡防止剤としてゼオライト
，生石灰等を添加することができる。[0030]Also, in order to adjust adhesive strength and adhesive strength, alkylphenol resin, terpene resin, terpenephenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, coumaron resin, aliphatic petroleum resin, alicyclic petroleum resin, and aromatic Tackifying agents such as family petroleum resins may also be used. Furthermore, to improve heat resistance and weather resistance, anti-aging agents such as hindered phenol, hindered amine, and henzotriazole are added, and red phosphorus and flame retardants are added.
Hexabromobenzene or the like may be added, a silicon compound or the like may be added as an antifoaming agent, or zeolite, quicklime, etc. may be added as an antifoaming agent.
【００３１】本発明の第１の組成物で（Ｃ）成分として
用いるゴムチップは、一般に使用されている天然ゴム，
合成ゴムおよびそれらの廃ゴムのいずれであってもよい
。具体的には、ＮＲ，ＳＢＲ，ＮＢＲ，ＥＰＤＭ等を挙
げることができ、これらの中でも特にＳＢＲ，ＥＰＤＭ
が好ましい。ゴムチップの粒径は０．５〜１０ｍｍが好
ましく、形状については特に問わない。The rubber chips used as component (C) in the first composition of the present invention are commonly used natural rubber,
It may be either synthetic rubber or its waste rubber. Specifically, NR, SBR, NBR, EPDM, etc. can be mentioned, and among these, SBR, EPDM, etc.
is preferred. The particle size of the rubber chips is preferably 0.5 to 10 mm, and the shape is not particularly limited.
【００３２】バインダーとして用いる液状重合体組成物
の（Ｃ）成分たるゴムチップへの添加量は、ゴムチップ
組成物中の液状重合体組成物の量が１〜３０重量％とな
るようにするのが好ましい。液状重合体組成物のゴムチ
ップへの添加量が１重量％未満であると、得られる硬化
体の物性が不充分であり好ましくなく、また３０重量％
を超えると、得られる硬化体においてゴムチップの有す
る弾力性，外観を損うため好ましくない。[0032] The amount of the liquid polymer composition used as a binder to be added to the rubber chips as component (C) is preferably such that the amount of the liquid polymer composition in the rubber chip composition is 1 to 30% by weight. . If the amount of the liquid polymer composition added to the rubber chip is less than 1% by weight, the resulting cured product will have insufficient physical properties, which is undesirable;
If it exceeds this amount, the elasticity and appearance of the rubber chips in the obtained cured product will be impaired, which is not preferable.
【００３３】本発明の第１の組成物は、前記（Ａ）成分
および（Ｂ）成分を所定割合で配合し混合して液状重合
体組成物を調製後、（Ｃ）成分であるゴムチップを配合
することにより得られる。液状重合体組成物の調製にあ
たっては、混合装置，混練装置等を用いて０〜１２０℃
、好ましくは１５〜１００℃の温度で０．５秒〜８時間
、好ましくは１秒〜５時間かく拌，混合すればよい。
液状重合体組成物の調製は、通常ワンショット法または
プレポリマー法により行う。The first composition of the present invention is prepared by blending and mixing the components (A) and (B) in a predetermined ratio to prepare a liquid polymer composition, and then blending the rubber chips as component (C). It can be obtained by In preparing the liquid polymer composition, a mixing device, a kneading device, etc. are used to prepare the liquid polymer composition at a temperature of 0 to 120°C.
, preferably at a temperature of 15 to 100°C for 0.5 seconds to 8 hours, preferably 1 second to 5 hours. The liquid polymer composition is usually prepared by a one-shot method or a prepolymer method.
【００３４】ワンショット法では、まず前記成分のうち
少なくともポリイソシアネート化合物を除く成分を配合
して上記の温度および時間の条件で混合し、混合物を得
る。この混合物にポリイソシアネート化合物および先の
混合で用いなかった添加剤成分を添加して上記の温度お
よび時間の条件で混合することにより、液状重合体組成
物が得られる。得られた液状重合体組成物に所定量のゴ
ムチップを配合し、０〜１５０℃、好ましくは１５〜１
２０℃の温度で１０秒〜１時間、好ましくは１５秒〜４
５分間かく拌混合すればゴムチップ含有硬化性組成物が
得られる。このときの好ましい反応当量比（ＮＣＯ／Ｏ
ＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ）は０．５〜２．５
である。[0034] In the one-shot method, first, among the above components, at least the components excluding the polyisocyanate compound are blended and mixed under the above temperature and time conditions to obtain a mixture. A liquid polymer composition is obtained by adding the polyisocyanate compound and additive components not used in the previous mixing to this mixture and mixing under the above temperature and time conditions. A predetermined amount of rubber chips is blended into the obtained liquid polymer composition, and the mixture is heated to 0-150°C, preferably 15-150°C.
10 seconds to 1 hour, preferably 15 seconds to 4 hours at a temperature of 20°C
A curable composition containing rubber chips can be obtained by stirring and mixing for 5 minutes. At this time, the preferred reaction equivalent ratio (NCO/O
H or NCO/(OH+NH2) is 0.5 to 2.5
It is.
【００３５】プレポリマー法では、所定の当量比（ＮＣ
Ｏ／ＯＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ））が１．７
〜２５の範囲で、水酸基含有液状イソプレン系重合体の
水素化物，ポリオール化合物，ポリアミン化合物のうち
少なくとも一つとポリイソシアネート化合物とを、その
他の添加剤の一部または全部の存在下あるいは非存在下
に反応させてプレポリマーを得る。この場合の反応温度
は上記条件と同じであり、反応時間は通常０．１〜１０
時間、好ましくは０．５〜８時間である。さらに、この
プレポリマーに残りの成分を上記の温度および時間の条
件で混合することにより、液状重合体組成物が得られる
。
このときの好ましい反応当量比（ＮＣＯ／ＯＨまたはＮ
ＣＯ／（ＯＨ＋ＮＨ２ ））は０．５〜２．５である。
このプレポリマーは空気中の湿気により硬化する性質を
有するので、そのまま用いることもできる。得られた液
状重合体組成物に所定量のゴムチップを配合し、０〜１
５０℃、好ましくは１５〜１２０℃の温度で１０秒から
１時間、好ましくは１５秒〜４５分間かく拌混合すれば
ゴムチップ含有硬化性組成物が得られる。In the prepolymer method, a predetermined equivalent ratio (NC
O/OH or NCO/(OH+NH2)) is 1.7
~25, at least one of a hydride of a hydroxyl group-containing liquid isoprene polymer, a polyol compound, a polyamine compound, and a polyisocyanate compound in the presence or absence of some or all of other additives. A prepolymer is obtained by reaction. The reaction temperature in this case is the same as the above conditions, and the reaction time is usually 0.1 to 10
time, preferably 0.5 to 8 hours. Furthermore, a liquid polymer composition is obtained by mixing the remaining components with this prepolymer under the above temperature and time conditions. At this time, the preferred reaction equivalent ratio (NCO/OH or N
CO/(OH+NH2)) is 0.5 to 2.5. Since this prepolymer has the property of being cured by moisture in the air, it can also be used as is. A predetermined amount of rubber chips is blended into the obtained liquid polymer composition, and 0 to 1
A curable composition containing rubber chips can be obtained by stirring and mixing at a temperature of 50° C., preferably 15 to 120° C., for 10 seconds to 1 hour, preferably 15 seconds to 45 minutes.
【００３６】上記の如くして得られたゴムチップ含有硬
化性組成物を硬化処理することにより、様々な形状の硬
化物を得ることができる。通常は、ゴムチップ含有硬化
性組成物を金型あるいは種々の形状の型枠を使用したり
、コテ塗り等によって任意の形状とすることができる。
この状態で０〜１５０℃、好ましくは１５〜１３０℃に
て２０秒〜１０日間、好ましくは７分間〜７日間硬化処
理することにより、硬化物とすることができる。この様
にして得られた硬化物は、比較的高温，高湿下において
光の照射を受けても変色することもないし、機械的強度
も優れているので亀裂が発生しにくい。By curing the rubber chip-containing curable composition obtained as described above, cured products of various shapes can be obtained. Usually, the rubber chip-containing curable composition can be formed into any desired shape by using a mold or a mold of various shapes, or by coating with a trowel. A cured product can be obtained by curing in this state at 0 to 150°C, preferably 15 to 130°C for 20 seconds to 10 days, preferably 7 minutes to 7 days. The cured product obtained in this manner does not discolor even when exposed to light at relatively high temperatures and high humidity, and has excellent mechanical strength so that cracks are less likely to occur.
【００３７】次に、本発明の第２の組成物について説明
する。本発明の第２の組成物は、（Ａ）水酸基含有液状
ジエン系重合体および／または水酸基含有液状イソプレ
ン系重合体の水素化物，（Ｂ）ポリイソシアネート化合
物，（Ｃ）ゴムチップおよび（Ｄ）有機過酸化物からな
るゴムチップ含有硬化性組成物であり、バインダーとし
て（Ａ），（Ｂ）および（Ｄ）成分からなる液状重合体
組成物を用いることに特徴を有する。Next, the second composition of the present invention will be explained. The second composition of the present invention comprises (A) a hydride of a hydroxyl group-containing liquid diene polymer and/or a hydroxyl group-containing liquid isoprene polymer, (B) a polyisocyanate compound, (C) a rubber chip, and (D) an organic This is a curable composition containing rubber chips made of peroxide, and is characterized by using a liquid polymer composition made of components (A), (B), and (D) as a binder.
【００３８】（Ａ）成分としては、水酸基含有液状ジエ
ン系重合体および／または水酸基含有液状イソプレン系
重合体を用いる。ここで、水酸基含有液状ジエン系重合
体としては、既知のものを任意に使用でき、または公知
の手法により容易に製造することができる。例えば炭素
数４〜２２のジエンモノマー（ブタジエン，イソプレン
，クロロプレン，１，３−ペンタジエン，シクロペンタ
ジエン等）を過酸化水系，水酸基を有するアゾ化合物（
例えば２，２’−アゾビス〔２−メチル−Ｎ−（２−ヒ
ドロキシエチル）プロピオンアミド〕等），水酸基を有
するパーオキシド（例えばシクロヘキサノンパーオキシ
ド等）などを重合開始剤としてラジカル重合することに
より水酸基含有液状ジエン系重合体が得られる。ここで
、重合開始剤の使用量は特に制限はないが、ジエンモノ
マー１００に対して過酸化水素１．０〜５０ｇ、２，２
’−アゾビス〔２−メチル−Ｎ−（２−ヒドロキシエチ
ル）プロピオンアミド〕５．０〜１００ｇ、シクロヘキ
サノンパーオキサイド５．０〜１００ｇが適当である。
重合は無溶媒で行うことも可能であるが、反応の制御の
容易さのため溶媒を用いるのが好ましく、溶媒としては
エタノール，イソプロパノール，ｎ−ブタノール等が通
常用いられる。また、反応温度は８０〜１５０℃、反応
時間は０．５〜１５時間が適当である。As component (A), a hydroxyl group-containing liquid diene polymer and/or a hydroxyl group-containing liquid isoprene polymer is used. Here, as the hydroxyl group-containing liquid diene polymer, any known one can be used, or it can be easily produced by a known method. For example, a diene monomer having 4 to 22 carbon atoms (butadiene, isoprene, chloroprene, 1,3-pentadiene, cyclopentadiene, etc.) is mixed with aqueous peroxide, and an azo compound with a hydroxyl group (
Hydroxyl groups can be added by radical polymerization using a polymerization initiator such as 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], etc.), or a peroxide having a hydroxyl group (e.g. cyclohexanone peroxide, etc.) as a polymerization initiator. A liquid diene polymer is obtained. Here, the amount of polymerization initiator used is not particularly limited, but hydrogen peroxide is 1.0 to 50 g, 2,2
Suitable amounts are 5.0 to 100 g of '-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and 5.0 to 100 g of cyclohexanone peroxide. Although the polymerization can be carried out without a solvent, it is preferable to use a solvent in order to easily control the reaction, and ethanol, isopropanol, n-butanol, etc. are usually used as the solvent. Further, the reaction temperature is suitably 80 to 150°C, and the reaction time is suitably 0.5 to 15 hours.
【００３９】さらに、ナフタレンジリチウム等の触媒を
用いてジエンモノマーをアニオン重合させてリビングポ
リマーを製造し、さらにモノエポキシ化合物等を反応さ
せることによっても目的とする水酸基含有液状ジエン系
重合体を得ることができる。この場合の重合は無溶媒で
行うことも可能であるが、ラジカル重合の場合と同様の
理由から溶媒を用いるのが好ましい。溶媒としてはヘキ
サン，シクロヘキサン等の飽和炭化水素が用いられる。
この時、反応温度は５０〜１００℃、反応時間は１〜１
０時間が適当である。また、重合時にジエンモノマーに
対し５０ｍｏｌ％以下の割合で炭素数２〜２２の付加重
合性モノマー、例えばブテン，ペンテン，スチレン，α
−メチルスチレン，アクリロニトリル，アクリル酸およ
びそのエステル，メタクリル酸およびそのエステル，塩
化ビニル，酢酸ビニル，アクリルアミド等を添加するこ
とも出来る。[0039] Furthermore, a living polymer is produced by anionically polymerizing a diene monomer using a catalyst such as naphthalene dilithium, and the desired hydroxyl group-containing liquid diene polymer is also obtained by further reacting with a monoepoxy compound or the like. be able to. Although the polymerization in this case can be carried out without a solvent, it is preferable to use a solvent for the same reasons as in the case of radical polymerization. Saturated hydrocarbons such as hexane and cyclohexane are used as the solvent. At this time, the reaction temperature is 50-100℃, and the reaction time is 1-1
0 hours is appropriate. In addition, addition polymerizable monomers having 2 to 22 carbon atoms, such as butene, pentene, styrene, α
- Methylstyrene, acrylonitrile, acrylic acid and its esters, methacrylic acid and its esters, vinyl chloride, vinyl acetate, acrylamide, etc. can also be added.
【００４０】重合反応終了後に溶媒を減圧下で蒸留すれ
ば溶剤が除去され、水酸基含有液状ジエン系重合体を得
られる。このようにして得られた水酸基含有液状ジエン
系重合体の数平均分子量は、通常３００〜２５０００、
好ましくは５００〜１００００であり、水酸基含有量は
０．１〜１０ｍｅｑ／ｇ、好ましくは０．３〜７ｍｅｑ
／ｇである。なお、液状ジエン系重合体の水酸基は分子
鎖末端あるいは分子鎖内部のいずれの位置にあってもよ
いが、分子鎖末端にあるものが望ましい。また、本発明
では二種類以上の水酸基含有液状ジエン系重合体を組合
せて使用することもできる。After the completion of the polymerization reaction, the solvent is removed by distillation under reduced pressure to obtain a liquid diene polymer containing hydroxyl groups. The number average molecular weight of the hydroxyl group-containing liquid diene polymer thus obtained is usually 300 to 25,000,
Preferably it is 500 to 10,000, and the hydroxyl group content is 0.1 to 10 meq/g, preferably 0.3 to 7 meq
/g. The hydroxyl group of the liquid diene polymer may be located at either the end of the molecular chain or inside the molecular chain, but it is preferably located at the end of the molecular chain. Further, in the present invention, two or more types of hydroxyl group-containing liquid diene polymers can be used in combination.
【００４１】上記水酸基含有液状ジエン系重合体の代わ
りに、あるいは該液状ジエン系重合体と共に、（Ａ）成
分として用いられる水酸基含有液状イソプレン系重合体
の水素化物は、前記本発明の第１の組成物において説明
した（Ａ）水酸基含有液状イソプレン系重合体の水素化
物と同様である。[0041] The hydrogenated product of the hydroxyl group-containing liquid isoprene polymer used as component (A) instead of or together with the hydroxyl group-containing liquid diene polymer is the one described in the first aspect of the present invention. This is the same as (A) the hydride of the hydroxyl group-containing liquid isoprene polymer described in the composition.
【００４２】（Ｂ）成分として用いるポリイソシアネー
ト化合物とは、１分子中に２個またはその以上のイソシ
アネート基を有する有機化合物であって、前記した水酸
基含有液状ジエン系重合体および／または水酸基含有液
状イソプレン系重合体の水素化物の水酸基に対する反応
性イソシアネート基を有するものである。このポリイソ
シアネート化合物の例としては、前記本発明の第１の組
成物における（Ｂ）ポリイソシアネート化合物と同様で
ある。The polyisocyanate compound used as component (B) is an organic compound having two or more isocyanate groups in one molecule, and is a hydroxyl group-containing liquid diene polymer and/or a hydroxyl group-containing liquid polymer. It has an isocyanate group that is reactive with the hydroxyl group of the hydride of the isoprene polymer. Examples of this polyisocyanate compound are the same as the polyisocyanate compound (B) in the first composition of the present invention.
【００４３】上記の如き（Ａ）成分と（Ｂ）成分の配合
割合については特に制限はないが、通常は（Ａ）成分で
ある水酸基含有液状ジエン系重合体および／または水酸
基含有液状イソプレン系重合体の水素化物の水酸基（Ｏ
Ｈ）に対する（Ｂ）成分であるポリイソシアネート化合
物のイソシアネート基（ＮＣＯ）の割合（ＮＣＯ／ＯＨ
）が、モル比で最終的に０．３〜２５、好ましくは０．
３〜５．０、さらに好ましくは０．５〜４．０となるよ
うに配合すればよい。There is no particular restriction on the blending ratio of component (A) and component (B) as described above, but usually component (A) is a hydroxyl group-containing liquid diene polymer and/or a hydroxyl group-containing liquid isoprene polymer. The hydroxyl group (O
The ratio of isocyanate groups (NCO) of the polyisocyanate compound which is the component (B) to H) (NCO/OH
) is finally in a molar ratio of 0.3 to 25, preferably 0.
What is necessary is just to mix|blend so that it may become 3-5.0, more preferably 0.5-4.0.
【００４４】また、本発明の組成物中に、後述する如き
ポリオール化合物，ポリアミン化合物などの、ポリイソ
シアネート化合物のイソシアネート基と反応する水酸基
やアミノ基を有する化合物を配合する場合には、配合す
る全ての水酸基を有する化合物（水素化物を含む）の水
酸化（ＯＨ）と全てのアミノ基を有する化合物のアミノ
基（ＮＨ２ ）に対するイソシアネート基の割合（ＮＣ
Ｏ／ＯＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ））が、モル
比で最終的に上記割合となるように配合する。ここで「
最終的」という言葉を用いているのは、実際の硬化体の
作製にあたって下記の様な種々の方法が用いられるから
である。[0044] In addition, when compounding a compound having a hydroxyl group or an amino group that reacts with the isocyanate group of a polyisocyanate compound, such as a polyol compound or a polyamine compound as described below, in the composition of the present invention, all the compounds to be blended Hydroxylation (OH) of compounds with hydroxyl groups (including hydrides) and the ratio of isocyanate groups to amino groups (NH2) of all compounds with amino groups (NC
O/OH or NCO/(OH+NH2)) are blended so that the final molar ratio becomes the above ratio. here"
The word "final" is used because various methods such as those described below are used in actually producing the cured product.
【００４５】ワンショット法：全配合成分のうち少なく
ともポリイソシアネート化合物を除く成分を混合し、混
合物を得る。この混合物にポリイソシアネート化合物お
よび先の混合で用いなかった配合成分を添加，混合して
液状重合体組成物を得る。このときの好ましいＮＣＯ／
ＯＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ）（モル比）は０
．３〜２．０である。One-shot method: A mixture is obtained by mixing all ingredients except at least the polyisocyanate compound. A polyisocyanate compound and ingredients not used in the previous mixing are added to this mixture and mixed to obtain a liquid polymer composition. Preferred NCO/
OH or NCO/(OH+NH2) (molar ratio) is 0
．． It is 3-2.0.
【００４６】プレポリマー法（１）：所定の当量比（Ｎ
ＣＯ／ＯＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ））が１．
７〜２５の範囲で、水酸基を有する化合物またはアミノ
基を有する化合物のうち少なくとも１つとポリイソシア
ネート化合物とを、その他の添加剤の一部または全部の
存在下あるいは非存在下に反応させてプレポリマーを得
るこのプレポリマーに残りの成分を混合し、液状重合体
組成物を得る。このときの好ましいＮＣＯ／ＯＨまたは
ＮＣＯ／（ＯＨ＋ＮＨ２ ）（モル比）は０．３〜２．
０である。この場合、プレポリマーを得るときに反応に
関与した官能基のモル比（ＮＣＯ／ＯＨまたはＮＣＯ／
（ＯＨ＋ＮＨ２ ））は実質的に１．０であるので、最
終的なＮＣＯ／ＯＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ）
は０．３〜２．０の範囲内にある。Prepolymer method (1): Predetermined equivalent ratio (N
CO/OH or NCO/(OH+NH2)) is 1.
7 to 25, reacting at least one compound having a hydroxyl group or a compound having an amino group with a polyisocyanate compound in the presence or absence of some or all of other additives to produce a prepolymer. The remaining components are mixed with this prepolymer to obtain a liquid polymer composition. At this time, the preferred NCO/OH or NCO/(OH+NH2) (molar ratio) is 0.3 to 2.
It is 0. In this case, when obtaining the prepolymer, the molar ratio of the functional groups involved in the reaction (NCO/OH or NCO/
(OH+NH2)) is essentially 1.0, so the final NCO/OH or NCO/(OH+NH2)
is within the range of 0.3 to 2.0.
【００４７】プレポリマー法（２）：所定の当量比ＮＣ
Ｏ／ＯＨまたはＮＣＯ／（ＯＨ＋ＮＨ２ ）が１．７〜
２５の範囲で配合全成分を配合し、反応させてプレポリ
マーを得る。このプレポリマーを空気中の湿気（水）と
反応させる。Prepolymer method (2): Predetermined equivalent ratio NC
O/OH or NCO/(OH+NH2) is 1.7~
All components are blended within a range of 25 and reacted to obtain a prepolymer. This prepolymer is reacted with moisture (water) in the air.
【００４８】次に、（Ｄ）成分として用いる有機過酸化
物としては特に制限はなく、一般に知られている有機過
酸化物であればよい。ただし、バインダーとゴムチップ
間のカップリング反応をより容易に起こさせるため、過
酸化物ラジカルの水素引抜き能力が大きいものを用いる
ことが望ましい。具体的にはジ−ｔ−ブチルペルキシド
、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキ
シ）ヘキサン、２，５−ジメチル２，５−ジ（ｔ−ブチ
ルペルオキシ）ヘキシン−３、ジ−ｔ−ブチルペルオキ
シジ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）バレエート、１，１−ジ（ｔ
−ブチルペルオキシ）−３，３，５−トリメチルシクロ
ヘキサン、ジクミルペルオキシド、１，３−ビス（ｔ−
ブチルペルオキシイソプロピル）ベンゼン、ｔ−ブチル
クミルペルオキシド、トリス−（ｔ−ブチルペルオキシ
）トリアジン等の三級炭素を有する過酸化物，メチルエ
チルケトンペルオキシド、メチルイソブチルケトンペル
オキシド、シクロヘキサノンペルオキシド、メチルシク
ロヘキサノンペルオキシド、アセチルアセトンペルオキ
シド等のケトンを有する過酸化物等を挙げることができ
る。これらの中でも、特にメチルエチルケトンペルオキ
シドやジクミルペルオキシドを用いるのが好ましい。Next, the organic peroxide used as component (D) is not particularly limited, and any generally known organic peroxide may be used. However, in order to more easily cause the coupling reaction between the binder and the rubber chips, it is desirable to use peroxide radicals that have a large hydrogen abstracting ability. Specifically, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, di -t-butylperoxydiisopropylbenzene, n-butyl-4,4-bis(t-butylperoxy)valerate, 1,1-di(t
-butylperoxy)-3,3,5-trimethylcyclohexane, dicumylperoxide, 1,3-bis(t-
Peroxides with tertiary carbon such as butylperoxyisopropyl)benzene, t-butylcumylperoxide, tris-(t-butylperoxy)triazine, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide Examples include peroxides having ketones such as. Among these, it is particularly preferable to use methyl ethyl ketone peroxide and dicumyl peroxide.
【００４９】（Ｄ）成分の配合量は、後述する（Ｃ）成
分であるゴムチップに対して０．０１〜５重量部、好ま
しくは０．１〜２．０重量部である。また、本発明では
（Ｄ）有機過酸化物と併用して、コバルト，マンガン，
鉄，銅，セリウム等の金属塩を助剤として用いることが
できる。これらは、金属イオンの形で有機過酸化物の分
解触媒となる。助剤の添加量は、（Ｄ）有機過酸化物に
対し０．５〜２０重量部、好ましくは２〜１０重量部で
ある。また、この他に硫黄、Ｎ，Ｎ−メチルアニリン等
のアミン系化合物、オキシム類、トリメチロールプロパ
ントリメタクリレート，エチレングリコールジメタクリ
レート等の多官能モノマー等も使用可能である。The blending amount of component (D) is 0.01 to 5 parts by weight, preferably 0.1 to 2.0 parts by weight, based on the rubber chips as component (C) described below. In addition, in the present invention, cobalt, manganese,
Metal salts such as iron, copper, cerium, etc. can be used as auxiliaries. These act as decomposition catalysts for organic peroxides in the form of metal ions. The amount of the auxiliary agent added is 0.5 to 20 parts by weight, preferably 2 to 10 parts by weight, based on the organic peroxide (D). In addition, sulfur, amine compounds such as N,N-methylaniline, oximes, and polyfunctional monomers such as trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate can also be used.
【００５０】本発明の第２の組成物では、上記（Ａ），
（Ｂ）および（Ｄ）成分からなる液状重合体組成物をバ
インダーとして用い、これに（Ｃ）ゴムチップを加えて
ゴムチップ含有硬化性組成物とする。バインダーとして
用いる液状重合体組成物は、上記（Ａ），（Ｂ）および
（Ｄ）成分を必須成分とするが、所望によりポリオール
化合物，ポリアミン化合物，無機充填材，有機充填材，
粘度調整剤，その他の添加剤を適宜配合することができ
る。これらは、前記本発明の第１の組成物において説明
したものと同様である。[0050] In the second composition of the present invention, the above (A),
A liquid polymer composition consisting of components (B) and (D) is used as a binder, and (C) rubber chips are added thereto to obtain a rubber chip-containing curable composition. The liquid polymer composition used as a binder has the above components (A), (B), and (D) as essential components, but optionally contains a polyol compound, a polyamine compound, an inorganic filler, an organic filler,
A viscosity modifier and other additives can be added as appropriate. These are the same as those explained in the first composition of the present invention.
【００５１】本発明の第２の組成物は、上記（Ａ），（
Ｂ）および（Ｄ）成分を所定割合で配合し混合して液状
重合体組成物を調製後、（Ｃ）成分であるゴムチップを
配合することにより得られる。上記（Ａ），（Ｂ）およ
び（Ｄ）成分からなる液状重合体組成物の調製方法は、
前記した本発明の第１の組成物における液状重合体組成
物の調製方法と同様に、ワンショット法またはプレポリ
マー法により行なえばよい。The second composition of the present invention comprises the above (A), (
It is obtained by blending and mixing components B) and (D) in a predetermined ratio to prepare a liquid polymer composition, and then blending the rubber chips as component (C). The method for preparing a liquid polymer composition consisting of the above components (A), (B) and (D) includes:
Similar to the method for preparing the liquid polymer composition in the first composition of the present invention described above, the one-shot method or the prepolymer method may be used.
【００５２】このようにして得られた液状重合体組成物
に、（Ｃ）ゴムチップを配合することにより、本発明の
第２のゴムチップ含有硬化性組成物が得られる。ここで
、（Ｃ）成分として用いるゴムチップは、前記した本発
明の第１の組成物における（Ｃ）成分のゴムチップと同
様である。By blending (C) rubber chips into the liquid polymer composition thus obtained, the second rubber chip-containing curable composition of the present invention can be obtained. Here, the rubber chips used as component (C) are the same as the rubber chips used as component (C) in the first composition of the present invention described above.
【００５３】バインダーとして用いる液状重合体組成物
のゴムチップへの添加量は、ゴムチップ組成物中の量が
１〜３０重量％となるようにするのが好ましい。液状重
合体組成物のゴムチップへの添加量が１重量％未満であ
ると、得られる硬化物の物性が不充分であり好ましくな
く、また３０重量％を超えると、得られる硬化体におい
てゴムチップの有する弾力性，外観を損うため好ましく
ない。また、（Ｃ）ゴムチップと共に所望に応じて歴青
物質を適宜配合することができる。歴青物質としては、
ストレートアスファルト，ブローンアスファルト，セミ
ブローンアスファルト，溶剤脱歴アスファルト等の石油
アスファルト、石油ピッチ、石炭タール、石炭ピッチな
どを用いることができ、その配合割合は（Ａ）成分であ
る水酸基含有液状ジエン系重合体および／または水酸基
含有液状イソプレン系重合体の水素化物１００重量部に
対し１０００重量部以下、好ましくは５００重量部以下
である。The amount of the liquid polymer composition used as a binder added to the rubber chips is preferably 1 to 30% by weight in the rubber chip composition. If the amount of the liquid polymer composition added to the rubber chips is less than 1% by weight, the physical properties of the resulting cured product will be unsatisfactory, and if it exceeds 30% by weight, the properties of the rubber chips will deteriorate in the resulting cured product. This is undesirable because it impairs elasticity and appearance. Moreover, a bituminous substance can be appropriately blended with (C) rubber chips as desired. As a bituminous substance,
Petroleum asphalt such as straight asphalt, blown asphalt, semi-blown asphalt, and solvent deasphalted asphalt, petroleum pitch, coal tar, coal pitch, etc. can be used, and the blending ratio is the hydroxyl group-containing liquid diene heavy duty as component (A). The amount is 1000 parts by weight or less, preferably 500 parts by weight or less, based on 100 parts by weight of the hydride of the liquid isoprene polymer containing a coalesced and/or hydroxyl group.
【００５４】本発明の第２のゴムチップ含有硬化性組成
物の調製にあたっては、上記の如くして得られた液状重
合体組成物に所定量の（Ｃ）ゴムチップを配合し、混合
装置，混練装置，撹拌装置を用いて０〜１２０℃、好ま
しくは１５〜１００℃の温度で２秒〜１０時間、好まし
くは５秒〜５時間混合すればよい。このようにして得ら
れたゴムチップ含有硬化性組成物を硬化処理することに
より、さまざまな形状の硬化物を得ることができる。通
常は、ゴムチップ含有硬化性組成物を金型あるいは種々
の形状の型枠を使用したり、コテ塗り等によって任意の
形状とすることができる。この状態で０〜１５０℃、好
ましくは１５〜１３０℃にて２０秒〜１０日間、好まし
くは７分間〜７日間硬化処理することにより硬化物とす
ることができる。得られた硬化物は、機械的強度が優れ
ている。In preparing the second rubber chip-containing curable composition of the present invention, a predetermined amount of (C) rubber chips is blended into the liquid polymer composition obtained as described above, and the mixture is mixed with a mixing device and a kneading device. , using a stirrer at a temperature of 0 to 120°C, preferably 15 to 100°C, for 2 seconds to 10 hours, preferably 5 seconds to 5 hours. By curing the rubber chip-containing curable composition thus obtained, cured products of various shapes can be obtained. Usually, the rubber chip-containing curable composition can be formed into any desired shape by using a mold or a mold of various shapes, or by coating with a trowel. A cured product can be obtained by curing in this state at 0 to 150°C, preferably 15 to 130°C for 20 seconds to 10 days, preferably 7 minutes to 7 days. The obtained cured product has excellent mechanical strength.
【００５５】[0055]
【実施例】次に、本発明を実施例により説明する。[Example] Next, the present invention will be explained with reference to an example.
【００５６】製造例１
（１）水酸基含有液状ポリイソプレンの調製１ｌのステ
ンレス製耐圧反応容器にイソプレン２００ｇ，濃度２０
％の過酸化水素水４０ｇおよびイソプロパノール１００
ｇを仕込み、温度１２０℃、反応時間２時間の条件で反
応を行った。反応中、圧力は最高８ｋｇ／ｃｍ２ Ｇに
達した。反応終了後、分液ロートに反応混合物を入れ、
６００ｇの水を添加して振とうし、次いで３時間静置し
た後、油層を分取した。この油層から溶媒，モノマー，
低沸点成分を２ｍｍＨｇ、１００℃、２時間の条件で留
去し、水酸基含有液状ポリイソプレン（収率６６重量％
）を得た。このものの数平均分子量は２２４０、水酸基
含有量は、０．９６ｍｅｑ／ｇ、粘度は６４ポイズ／３
０℃、臭素価２２０ｇ／１００ｇであった。
このときの１分子当たりの平均水酸基数は２．１５であ
る。Production Example 1 (1) Preparation of liquid polyisoprene containing hydroxyl groups 200 g of isoprene, concentration 20, was placed in a 1 liter stainless steel pressure-resistant reaction vessel.
% hydrogen peroxide solution 40g and isopropanol 100g
The reaction was carried out at a temperature of 120° C. and a reaction time of 2 hours. During the reaction, the pressure reached a maximum of 8 kg/cm2G. After the reaction is complete, put the reaction mixture into a separatory funnel,
After adding 600 g of water and shaking, the mixture was allowed to stand for 3 hours, and then the oil layer was separated. From this oil layer, solvent, monomer,
The low-boiling components were distilled off at 2 mmHg, 100°C, and for 2 hours to obtain hydroxyl group-containing liquid polyisoprene (yield: 66% by weight).
) was obtained. The number average molecular weight of this product is 2240, the hydroxyl group content is 0.96 meq/g, and the viscosity is 64 poise/3.
The temperature was 0°C and the bromine number was 220g/100g. The average number of hydroxyl groups per molecule at this time is 2.15.
【００５７】（２）水酸基含有液状ポリイソプレンの水
素化物の調製
製造例１の（１）で得た水酸基含有液状ポリイソプレン
１００ｇ，ルテニウム含量５重量％のルテニウムカーボ
ン触媒５ｇおよび溶媒としてシクロヘキサン１００ｇを
仕込み、５０ｋｇ／ｃｍ２ Ｇの水素圧下で１５０℃に
て６時間水素化反応を行った。反応終了後、０．４５μ
のメンブランフィルターを通して反応溶液から触媒を分
離除去した後、２ｍｍＨｇ、１１０℃、２時間の条件で
溶媒を留去した。その結果、水酸基含有液状ポリイソプ
レンの水素化物が得られた。このものの数平均分子量２
３１０、水酸基含有量は０．９４ｍｅｑ／ｇ、粘度は６
５０ポイズ／３０℃、臭素価１ｇ／１００ｇであった。
このときの１分子当たりの平均水酸基数は２．１７であ
る。(2) Preparation of hydride of hydroxyl group-containing liquid polyisoprene 100 g of hydroxyl group-containing liquid polyisoprene obtained in (1) of Production Example 1, 5 g of a ruthenium carbon catalyst with a ruthenium content of 5% by weight, and 100 g of cyclohexane as a solvent were charged. The hydrogenation reaction was carried out at 150° C. for 6 hours under a hydrogen pressure of 50 kg/cm 2 G. After the reaction, 0.45μ
After separating and removing the catalyst from the reaction solution through a membrane filter, the solvent was distilled off under conditions of 2 mmHg, 110° C., and 2 hours. As a result, a hydride of liquid polyisoprene containing hydroxyl groups was obtained. Number average molecular weight of this substance 2
310, hydroxyl group content is 0.94 meq/g, viscosity is 6
It was 50 poise/30°C, and the bromine number was 1 g/100 g. The average number of hydroxyl groups per molecule at this time was 2.17.
【００５８】製造例２
（１）水酸基含有液状ポリイソプレンの調製１ｌのステ
ンレス製耐圧反応容器にイソプレン２００ｇ，濃度３０
％の過酸化水素水１００ｇおよびイソプロパノール３０
０ｇを仕込み、温度１１５℃、反応時間２．５時間の条
件で反応を行った。反応中、圧力は最高７ｋｇ／ｃｍ２
Ｇに達した。反応終了後、分液ロートに反応混合物を入
れ、６００ｇの水を添加して振とうし、次いで３時間静
置した後、油層を分取した。この油層から溶媒，モノマ
ー，低沸点成分を２ｍｍＨｇ、１００℃、２時間の条件
で留去し、水酸基含有液状ポリイソプレン（収率７１重
量％）を得た。このものの数平均分子量は１３８０、水
酸基含有量は１．５５ｍｅｑ／ｇ、粘度は４６ポイズ／
３０℃であった。このときの１分子当たりの平均水酸基
数は２．１４である。Production Example 2 (1) Preparation of hydroxyl group-containing liquid polyisoprene 200 g of isoprene, concentration 30, was placed in a 1 liter stainless steel pressure-resistant reaction vessel.
% hydrogen peroxide solution 100g and isopropanol 30g
0 g was charged, and the reaction was carried out at a temperature of 115° C. and a reaction time of 2.5 hours. During the reaction, the maximum pressure is 7 kg/cm2
It reached G. After the reaction was completed, the reaction mixture was placed in a separatory funnel, 600 g of water was added thereto, and the mixture was shaken. After being allowed to stand for 3 hours, the oil layer was separated. The solvent, monomer, and low-boiling components were distilled off from this oil layer under conditions of 2 mmHg, 100° C., and 2 hours to obtain hydroxyl group-containing liquid polyisoprene (yield: 71% by weight). The number average molecular weight of this product is 1380, the hydroxyl group content is 1.55 meq/g, and the viscosity is 46 poise/
The temperature was 30°C. The average number of hydroxyl groups per molecule at this time was 2.14.
【００５９】（２）水酸基含有液状ポリイソプレンの水
素化物の調製
製造例２の（１）で得た水酸基含有液状ポリイソプレン
１００ｇ，ルテニウム含量５重量％のルテニウムカーボ
ン触媒５ｇおよび溶媒としてシクロヘキサン１００ｇを
仕込み、５０ｋｇ／ｃｍ２ Ｇの水素圧下で１５０℃に
て６時間水素化反応を行った。反応終了後、０．４５μ
のメンブランフィルターを通して反応溶液から触媒を分
離除去した後、２ｍｍＨｇ、１１０℃、２時間の条件で
溶媒を留去した。その結果、水酸基含有液状ポリイソプ
レンの水素化物が得られた。このものの数平均分子量１
４２０、水酸基含有量は１．５４ｍｅｑ／ｇ、粘度は２
９８ポイズ／３０℃、臭素価１ｇ／１００ｇであった。
このときの１分子当たりの平均水酸基数は２．１９であ
る。(2) Preparation of hydride of hydroxyl group-containing liquid polyisoprene 100 g of hydroxyl group-containing liquid polyisoprene obtained in (1) of Production Example 2, 5 g of a ruthenium carbon catalyst with a ruthenium content of 5% by weight, and 100 g of cyclohexane as a solvent were charged. The hydrogenation reaction was carried out at 150° C. for 6 hours under a hydrogen pressure of 50 kg/cm 2 G. After the reaction, 0.45μ
After separating and removing the catalyst from the reaction solution through a membrane filter, the solvent was distilled off under conditions of 2 mmHg, 110° C., and 2 hours. As a result, a hydride of liquid polyisoprene containing hydroxyl groups was obtained. The number average molecular weight of this substance is 1
420, hydroxyl group content is 1.54 meq/g, viscosity is 2
It was 98 poise/30°C, and the bromine number was 1 g/100 g. The average number of hydroxyl groups per molecule at this time was 2.19.
【００６０】実施例１〜３
表１に示した所定量の水酸基含有液状イソプレンの水素
化物を反応容器に採取し、これに所定量のポリイソシア
ネート化合物を配合し、２５℃で５分間かく拌して液状
重合体組成物を得た。得られた組成物１００重量部に対
し、粒径２ｍｍのＳＢＲゴムチップ１０００重量部を配
合し、２５℃にて１０分間かく拌してゴムチップ含有硬
化性組成物を得た。得られた組成物を１０×１５０×３
００ｍｍの金型に採取し、１２０℃にて２００ｋｇｆ／
ｃｍ２ Ｇの加圧下で１５分間プレスして硬化体を得た
。
得られた硬化体を、キセノンウェザーメーター（スガ試
験機製）にて所定時間キセノン照射（試験条件：ブラッ
クパネル温度６０℃，湿度６０％，１２０分／１サイク
ル中１８分間降雨）後、耐黄変性（キセノン照射５００
時間），耐クラック性（キセノン照射２０００時間）を
評価した。耐候性（キセノン照射１０００時間）はＪＩ
Ｓ Ｋ−６３０１に準拠した引張試験（下式にて引張
り強さ低下率（％）を算出）にて評価した。結果を表１
に示す。Examples 1 to 3 A predetermined amount of hydroxyl group-containing liquid isoprene hydride shown in Table 1 was collected in a reaction vessel, and a predetermined amount of a polyisocyanate compound was added thereto, followed by stirring at 25° C. for 5 minutes. A liquid polymer composition was obtained. 1000 parts by weight of SBR rubber chips having a particle size of 2 mm were blended with 100 parts by weight of the obtained composition, and the mixture was stirred at 25° C. for 10 minutes to obtain a curable composition containing rubber chips. The resulting composition was 10 x 150 x 3
Sampled in a 00mm mold and heated to 200kgf/at 120℃.
A cured product was obtained by pressing for 15 minutes under a pressure of cm 2 G. The obtained cured product was irradiated with xenon for a predetermined period of time using a xenon weather meter (manufactured by Suga Test Instruments) (test conditions: black panel temperature 60°C, humidity 60%, 120 minutes/18 minutes of rain in one cycle), and then yellowing resistance was determined. (Xenon irradiation 500
time) and crack resistance (xenon irradiation for 2000 hours). Weather resistance (1000 hours of xenon irradiation) is JI
It was evaluated by a tensile test based on SK-6301 (tensile strength reduction rate (%) was calculated using the formula below). Table 1 shows the results.
Shown below.
【００６１】[0061]
【数２】[Math 2]
【００６２】実施例４および５
表１に示した所定量の水酸基含有液状イソプレンの水素
化物を反応容器に採取し、８０℃に昇温した後、１時間
真空脱水を実施した。次いで、徐々に２５℃まで降温し
、所定量のポリイソシアネート化合物を配合し、８０℃
にて４時間反応させて分子鎖末端にイソシアネート基を
有する液状重合体組成物を得た。得られた組成物１００
重量部に対し、粒径２ｍｍのＳＢＲゴムチップ１０００
重量部を配合し、２５℃にて１０分間かく拌してゴムチ
ップ含有硬化性組成物を得た。得られた組成物より実施
例１と同様の方法で硬化体を得、その物性を評価した。
結果を表１に示す。Examples 4 and 5 A predetermined amount of hydroxyl group-containing liquid isoprene hydride shown in Table 1 was collected in a reaction vessel, heated to 80° C., and then subjected to vacuum dehydration for 1 hour. Next, the temperature was gradually lowered to 25°C, a predetermined amount of polyisocyanate compound was added, and the temperature was lowered to 80°C.
The mixture was reacted for 4 hours to obtain a liquid polymer composition having an isocyanate group at the end of the molecular chain. Obtained composition 100
1000 SBR rubber chips with a particle size of 2 mm per weight part
Parts by weight were blended and stirred at 25° C. for 10 minutes to obtain a curable composition containing rubber chips. A cured product was obtained from the obtained composition in the same manner as in Example 1, and its physical properties were evaluated. The results are shown in Table 1.
【００６３】[0063]
【表１】[Table 1]
【００６４】＊１ 水添ジフェニルメタンジイソシア
ネート，ディスモジュールＷ，住友バイエルウレタン（
株）製，ＮＣＯ含量３１．８重量％
＊２ 純ジフェニルメタンジイソシアネート，日本ポ
リウレタン（株）製，ＮＣＯ含量３３．６重量％＊３
目視により観察
＊４ サンプルを折り曲げて、目視で観察＊５ Ｊ
ＩＳ Ｋ６３０１に準拠*1 Hydrogenated diphenylmethane diisocyanate, Dismodur W, Sumitomo Bayer urethane (
Co., Ltd., NCO content 31.8% by weight *2 Pure diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Co., Ltd., NCO content 33.6% by weight *3
Visually observe*4 Fold the sample and visually observe*5 J
Compliant with IS K6301
【００６５】比較例１〜３
実施例１において、水酸基含有液状イソプレンの水素化
物の代わりに水酸基含有液状ポリブタジエンＲ−４５Ｈ
Ｔ（出光アトケム（株）製，ＯＨ含量０．８４ｍｅｑ／
ｇ）を用いたこと、およびその他の原料を表２に示す所
定量用いたこと以外は同様にしてゴムチップ含有硬化性
組成物を得、さらに硬化体を得て、実施例１と同様にし
てその物性を評価した。結果を表２に示す。Comparative Examples 1 to 3 In Example 1, hydroxyl group-containing liquid polybutadiene R-45H was used instead of the hydroxyl group-containing liquid isoprene hydride.
T (manufactured by Idemitsu Atochem Co., Ltd., OH content 0.84 meq/
A rubber chip-containing curable composition was obtained in the same manner except that g) and other raw materials were used in the predetermined amounts shown in Table 2, and a cured product was obtained. Physical properties were evaluated. The results are shown in Table 2.
【００６６】比較例４
液状重合体組成物としてＭＣ−５０（出光アトケム（株
）製，分子鎖末端にイソシアネート基を有する液状ジエ
ン系重合体，ＮＣＯ含量５．０重量％）１００重量部に
対し粒径２ｍｍのＳＢＲゴムチップ１０００重量部配合
し、２５℃にて１０分間かく拌混合してゴムチップ含有
硬化性組成物を得た。得られた組成物を実施例１と同様
の方法より硬化体とし、その物性を評価した。結果を表
２に示す。Comparative Example 4 As a liquid polymer composition, 100 parts by weight of MC-50 (manufactured by Idemitsu Atochem Co., Ltd., liquid diene polymer having an isocyanate group at the end of the molecular chain, NCO content 5.0% by weight) was used. 1,000 parts by weight of SBR rubber chips with a particle size of 2 mm were blended and stirred and mixed at 25° C. for 10 minutes to obtain a curable composition containing rubber chips. The obtained composition was made into a cured product in the same manner as in Example 1, and its physical properties were evaluated. The results are shown in Table 2.
【００６７】[0067]
【表２】[Table 2]
【００６８】実施例６，７および参考例１，２表３に示
した所定量の水酸基含有液状イソプレンの水素化物を採
取し、これにゴムチップを除く原料を所定量配合し、２
５℃で１分間十分にかく拌した。これに、所定量のゴム
チップを添加し、混合機を用いて２５℃で２分間よく混
合してゴムチップ含有硬化性組成物を得た。得られた組
成物を３００×１５０×１０ｍｍの金型に流し込み、１
２０℃にて１８０ｋｇｆ／ｃｍ２ Ｇの加圧下で１時間
プレスして硬化体を得た。得られた硬化体の物性をＪＩ
Ｓ Ｋ６３０１に準拠して評価した。結果を表３に示
す。Examples 6 and 7 and Reference Examples 1 and 2 A predetermined amount of hydroxyl group-containing liquid isoprene hydride shown in Table 3 was collected, and a predetermined amount of raw materials excluding rubber chips was blended with it.
The mixture was thoroughly stirred at 5°C for 1 minute. A predetermined amount of rubber chips was added to this, and the mixture was thoroughly mixed using a mixer at 25° C. for 2 minutes to obtain a curable composition containing rubber chips. The obtained composition was poured into a mold of 300 x 150 x 10 mm, and 1
A cured product was obtained by pressing at 20° C. for 1 hour under a pressure of 180 kgf/cm 2 G. The physical properties of the obtained cured product were determined by JI
Evaluation was made in accordance with SK6301. The results are shown in Table 3.
【００６９】[0069]
【表３】[Table 3]
【００７０】実施例８，９および比較例５表４に示した
所定量の水酸基含有液状ジエン系重合体ＭＣ−５０（水
酸基含有液状ジエン系重合体のＭＤＩプレポリマー，出
光アトケム（株）製，イソシアネート含量５．０重量％
）を採取し、これにゴムチップを除く原料を所定量配合
し、２５℃で２分間十分にかく拌した。これに所定量の
ゴムチップを添加し、混合機を用いて１５分間よく混合
してゴムチップ含有硬化性組成物を得た。
得られた組成物を３００×１５０×１０ｍｍの金型に流
し込み、３０℃にて１週間硬化させて硬化体を得た。得
られた硬化体の物性をＪＩＳ Ｋ６３０１に準拠して
評価した。結果を表４に示す。Examples 8, 9 and Comparative Example 5 A predetermined amount of hydroxyl group-containing liquid diene polymer MC-50 (MDI prepolymer of hydroxyl group-containing liquid diene polymer, manufactured by Idemitsu Atochem Co., Ltd.) shown in Table 4 was used. Isocyanate content 5.0% by weight
), and a predetermined amount of raw materials except rubber chips were blended therewith, and the mixture was thoroughly stirred at 25° C. for 2 minutes. A predetermined amount of rubber chips was added thereto, and mixed well for 15 minutes using a mixer to obtain a curable composition containing rubber chips. The obtained composition was poured into a mold of 300 x 150 x 10 mm and cured at 30°C for one week to obtain a cured product. The physical properties of the obtained cured product were evaluated in accordance with JIS K6301. The results are shown in Table 4.
【００７１】[0071]
【表４】[Table 4]
【００７２】＊１ 液状ジフェニルメタンジイソシア
ネート（カルボジイミド化ジフェニルメタンジイソシア
ネート），日本ポリウレタン（株）製，ＮＣＯ含量２９
．１重量％
＊２ メチルエチルケトンパーオキサイド，カヤメッ
クＭ，化薬アクゾ（株）製
＊３ カヤクミル−Ｄ，化薬アクゾ（株）製＊４
ナフテックスコバルト６％Ｔ（日本化学産業（株）製）
＊５ 半井化学薬品（株）製
＊６ ＳＢＲゴムチップ，平均粒径３ｍｍ，チップ状
*1 Liquid diphenylmethane diisocyanate (carbodiimidized diphenylmethane diisocyanate), manufactured by Nippon Polyurethane Co., Ltd., NCO content 29
．． 1% by weight *2 Methyl ethyl ketone peroxide, Kayamec M, manufactured by Kayaku Akzo Co., Ltd. *3 Kayacumyl-D, manufactured by Kayaku Akzo Co., Ltd. *4
Naftex cobalt 6% T (manufactured by Nihon Kagaku Sangyo Co., Ltd.) *5 Manufactured by Hani Chemical Co., Ltd. *6 SBR rubber chips, average particle size 3 mm, chip shape
【００７３】[0073]
【発明の効果】本発明のゴムチップ含有硬化性組成物よ
り得られる硬化体は、比較的高温，高湿下において光の
照射を受けても変色することがない上に、機械的強度が
優れているので亀裂を生ずることがない。従って、本発
明のゴムチップ含有硬化性組成物は、道路舗装材，床材
，緩衝材等の材料として有用である。[Effects of the Invention] The cured product obtained from the rubber chip-containing curable composition of the present invention does not discolor even when exposed to light at relatively high temperatures and high humidity, and has excellent mechanical strength. Since there are no cracks, no cracks will occur. Therefore, the rubber chip-containing curable composition of the present invention is useful as a material for road paving materials, flooring materials, cushioning materials, and the like.
Claims (2)
合体の水素化物，（Ｂ）ポリイソシアネート化合物およ
び（Ｃ）ゴムチップからなるゴムチップ含有硬化性組成
物。1. A curable composition containing rubber chips, comprising (A) a hydride of a liquid isoprene-based polymer containing hydroxyl groups, (B) a polyisocyanate compound, and (C) rubber chips.
および／または水酸基含有液状イソプレン系重合体の水
素化物，（Ｂ）ポリイソシアネート化合物，（Ｃ）ゴム
チップおよび（Ｄ）有機過酸化物からなるゴムチップ含
有硬化性組成物。Claim 2: Consisting of (A) a hydride of a hydroxyl group-containing liquid diene polymer and/or a hydroxyl group-containing liquid isoprene polymer, (B) a polyisocyanate compound, (C) a rubber chip, and (D) an organic peroxide. Curable composition containing rubber chips.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3027637A JP3046367B2 (en) | 1991-01-30 | 1991-01-30 | Rubber chip-containing curable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3027637A JP3046367B2 (en) | 1991-01-30 | 1991-01-30 | Rubber chip-containing curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04246462A true JPH04246462A (en) | 1992-09-02 |
| JP3046367B2 JP3046367B2 (en) | 2000-05-29 |
Family
ID=12226460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3027637A Expired - Lifetime JP3046367B2 (en) | 1991-01-30 | 1991-01-30 | Rubber chip-containing curable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3046367B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018051740A1 (en) * | 2016-09-15 | 2018-03-22 | 日清紡ホールディングス株式会社 | Resin composition, heat-conductive flexible sheet using same, and heat dissipation structure |
-
1991
- 1991-01-30 JP JP3027637A patent/JP3046367B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018051740A1 (en) * | 2016-09-15 | 2018-03-22 | 日清紡ホールディングス株式会社 | Resin composition, heat-conductive flexible sheet using same, and heat dissipation structure |
| US11225548B2 (en) | 2016-09-15 | 2022-01-18 | Nisshinbo Holdings Inc. | Resin composition, heat-conductive flexible sheet using same, and heat dissipation structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3046367B2 (en) | 2000-05-29 |
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