CN115975584A - Urethane adhesive composition, vulcanized rubber bonding method, and conveyor belt - Google Patents
Urethane adhesive composition, vulcanized rubber bonding method, and conveyor belt Download PDFInfo
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- CN115975584A CN115975584A CN202211252784.8A CN202211252784A CN115975584A CN 115975584 A CN115975584 A CN 115975584A CN 202211252784 A CN202211252784 A CN 202211252784A CN 115975584 A CN115975584 A CN 115975584A
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- Prior art keywords
- polyol
- adhesive composition
- present
- urethane adhesive
- component
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 124
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 85
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920005862 polyol Polymers 0.000 claims abstract description 237
- 150000003077 polyols Chemical class 0.000 claims abstract description 226
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 102
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 41
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 41
- -1 polyol compound Chemical class 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 11
- 150000004678 hydrides Chemical class 0.000 claims abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 8
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims description 92
- 239000005060 rubber Substances 0.000 claims description 92
- 239000005062 Polybutadiene Substances 0.000 claims description 60
- 229920002857 polybutadiene Polymers 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 20
- 229920000515 polycarbonate Polymers 0.000 claims description 19
- 239000004417 polycarbonate Substances 0.000 claims description 19
- 229920001195 polyisoprene Polymers 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 46
- 238000004073 vulcanization Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 21
- 229920005906 polyester polyol Polymers 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 16
- 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 15
- 239000002253 acid Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920001084 poly(chloroprene) Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000006238 High Abrasion Furnace Substances 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 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 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-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
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000006237 Intermediate SAF Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000006236 Super Abrasion Furnace Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- IHYOEGZUFPLXIS-UHFFFAOYSA-N 3,3-diethylpentane-1,5-diol Chemical compound OCCC(CC)(CC)CCO IHYOEGZUFPLXIS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229920013701 VORANOL™ Polymers 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000004927 clay Substances 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000004927 fusion Effects 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000012966 insertion method Methods 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The purpose of the present invention is to provide an adhesive composition having excellent adhesion to a vulcanized rubber containing BR at a high proportion, a method for adhering a vulcanized rubber using the adhesive composition, and a conveyor belt. The solution is a urethane adhesive composition, which contains a polyol component and a polyisocyanate component, wherein the polyol component comprises the following polyol 1 and polyol 2, and the urethane adhesive composition is used for bonding vulcanized rubber. Polyol 1: is a polyhydric alcohol compound having a glass transition temperature of-30 to +60 ℃ and a hydroxyl value of 1 to 20KOHmg/g and having an ester bond, a polyhydric alcohol 2: the polyol compound has a hydroxyl value of more than 20KOHmg/g and 500KOHmg/g or less and has a skeleton comprising at least 1 selected from the group consisting of polymers of isoprene and/or butadiene, hydrides thereof, polyolefins, ester bonds, and carbonate bonds.
Description
Technical Field
The invention relates to a urethane adhesive composition, a vulcanized rubber bonding method and a conveyor belt.
Background
Conventionally, in order to make a belt endless (for example, elongate and/or endless) such as a conveyor belt, rubber and rubber are joined by joining vulcanized rubber or unvulcanized rubber. In the above joining method, generally, vulcanization joining in which unvulcanized rubbers are vulcanized to each other and joined and natural vulcanization bonding in which vulcanized rubbers are bonded to each other with an adhesive are used.
For vulcanization joining, equipment for vulcanizing unvulcanized rubbers with each other is required. In particular, when a large product such as a conveyor is endless, it is necessary to make the above-described apparatus large.
On the other hand, natural vulcanization bonding has an advantage that such a large-scale facility is not required. As an adhesive that can be used for the natural vulcanization adhesive (the adhesive is also referred to as a natural vulcanization adhesive), for example, patent documents 1 and 2 are known.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6733436
Patent document 2: japanese patent laid-open No. 2021-031562
Disclosure of Invention
Problems to be solved by the invention
Among them, the present inventors have made reference to patent document 1 to prepare an adhesive for natural vulcanization and evaluated the adhesive, and as a result, they have found that: an adhesive containing chloroprene rubber and polyisocyanate may have low adhesion to a vulcanized rubber of a rubber composition containing Butadiene Rubber (BR) in an amount exceeding 30 mass% in the rubber component (comparative example 6).
Further, as a result of preparing an adhesive composition by referring to patent document 2 and evaluating it, it was clarified that: the adhesive composition containing the polyisocyanate compound and the polyester sometimes has low adhesion to a vulcanized rubber containing Butadiene Rubber (BR) in an amount exceeding 30% by mass in the rubber component (comparative examples 3 to 5 and 8).
Accordingly, an object of the present invention is to provide an adhesive composition having excellent adhesion to a vulcanized rubber containing BR in a high proportion. Further, it is an object to provide a method for bonding vulcanized rubber using the adhesive composition and a conveyor belt manufactured using the adhesive composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a desired effect can be obtained by containing a polyol component and a polyisocyanate component, the polyol component containing a polyol 1 and a polyol 2 having a hydroxyl value or the like in a specific range, and have completed the present invention.
The present invention solves the above problems based on the above findings and the like, and specifically, with the following configurations.
[1]
A urethane adhesive composition comprising a polyol component and a polyisocyanate component, wherein the polyol component comprises the following polyol 1 and polyol 2, and the urethane adhesive composition is used for bonding a vulcanized rubber.
Polyol 1: a polyhydric alcohol compound having a glass transition temperature of-30 to +60 ℃, a hydroxyl value of 1 to 20KOHmg/g and an ester bond
Polyol 2: a polyol compound having a hydroxyl value of more than 20KOHmg/g and not more than 500KOHmg/g and having a skeleton comprising at least 1 selected from the group consisting of polymers of isoprene and/or butadiene, hydrides thereof, polyolefins, ester bonds, and carbonate bonds
[2]
The urethane adhesive composition according to item [1], wherein the proportion of the hydroxyl group of the polyol 1 in all the hydroxyl groups of the polyol component is 10 to 30 mol%.
[3]
The urethane adhesive composition according to item [1] or [2], wherein the proportion of the hydroxyl group of the polyol 2 in all the hydroxyl groups of the polyol component is 40 to 70 mol%.
[4]
The urethane adhesive composition according to any one of [1] to [3], wherein the polyol component further contains a polyol 3 having a hydroxyl value of more than 500KOHmg/g and not more than 1300KOHmg/g.
[5]
The urethane adhesive composition according to [4], wherein the polyol 3 has a hydroxyl value of 1000 to 1300KOHmg/g.
[6]
The urethane adhesive composition according to [4] or [5], wherein the proportion of the hydroxyl group of the polyol 3 in all the hydroxyl groups of the polyol component is 10 to 40 mol%.
[7]
The urethane adhesive composition according to any one of [1] to [6], wherein a molar ratio of all isocyanate groups of the polyisocyanate component to all hydroxyl groups of the polyol component is 1.0 to 3.0.
[8]
The urethane adhesive composition according to any one of [1] to [7], wherein the glass transition temperature of the polyol 1 is 0 to +50 ℃.
[9]
The urethane adhesive composition according to any one of [1] to [8], wherein the polyol 1 has a number average molecular weight of 6,000 to 23,000.
[10]
The urethane adhesive composition according to any one of [1] to [9], wherein the polyol 2 has at least polyisoprene, polybutadiene, a hydride thereof, or polycarbonate as a skeleton.
[11]
The urethane adhesive composition according to any one of [1] to [10], further comprising a solvent, wherein the solvent contains at least an acetate-based solvent.
[12]
A method for bonding vulcanized rubbers, wherein the vulcanized rubbers are bonded to each other using the urethane adhesive composition according to any one of [1] to [11 ].
[13]
A conveyor belt, wherein the ends of the belt are bonded to each other using the urethane adhesive composition according to any one of [1] to [11 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The urethane adhesive composition of the present invention has excellent adhesion to a vulcanized rubber containing BR at a high ratio. Further, a vulcanized rubber bonding method using the urethane adhesive composition of the present invention and a conveyor belt manufactured using the urethane adhesive composition of the present invention can be provided.
Drawings
Fig. 1 is a schematic view showing an example of the bonding form of the conveyor belt of the present invention.
Detailed Description
The present invention will be described in detail below.
In the present specification, the numerical range represented by the term "to" means a range including the numerical values recited before and after the term "to".
In the present specification, unless otherwise specified, each component may be used alone or in combination of 2 or more kinds of the substances corresponding to the component. When the component contains 2 or more substances, the content of the component refers to the total content of the 2 or more substances.
In this specification, the joining of vulcanized rubbers to each other by an adhesive may be simply referred to as "adhesion".
In this specification, the adhesiveness to a vulcanized rubber containing BR in a high proportion is sometimes simply referred to as "adhesiveness". Further, the more excellent adhesion to a vulcanized rubber containing BR at a high ratio may be referred to as more excellent effect of the present invention.
[ urethane adhesive composition ]
The urethane adhesive composition of the present invention (the adhesive composition of the present invention) is the following urethane adhesive composition:
the adhesive composition contains a polyol component and a polyisocyanate component, wherein the polyol component contains the following polyol 1 and polyol 2, and the urethane adhesive composition is used for bonding vulcanized rubber.
Polyol 1: a polyhydric alcohol compound having a glass transition temperature of-30 to +60 ℃, a hydroxyl value of 1 to 20KOHmg/g and an ester bond
Polyol 2: a polyol compound having a hydroxyl value of more than 20KOHmg/g and not more than 500KOHmg/g and a skeleton comprising at least 1 selected from the group consisting of polymers of isoprene and/or butadiene, hydrides thereof, polyolefins, ester bonds, and carbonate bonds
It is considered that the adhesive composition of the present invention has such a structure, and therefore, the desired effects can be obtained. The reason for this is not clear, but is presumed to be as follows.
It is considered that when the adhesive composition of the present invention is applied to a vulcanized rubber containing BR at a high proportion, polyol 2 having a hydroxyl value of more than 20KOHmg/g and not more than 500KOHmg/g migrates and/or invades into the surface of the vulcanized rubber, and in the above state, the polyol component and the polyisocyanate component react with each other, so that a cured product (adhesive) exerts a crosslinking effect and an anchoring effect, and as a result, the vulcanized rubbers are strongly bonded to each other.
The components contained in the adhesive composition of the present invention will be described in detail below.
[ polyol component ]
The polyol component contained in the adhesive composition of the present invention is a compound having a plurality of hydroxyl groups. The number of hydroxyl groups in the polyol component may be 2 or more, preferably 2 to 4, on average per 1 molecule.
In the present invention, the polyol component includes polyol 1 and polyol 2. Thus, the adhesive composition of the present invention has excellent adhesiveness.
[ polyol 1]
In the present invention, the polyol 1 contained in the polyol component is a polyol compound having a glass transition temperature of-30 to +60 ℃ and a hydroxyl value of 1 to 20KOHmg/g and having an ester bond.
[ glass transition temperature of polyol 1]
In the present invention, the polyol 1 has a glass transition temperature (Tg) of-30 to +60 ℃ (-30 ℃ to +60 ℃). When the Tg of the polyol 1 is in the above range, the adhesive composition of the present invention has excellent adhesiveness.
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, the Tg of the polyol 1 is preferably 0 to +60 ℃, more preferably +10 to +50 ℃, and even more preferably +15 to +50 ℃.
From the viewpoint of further excellent effects and large initial strength of the present invention, the Tg of the polyol 1 is preferably 0 to +60 ℃, more preferably +10 to +50 ℃, and even more preferably +15 to +40 ℃.
In the present invention, the glass transition temperature of each polyol component can be measured by a differential scanning calorimeter. For example, the measurement can be performed at a temperature rise rate of 20 ℃/min, and the glass transition temperature can be calculated from the result by the midpoint method.
[ hydroxyl value of polyol 1]
In the present invention, the hydroxyl value (OH value) of polyol 1 is 1 to 20KOHmg/g. When the OH value of the polyol 1 is in the above range, the adhesive composition of the present invention has excellent adhesiveness.
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, the OH value of the polyol 1 is preferably 5 to 20KOHmg/g, more preferably 10 to 20KOHmg/g.
In the present invention, the hydroxyl value of each polyol component may be determined in accordance with JIS K1557-1: 2007.
(ratio of hydroxyl group in polyol 1)
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, the proportion of hydroxyl groups in the polyol 1 among all hydroxyl groups in the polyol component is preferably 10 to 30 mol%, more preferably 10.0 to 20.0 mol%.
The above-mentioned ratio range may be the same in the case where the polyol component further contains a polyol 3 described later.
(acid value of polyol 1)
The acid value of the polyol 1 is preferably 1 to 20KOHmg/g, more preferably 2 to 10KOHmg/g, from the viewpoint of more excellent effects of the present invention and excellent initial strength expression.
In the present invention, the acid value of each polyol component may be determined in accordance with JIS K0070: 1992.
[ ester bond of polyol 1]
In the present invention, the polyol 1 has an ester bond in addition to a plurality of hydroxyl groups. Since the polyol 1 has an ester bond, the adhesive composition of the present invention has excellent adhesion.
From the viewpoint of the excellent effect and the excellent initial strength expression of the present invention, the polyol 1 preferably has an ester bond in the skeleton of the polyol 1, and more preferably has a polyester in the skeleton.
(examples of polyol 1)
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, the polyol 1 preferably contains a polyester polyol (a compound having a polyester polymer as a skeleton and having a plurality of hydroxyl groups).
(number average molecular weight of polyol 1)
From the viewpoint of further improving the effect of the present invention and of excellent initial strength expression, the number average molecular weight of the polyol 1 is preferably 6,000 to 23,000.
In the present invention, when each polyol component is a polymer (for example, a polyester polyol as the polyol 1), the number average molecular weight of each polyol component may be a polystyrene equivalent value obtained by gel permeation chromatography using tetrahydrofuran as a solvent.
[ polyol 2]
In the present invention, the polyol 2 contained in the polyol component is a polyol compound having a hydroxyl value of more than 20KOHmg and not more than 500KOHmg, and having a skeleton comprising at least 1 selected from the group consisting of polymers of isoprene and/or butadiene, hydrides thereof, polyolefins, ester bonds, and carbonate bonds.
[ hydroxyl value of polyol 2]
In the present invention, the hydroxyl value (OH value) of polyol 2 is more than 20KOHmg/g and 500KOHmg/g or less. When the OH value of the polyol 2 is in the above range, the adhesive composition of the present invention has excellent adhesiveness.
From the viewpoint of further improving the effect of the present invention and of excellent initial strength expression, the OH number of the polyol 2 is preferably from 21 to 400KOHmg/g, more preferably from 30 to 300KOHmg/g, and still more preferably from 45 to 225KOHmg/g.
In the case where the polyol 2 contains a polyol having a polyester skeleton (polyester polyol), the OH value of the polyester polyol as the polyol 2 is preferably 21 to 200KOHmg, more preferably 21 to 100KOHmg, from the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression.
When the polyol 2 contains a polyol having a polybutadiene skeleton (polybutadiene polyol), the polybutadiene polyol preferably has an OH value of 30 to 200KOHmg/g, more preferably 35 to 90KOHmg/g, from the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression.
When the polyol 2 contains a polyol having a polycarbonate skeleton (polycarbonate polyol), the OH value of the polycarbonate polyol is preferably from 30 to 300KOHmg, and more preferably from 100 to 225KOHmg, from the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression.
(ratio of hydroxyl groups of polyol 2)
From the viewpoint of further improving the effect of the present invention and excellent initial strength expression, the proportion of the hydroxyl groups of the polyol 2 in all the hydroxyl groups of the polyol component is preferably 10.0 to 70.0 mol%.
The proportion of the hydroxyl groups of the polyol 2 may be the same when the polyol component further contains a polyol 3 described later.
[ skeleton of polyol 2]
In the present invention, the polyol 2 has at least 1 selected from among polymers of isoprene and/or butadiene, hydrides thereof, polyolefins, ester bonds, and carbonate bonds as a skeleton in addition to a plurality of hydroxyl groups. The adhesive composition of the present invention has excellent adhesiveness because the polyol 2 has the above structure in the skeleton.
In the case where the polyol 2 has an ester bond in the skeleton, the skeleton of the polyol 2 preferably has a polyester. Examples of the polyol 2 include polyester polyols (compounds having a polyester polymer as a skeleton and having a plurality of hydroxyl groups).
In the case where the polyol 2 has a carbonate bond in the skeleton, the skeleton preferably has a polycarbonate. Examples of the polyol 2 include polycarbonate polyols (compounds having a polycarbonate polymer as a skeleton and having a plurality of hydroxyl groups).
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, the polyol 2 preferably has at least polyisoprene, polybutadiene, a hydride thereof, or polycarbonate as a skeleton, and more preferably at least polybutadiene, a hydride thereof, or polycarbonate.
(viscosity of polyol 2)
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, the viscosity of polyol 2 (e.g., polybutadiene polyol) at 30 ℃ is preferably 6.0Pa · s or less.
From the viewpoint of the excellent effect of the present invention and the excellent initial strength expression, the viscosity of polyol 2 (e.g., polyisoprene polyol) at 75 ℃ is preferably 1000mPa · s or less.
(examples of polyol 2)
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, polyol 2 preferably contains at least 1 selected from the group consisting of polyisoprene polyol, polybutadiene polyol, hydride polyol thereof, and polycarbonate polyol, and more preferably contains at least 1 selected from the group consisting of polybutadiene polyol, hydride polyol thereof, and polycarbonate polyol.
(number average molecular weight of polyol 2)
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, the number average molecular weight of the polyol 2 is preferably 500 to 5,000, more preferably 500 to 3,000.
(polyol 3)
From the viewpoint of further improving the effects of the present invention and of excellent initial strength expression, the polyol component preferably further contains polyol 3 having a hydroxyl value of more than 500KOHmg/g and 1300KOHmg/g or less.
For the same reason as described above, the hydroxyl value of the polyol 3 is more preferably 1000 to 1300KOHmg/g.
(proportion of hydroxyl group in polyol 3)
In the case where the polyol component further contains polyol 3, the proportion of the hydroxyl groups of polyol 3 among all the hydroxyl groups of the polyol component is preferably 10 to 70 mol%, more preferably 20 to 65 mol%, from the viewpoint of the more excellent effect of the present invention and the excellent expression of the initial strength.
(ratio of hydroxyl groups contained in polyols 2 and 3 when polyol 3 is further contained in the polyol component)
In the case where the polyol component further contains the polyol 3 and the polycarbonate polyol is contained as the polyol 2, the proportion of the hydroxyl groups of the polyol 2 (containing the polycarbonate polyol) among all the hydroxyl groups of the polyol component is preferably 10.0 to 50.0 mol%, more preferably 20.0 to 40.0 mol%, from the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression.
In the above case, from the viewpoint of the more excellent effect of the present invention and the excellent expression of the initial strength, the proportion of the hydroxyl groups of the polyol 3 among all the hydroxyl groups of the polyol component is preferably 20.0 to 70.0 mol%, more preferably 40.0 to 65.0 mol%.
(Structure of polyol 3)
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, it is preferable that the polyol 3 be a low-molecular-weight compound (monomer) having a plurality of hydroxyl groups.
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, in the polyol 3, a plurality of hydroxyl groups are preferably bonded to a hydrocarbon group, and more preferably bonded to a hydrocarbon group composed of only carbon atoms and hydrogen atoms.
The hydrocarbon group preferably has 2 to 15 carbon atoms, more preferably 3 to 5 carbon atoms, from the viewpoint of further improving the effect of the present invention and the initial strength expression.
The hydrocarbon group is preferably a linear or branched alkyl group from the viewpoint of further improving the effect of the present invention and excellent initial strength expression.
Examples of the polyhydric alcohol 3 include butanediol, diethyl-1,5-pentanediol, butylethylpropanediol, and nonanediol.
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, the polyol 3 preferably contains butanediol, and more preferably 1,4-butanediol.
(molecular weight of polyol 3)
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, the molecular weight of the polyol 3 is preferably less than 500.
In the present invention, when the polyol component has a low molecular weight (monomer), the molecular weight of the polyol component can be measured by a usual method used for measuring the molecular weight of a low-molecular compound.
[ polyisocyanate ]
The adhesive composition of the present invention contains a polyisocyanate component. The polyisocyanate component is a compound having a plurality of isocyanate groups.
Examples of the polyisocyanate component include aromatic polyisocyanates such as Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-Naphthalene Diisocyanate (NDI), and triphenylmethane triisocyanate;
1,6 Hexamethylene Diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), trans cyclohexane 1,4 diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H 6 XDI), dicyclohexylmethane diisocyanate (H) 12 MDI), or an aliphatic polyisocyanate (the aliphatic group is a concept including a straight chain, a branched chain, and an alicyclic group);
their carbodiimide-modified polyisocyanates.
From the viewpoint of more excellent effects and excellent initial strength expression of the present invention, the polyisocyanate component preferably contains an aromatic polyisocyanate, more preferably at least 1 selected from MDI, polymeric MDI, carbodiimide-modified products thereof, and triphenylmethane triisocyanate, and still more preferably contains polymeric MDI and/or triphenylmethane triisocyanate.
The polymeric MDI is polymethylene polyphenyl polyisocyanate. The polymeric MDI may be a mixture of polymethylene polyphenyl polyisocyanates having different degrees of polymerization. The polymeric MDI may further comprise MDI in addition to the polymethylene polyphenyl polyisocyanate. The polymeric MDI is not particularly limited.
Triphenylmethane triisocyanate may be, for example, triphenylmethane-4,4', 4' -triisocyanate.
From the viewpoint of further improving the effect of the present invention and of excellent initial strength expression, the polyisocyanate component is preferably in a liquid state at room temperature (23 ℃).
Examples of the polyisocyanate component which is liquid at ordinary temperature include polymeric MDI.
The polyisocyanate component may be dissolved in a solvent.
(combination of polyol component and polyisocyanate component)
From the viewpoint of more excellent effects of the present invention and excellent initial strength expression, the polyol component and the polyisocyanate component are preferably: combination 1 of a polyol component comprising polyol 1, a polycarbonate polyol as polyol 2, and polyol 3 and a polyisocyanate component comprising triphenylmethane triisocyanate,
combination 2 of a polyol component comprising polyol 1, polybutadiene polyol or polyisoprene polyol as polyol 2, and polyol 3, and a polyisocyanate component comprising polymeric MDI.
Combination 1
From the viewpoint of the superior effects of the present invention, the initial strength expression, and the magnitude of the initial strength, the combination 1 preferably includes a polyester polyol having a Tg of 0 to +40 ℃ in the polyol 1, and/or
The proportion of hydroxyl groups of the polyol 2 among all hydroxyl groups of the polyol component is 10.0 to 40.0 mol%, and the proportion of hydroxyl groups of the polyol 3 is 20.0 to 70.0 mol%,
more preferably, the polyol 1 contains a polyester polyol having a Tg of 0 to +40 ℃, and the proportion of the hydroxyl groups of the polyol 2 in all the hydroxyl groups of the polyol component is 10.0 to 40.0 mol%, and the proportion of the hydroxyl groups of the polyol 3 is 20.0 to 70.0 mol%.
Combination 2
From the viewpoint of the superior effects of the present invention, the initial strength expression, and the magnitude of the initial strength, the combination 2 preferably includes a polyester polyol having a Tg of 0 to +40 ℃,
polyol 2 comprises a polybutadiene polyol,
polyol 2 comprises a polybutadiene polyol having a hydroxyl value of 30 to 90KOHmg/g, and/or
The proportion of hydroxyl groups of the polyol 2 among all hydroxyl groups of the polyol component is 50.0 to 70.0 mol%, and the proportion of hydroxyl groups of the polyol 3 is 20.0 to 40.0 mol%,
more preferably the polyol 1 comprises a polyester polyol having a Tg of 0 to +40 ℃,
the polyol 2 contains a polybutadiene polyol having a hydroxyl value of 30 to 90KOHmg/g, and the proportion of hydroxyl groups of the polyol 2 is 50.0 to 70.0 mol% and the proportion of hydroxyl groups of the polyol 3 is 20.0 to 40.0 mol% of all hydroxyl groups of the polyol component.
(NCO/OH molar ratio)
From the viewpoint of the more excellent effect of the present invention and the excellent initial strength expression, the molar ratio (NCO/OH) of all isocyanate groups in the polyisocyanate component to all hydroxyl groups in the polyol component is preferably 0.7 to 5.5, more preferably 1.0 to 3.0, and even more preferably 1.5 to 2.5.
(solvent)
From the viewpoint of further improving the effects of the present invention and of excellent initial strength expression, the adhesive composition of the present invention preferably further contains a solvent.
The solvent is not particularly limited as long as it is a substance having solubility or compatibility with the polyol component and no reactivity. The same applies to the polyisocyanate component.
Examples of the solvent include organic solvents, and specifically, ester solvents, ketones such as methyl ethyl ketone, and ethers such as tetrahydrofuran.
From the viewpoint of the excellent effects and the excellent initial strength expression of the present invention, the solvent preferably contains an ester-based solvent, more preferably contains an acetate-based solvent, and still more preferably contains ethyl acetate.
(content of solvent)
When the adhesive composition of the present invention further contains a solvent, the content of the solvent is preferably 30 to 80% by mass of the total amount of the adhesive composition of the present invention. In the above case, the total amount of the polyol component and the polyisocyanate component may be 20 to 70% by mass of the total amount of the adhesive composition of the present invention.
When the polyisocyanate component is dissolved in the solvent, the amount of the solvent used together with the polyisocyanate component is contained in the content of the solvent.
(other Components)
The adhesive composition of the present invention may further contain, in addition to the above components, additives such as a catalyst, carbon black, a white filler (e.g., silica, calcium carbonate, clay, talc), an antioxidant, a pigment (dye), a plasticizer, a softener, and a flame retardant, if necessary. The kind and content of each additive can be selected as appropriate.
(catalyst)
From the viewpoint of further improving the effects of the present invention and the initial strength expression, the adhesive composition of the present invention preferably further contains a catalyst.
Examples of the catalyst include carboxylic acids such as 2-ethylhexanoic acid and oleic acid; phosphoric acids such as polyphosphoric acid, ethyl acid phosphate, and butyl acid phosphate; bismuth catalysts such as bismuth octoate; tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; 1,4-diazabicyclo [2.2.2] octane, 2,4,6-tris (dimethylaminomethyl) phenol (e.g., DMP-30), bis (2-dimethylaminoethyl) ether, and other amine-based catalysts.
The catalyst preferably contains a tin-based catalyst and/or an amine-based catalyst, and more preferably contains a tin-based catalyst and an amine-based catalyst.
The amount of the catalyst may be appropriately selected.
(method for producing adhesive composition 1)
The adhesive composition of the present invention can be produced by, for example, mixing the above components. In addition, when produced as described above, the adhesive composition of the present invention may be a 1-component system.
(method for producing adhesive composition 2)
The adhesive composition of the present invention is preferably a 2-component system in view of excellent storage stability.
When the adhesive composition of the present invention is a 2-component system, at least the polyol component may be added to the 1 st liquid, and the polyisocyanate component may be added to the 2 nd liquid. The other components may be added to the 1 st liquid and/or the 2 nd liquid as appropriate.
When the adhesive composition of the present invention is a 2-component system, the 1 st liquid and the 2 nd liquid may be mixed and used.
[ urethane adhesive composition ]
The adhesive composition of the present invention may be a polyurethane adhesive obtained by reacting a polyol component with a polyisocyanate component.
[ bonding of vulcanized rubber ]
The adhesive composition of the present invention can be used for bonding vulcanized rubber.
The vulcanized rubber is rubber which has been vulcanized. The adhesive composition of the present invention may be used as long as at least one of the adherends is vulcanized rubber, and one of the preferable embodiments is that both of the adherends are vulcanized rubber. When both adherends are vulcanized rubbers, the types of the vulcanized rubbers may be the same or different. In the case where both adherends are vulcanized rubbers, the types of both vulcanized rubbers are preferably the same from the viewpoint of further improving the effect of the present invention and of excellent initial strength expression. In addition, when adherends having a plurality of layers of different types of vulcanized rubbers are bonded to each other, it is preferable to bond homogeneous vulcanized rubbers to each other for the same reason as described above. For example, in the case of bonding adherends having a layer of vulcanized rubber a and a layer of vulcanized rubber B to each other, it is preferable to bond the layers of vulcanized rubber a and/or the layers of vulcanized rubber B to each other.
Examples of the rubber component contained in the vulcanized rubber include diene rubbers such as Natural Rubber (NR), isoprene Rubber (IR), butadiene Rubber (BR), aromatic vinyl compound-conjugated diene copolymer rubber (e.g., styrene-butadiene rubber), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (BR-IIR, cl-IIR), and Chloroprene Rubber (CR).
The vulcanized rubber may further contain various additives generally used in rubber compositions such as fillers such as carbon black and silica, silane coupling agents, zinc oxide, stearic acid, antioxidants, processing aids, oils (e.g., processing oils and aromatic oils), liquid polymers, vulcanizing agents (e.g., sulfur), and vulcanization accelerators, in addition to the rubber component.
The vulcanized rubber is preferably a vulcanized rubber obtained by using sulfur. The vulcanization conditions are not particularly limited.
The adhesive composition of the present invention has excellent adhesion to a vulcanized rubber containing BR at a high ratio (for example, the content of BR in the rubber component exceeds 30 mass%). The adhesive composition of the present invention is also excellent in adhesion to a vulcanized rubber containing BR at a low proportion (for example, the content of BR in the rubber component is less than 30 mass%) or a vulcanized rubber not containing BR.
The adhesive composition of the present invention can be cured at 5 to 40 ℃ and 10 to 80% RH, for example.
The adhesive composition of the present invention can easily perform endless processing of rubber products (particularly, elongated products), and is therefore preferably used for bonding conveyor belts, for example.
[ method of bonding vulcanized rubber ]
Next, the vulcanized rubber bonding method of the present invention will be described.
The vulcanized rubber bonding method of the present invention is a vulcanized rubber bonding method of bonding vulcanized rubbers to each other using the urethane adhesive composition of the present invention.
The adhesive composition used in the vulcanized rubber bonding method of the present invention is not particularly limited as long as it is the urethane adhesive composition of the present invention.
The vulcanized rubber used in the vulcanized rubber bonding method of the present invention is not particularly limited as long as it is a rubber that has been vulcanized. The vulcanized rubber may be the same as the vulcanized rubber described in the above [ adhesive vulcanized rubber ].
The vulcanized rubber bonding method of the present invention uses an adhesive composition having excellent adhesiveness to vulcanized rubber as described above, and is therefore useful for bonding vulcanized rubber, particularly vulcanized rubber containing BR at a high ratio (for example, more than 30 mass% in the rubber component).
After vulcanization, the vulcanized rubber may be subjected to physical surface treatment such as grinding (バフ dang け) or chemical surface treatment such as a surface treatment agent (e.g., primer), as needed.
In view of the fact that the vulcanized rubber has a large surface roughness and thus easily penetrates the adhesive composition, and the effect of the present invention is further excellent, it is preferable to perform a physical surface treatment such as grinding.
The method for bonding vulcanized rubbers according to the present invention can be carried out, for example, by applying the adhesive composition according to the present invention to the vulcanized rubbers, bonding the vulcanized rubbers to each other by bonding the vulcanized rubbers to each other and curing the bonded rubbers at a temperature of 15 to 35 ℃ and a RH of 40 to 70%.
When the vulcanized rubbers are bonded to each other, the position where the bonding is performed in the vulcanized rubbers is not particularly limited. Examples of the position include a surface and an end of the vulcanized rubber.
When there are a plurality of vulcanized rubbers, the plurality of vulcanized rubbers may be connected to each other to be elongated.
In addition, in 1 vulcanized rubber or the vulcanized rubber integrated as described above, the ends of the vulcanized rubber may be bonded to each other, and the vulcanized rubber may be formed into a ring shape (annular shape).
[ conveyor belt ]
The conveyor belt of the present invention is a conveyor belt in which the ends of the belt are bonded to each other using the urethane adhesive composition of the present invention.
The adhesive composition used for the conveyor belt of the present invention is not particularly limited as long as it is the urethane adhesive composition of the present invention.
The belt used for the conveyor belt of the present invention is not particularly limited as long as it can be used for a conveyor belt.
Examples of the belt (conveyor belt as a raw material) include a belt having a structure in which a coating rubber in which a tensile material is embedded is provided on and under the coating rubber. The tensile member is not particularly limited, and examples thereof include canvas and a steel cord.
The vulcanized rubber constituting the belt is not particularly limited as long as it can be used for a conveyor belt. For example, the vulcanized rubber may be the same as the vulcanized rubber described in the above [ adhesive vulcanized rubber ].
The vulcanized rubber may be subjected to, after vulcanization, physical surface treatment such as grinding, or chemical surface treatment such as a surface treatment agent (e.g., primer), as required.
In the vulcanized rubber in the portion bonded to the belt, it is preferable to perform a physical surface treatment such as grinding by a grinding wheel, from the viewpoint that the surface unevenness is large and the adhesive composition is likely to penetrate, and the effect of the present invention is more excellent.
[ end portions of the belt with each other ]
In the present invention, when the end portions of the tape are bonded to each other, the bonding surface of the tape preferably contains vulcanized rubber.
In the case where a plurality of belts are used in the conveyor belt of the present invention, the plurality of belts may be connected to each other at the end of each belt, and the belts may be elongated and integrated.
Further, the ends of 1 band may be bonded to each other so that the band may have a loop shape (ring shape). The same applies to the integrally formed elongated belt as described above.
The conveyor belt of the present invention is preferably endless (endless) by bonding the ends of 1 belt or the ends of a belt integrally formed into a long belt as described above with the adhesive composition of the present invention.
As a method for producing the conveyor belt of the present invention (bonding method, endless method), for example, a method in which a belt-like belt (conveyor belt as a raw material, the same applies hereinafter) is produced by vulcanization as usual, and then the adhesive composition of the present invention is applied to the end portions of the belt to bond the end portions of the belt to each other is cited. The tape may be processed as described below before the adhesive composition of the present invention is applied to the end of the tape, or may be unprocessed. Examples of the processing (bonding form) include a peeling method in which an end portion of the tape is cut obliquely with respect to the running direction and bonded; a step method in which each layer of a cover rubber, a coating rubber, a tension-resistant material, or the like at the end of a belt is peeled off and cut in a step-like manner and bonded; a lap type (no special tape processing) in which the ends of the tape are overlapped and bonded; a finger joint method (electro-optical joint method or insertion method) in which the end portions of the tapes are cut into a wedge shape and butted and bonded, a method in which the end portions of the tapes are cut into a wedge shape with respect to the running direction and butted and bonded, an improvement type or fusion type of each method, and the like.
An example of a method for manufacturing a conveyor belt according to the present invention is a method of attaching a belt as shown in fig. 1. The invention is not limited to the attached drawings. Fig. 1 is a schematic view showing an example of the bonding form of the conveyor belt of the present invention. Fig. 1 specifically shows an example of a step method in which each layer of a cover rubber, a coating rubber, and a tensile member (not shown) at the end of the tape is peeled off and cut in a step-like manner to be bonded with respect to the above bonding form.
As the tape (adherend rubber), as shown in fig. 1 (a), a tape 1 in which the layers of the covering rubbers 2a and 2b, the coating rubber 3, and the tensile material (not shown) are peeled and cut stepwise in the end region 4, and a tape 1' in which the layers of the covering rubbers 2a ' and 2b ', the coating rubber 3', and the tensile material (not shown) are peeled and cut stepwise in the end region 4' are prepared. Next, the adhesive composition of the present invention is applied to the adhesive interface in the end region 4 and/or the adhesive interface in the end region 4', and then the end region 4 and the end region 4' are bonded as shown in fig. 1 (b), thereby manufacturing a conveyor belt. That is, in the conveyor belt shown in fig. 1 (b), vulcanized rubbers at the ends of the belt are bonded to each other using the adhesive composition of the present invention. The adhesion of the vulcanized rubbers to each other and the combination thereof include, for example, in fig. 1 (b), the vulcanized rubbers of the same kind as those of the covering rubbers 2a and 2a ', the covering rubbers 2b and 2b ', and the coating rubbers 3 and 3', and the vulcanized rubbers of different kinds (or compounded) as those of the covering rubbers 2a and 3', and the coating rubbers 3 and 2b '.
The method for producing the conveyor belt of the present invention includes, for example, a method in which the adhesive composition of the present invention is applied to a vulcanized rubber (any one of vulcanized rubbers of belts such as a covering rubber and a coating rubber) of a belt, dried, and then the vulcanized rubbers (adherend rubbers) of the belts are bonded to each other and pressure-bonded, and left to stand at 0 to 35 ℃ (preferably 15 to 30 ℃, more preferably 20 to 25 ℃) for 3 to 72 hours (preferably 3 to 24 hours, more preferably 6 to 18 hours). Further, by heating and pressurizing, the reaction of the adhesive composition is accelerated, and the time required for the bonding treatment can be shortened. However, in order to avoid over-vulcanization of the vulcanized rubber, the heating is preferably 100 ℃ or lower.
Examples
The following examples illustrate the present invention in detail. However, the present invention is not limited thereto.
< production of adhesive composition >
Each component shown in "solution 1 (compounding/part by mass)" in the following table was used in the composition (part by mass) shown in the table, and these were mixed with a mixer to prepare solution 1.
Each component shown in "liquid 2 (compounding/part by mass)" in the following table was used in the composition (part by mass) shown in the table, and these were mixed with a mixer to prepare liquid 2.
Next, the 1 st liquid and the 2 nd liquid prepared as described above were mixed in an amount (parts by mass) shown in "mixing of 1 st liquid/2 nd liquid" in the following table to produce each adhesive composition.
< preparation of adherend rubber 1 >
Each component (part by mass) shown below (BR-based compound 1) was mixed with a mixer to prepare an unvulcanized rubber composition. The following (BR-based compound 1) is the same as BR-based compound 1 shown in table 7 described later.
(BR Compound 1)
100 parts by mass of a rubber component NR/SBR/BR =28/36/36 (parts by mass)
Carbon black: 65 parts by mass of ISAF carbon black
Oil: 6 parts by mass
Sulfur: 1.4 parts by mass
Vulcanization accelerator D:0.2 part by mass
Vulcanization accelerator CZ:1.0 part by mass
Subsequently, the unvulcanized rubber composition obtained as described above was vulcanized at 148 ℃ to obtain a vulcanized rubber (a vulcanized sheet having a thickness of 2mm and a square size of 6 × 4 inches), the surface of the vulcanized rubber was ground with a sand paper, and then a surface treatment agent (product name アフトリート, manufactured by tokyo corporation) was applied and dried to prepare an adherend rubber 1.
< preparation of multilayer body 1 >
2 pieces of the adherend rubber 1 prepared as described above were prepared, the adhesive compositions prepared as described above were applied to the respective adherend rubbers 1, the adherend rubbers 1 were bonded to each other on the surfaces to which the adhesive compositions were applied to prepare samples, a weight having a mass of 10kg was placed on the samples, and the samples were cured for 3 hours or 1 week under conditions of 23 ℃ and 50% rh to prepare respective laminates 1.
< evaluation >
The laminate 1 prepared as described above was used to perform the following evaluation. The results are shown in "evaluation results" in tables 1 to 6.
< adhesion >
Using each laminate 1 after curing for 1 week, a T-type peel test was performed at room temperature (23 ℃ C.) and a peel speed of 50 mm/min, and the peel strength (maximum peak strength, unit: N/25 mm) was measured, and the state of failure after the peel test was visually confirmed.
Peel Strength (after 1 week)
Represents that the peel strength of the laminate 1 after curing for 1 week is 80N/25mm or more.
The peel strength was larger than 60N/25mm and smaller than 80N/25mm.
Delta represents the peel strength of 40 to 60N/25mm.
And x represents that the peel strength is less than 40N/25mm.
Fracture State after peeling test (after 1 week)
CF means agglutination failure. MF indicates that the vulcanized rubber is broken. "CF/MF" means that CF is present in admixture with MF.
AF denotes interface destruction. "CF/AF" means that CF is present in admixture with AF.
Evaluation criteria for adhesion to vulcanized rubber
In the present invention, the adhesiveness to a vulcanized rubber containing BR at a high ratio was evaluated in terms of the peel strength of each laminate 1 after curing for 1 week and the fracture state after the peel test.
That is, in the present invention, when the laminate 1 after curing for 1 week had the peel strength exceeding 60N/25mm and the fracture state was CF and/or MF, it was evaluated that the adhesiveness to the vulcanized rubber containing BR at a high ratio was excellent. The more the peel strength is greater than 60N/25mm, the more excellent the adhesiveness is.
On the other hand, in the laminate 1 after curing for 1 week, when the peel strength was 60N/25mm or less or when the fracture state was AF, it was evaluated that the adhesiveness to a vulcanized rubber containing BR at a high ratio was poor.
< expression of initial Strength >
Using each laminate 1 after curing for 3 hours, a T-type peel test was performed at room temperature (23 ℃ C.) and a peel speed of 50 mm/min, and the peel strength (maximum peak strength, unit: N/25 mm) was measured, and the state of failure after the peel test was visually confirmed.
Peel Strength (after 3 hours)
Represents that the peel strength of each laminate 1 after curing for 3 hours is 25N/25mm or more.
The peel strength was larger than 10N/25mm and smaller than 25N/25mm.
Delta represents the peel strength of 5 to 10N/25mm.
X represents that the peel strength is less than 5N/25mm.
The fracture state after the peel test (after 3 hours) is the same as the fracture state after the peel test (after 1 week).
Evaluation criteria for initial Strength Performance
In the present invention, the peel strength of each laminate 1 after curing for 3 hours and the fracture state after the peel test were evaluated for the expression of the initial strength of the vulcanized rubber containing BR at a high ratio.
In the present invention, each laminate 1 after curing for 3 hours was evaluated to have excellent initial strength in a vulcanized rubber containing BR at a high ratio when the peel strength (after 3 hours) exceeded 10N/25mm and the fracture state was CF and/or MF. The more the peel strength is greater than 10N/25mm, the more excellent the adhesiveness is.
On the other hand, when the peel strength is 10N/25mm or less, or when the fracture state is AF, the evaluation is that the initial strength of the vulcanized rubber containing BR at a high ratio is poor.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
The details of each component shown in tables 1 to 6 are as follows.
[ solution 1]
(polyol 1)
Polyester polyol 1-1: バイロン GK-810, manufactured by Toyo Boseki K.K. Tg of 46 ℃, hydroxyl value of 19KOHmg/g, acid value of 5KOHmg/g, mn6,000.
Polyester polyol 1-2: バイロン GK-890, manufactured by Toyo Boseki. Tg of 17 ℃, hydroxyl value of 13KOHmg/g, acid value of 5KOHmg/g, mn11,000.
Polyester polyols 1-3: バイロン 630, manufactured by TOYOBO. Tg of 7 ℃, hydroxyl value of 5KOHmg/g, acid value of less than 2KOHmg/g, mn23,000.
Polyester polyols 1 to 4: バイロン 500, manufactured by TOYOBO. Tg4 ℃, hydroxyl value 5KOHmg/g, acid value < 2KOHmg/g, mn23,000.
Polyester polyols 1 to 5: バイロン 550, manufactured by TOYOBO. Tg-15 ℃, hydroxyl value 4KOHmg/g, acid value less than 2KOHmg/g, mn28,000.
Polyester polyols 1 to 6: バイロン UR-3210, manufactured by Toyo Boseki. Tg-3 ℃, hydroxyl value of 2.5KOHmg/g, acid value of less than 1KOHmg/g, mn40,000.
Polyester polyols 1 to 7: バイロン UR-6100, manufactured by TOYOBO. Tg-30 ℃, hydroxyl value of 5KOHmg/g, acid value of less than 1KOHmg/g, mn32,000.
Comparative polyester polyol: バイロン 200, manufactured by Toyo Boseki K.K. Tg of 67 ℃, hydroxyl value of 6KOHmg/g, acid value of less than 2KOHmg/g, mn17,000.
(polyol 2)
Polyester polyol 2-1: バイロン GK-680, toyo Boseki. Tg of 10 ℃, hydroxyl value of 21KOHmg/g, acid value of less than 2KOHmg/g, mn6,000.
Butadiene skeleton polyol 2-1: poly bd 15HT, manufactured by Shikko Kogyo. Hydroxyl value 102.7KOHmg/g, mn1,200. Hydroxyl terminated liquid polybutadiene. 1.5 Pa.s @ 30 deg.C
Butadiene skeleton polyol 2-2: poly bd 45HT, manufactured by Shikko Kogyo. Hydroxyl number 46.6KOHmg/g, mn2,800. Hydroxyl terminated liquid polybutadiene. 5.0 Pa.s @ 30 deg.C
Isoprene skeleton polyol 2: poly ip, manufactured by shinning Kogyo. Hydroxyl number 46.6KOHmg/g, mn2,500. Hydroxyl terminated liquid polyisoprene. 7.5 Pa.s @ 30 deg.C
Polyolefin backbone polyol 2: エポール, manufactured by mitsunken co. Hydroxyl value 50.5KOHmg/g, mn2,500. A hydroxyl terminated liquid polyolefin. 75Pa s @ 30 deg.C
Polyester polyols 2-2:2,4-diethyl-1,5-pentanediol polyester polyol with phthalic anhydride. HS 2N-226P, feng Guo, manufactured by Okinawa. Hydroxyl number 56.1KOHmg/g, mn2,000
Polycarbonate polyol 2-1: EATERNACOLL PH200D, a product of Uyu JUN. Hydroxyl value 57.3KOHmg/g, acid value 0.03KOHmg/g, mn2,000. The polycarbonate polyol is prepared from 1,5-pentanediol and 1,6-hexanediol. 2200-3400 mPa @ 75 deg.C (liquid state).
Polycarbonate polyol 2-2: EATERNACOLL UP-50, produced by Utsumadi Kaisha, hydroxyl value 224.4KOHmg/g, mn500, 300mPa & s @ 75 deg.C (normal temperature liquid). Polycarbonate polyol using 2-methyl-1,3-propylene glycol as raw material
Comparative polyether polyol 1: EXCENOL2020, asahi glass Co., ltd., hydroxyl value 56.1KOHmg/g, mn2,000
Comparative polyether polyol 2: VORANOL TM P400polyol, manufactured by Dow Chemical Co., ltd., hydroxyl value 260KOHmg/g, mn431
(polyol 3)
1,4BD:1,4-butanediol (commercially available from Mitsubishi ケミカル Co., ltd.), hydroxyl number of 1245KOHmg/g, molecular weight of 431 KOHmg/g
PD-9:2,4-diethyl-1,5-pentanediol (commercially available, KH ネオケム Co., ltd.), hydroxyl value of 700KOHmg/g, molecular weight of 160.3
BEPG: 2-butyl-2-ethyl-1,3-propanediol (commercially available from KH ネオケム), hydroxyl number 700KOHmg/g, molecular weight 160.3
ND:1,9-nonanediol (commercially available product, クラレ Co.), hydroxyl number 700KOHmg/g, molecular weight 160.3
(catalyst)
Metal catalyst: dioctyl tin dilaurate. Trade name U-810, manufactured by Nindong chemical Co., ltd
Amine-based catalyst: bis (dimethylaminoethyl) ether. Product name of BL-19, エボニック
[ solution 2]
Aromatic polyisocyanate 1: polymeric MDI. スミジュール 44V-10, manufactured by Showa コベストロウレタン, solid content 100%, NCO%32.0%
Aromatic polyisocyanate 2: carbodiimide modified MDI. The product is ミリオネート MTL manufactured by ソー, DONG. 100% solids, 29.0% NCO
Aromatic polyisocyanate 3: triphenylmethane-4,4',4"-triisocyanate (triphenylmethane-4,4', 4" -triisocyanate) (Mw 367.36) デスモジュール RE, manufactured by shochu コベストロウレタン. 27% by mass of a solid content, and 9.3% by mass of NCO%
Aliphatic polyisocyanate: a mixture of an isocyanurate body of pentamethylene diisocyanate and an allophanate body of pentamethylene diisocyanate. スタビオ D-376N, manufactured by Mitsui chemical. 100% of solid content, 22.0% of NCO
From the results shown in tables 1 to 6, comparative examples 1 and 2, which did not contain polyol 1, had poor adhesion to a vulcanized rubber containing BR at a high ratio.
In comparative examples 3 to 5 and 8 containing no polyol 2, adhesiveness to a vulcanized rubber containing BR at a high ratio was poor.
In comparative example 6, which contained no polyols 1 and 2 and instead contained chloroprene rubber, adhesiveness to a vulcanized rubber containing BR at a high ratio was poor.
In comparative example 7 containing no polyol 1, adhesiveness to a vulcanized rubber containing BR at a high ratio was poor.
In contrast, the adhesive composition of the present invention has excellent adhesion to a vulcanized rubber containing BR at a high ratio.
< adhesion to various adherend rubbers >
As the adherend rubber, 6 belts (BR-based compounds 1 to 3, wear-resistant belts, heat-resistant belts, oil-resistant belts) and general-purpose coated rubbers, which are commonly used as covering rubbers of conveyor belts, were used. The main components and vulcanization system of each belt are shown in table 7. In the following examples, adhesion of homogeneous vulcanized rubbers was evaluated.
In the polymer column in the table, "NR" means natural rubber, "NBR" means nitrile rubber, "SBR" means styrene-butadiene rubber, and "BR" means butadiene rubber.
In addition, in the carbon black column, "ISAF" means "intermediate Super Abrasion Furnace black (intermediate Super Abrasion Furnace black)", "HAF" means "High Abrasion Furnace black (High Abrasion Furnace black)", and "GPF" means "General Purpose Furnace black (General Abrasion Furnace black)".
In addition, in the vulcanization system column (vulcanization component column),
"D" is a guanidine-based vulcanization accelerator (trade name "サンセラー D-G" manufactured by Sanxin chemical Co., ltd.),
"CZ" means a sulfenamide-based vulcanization accelerator (trade name "ノクセラー CZ-G" manufactured by Dainiji New chemical industries, ltd.),
"NS" refers to a sulfenamide-based vulcanization accelerator (trade name "サンセラー NS-G" manufactured by Sanxin chemical Co., ltd.),
"TS" refers to a thiuram-based vulcanization accelerator (trade name "サンセラー TS-G" manufactured by Sanxin chemical Co., ltd.),
"M" means a thiazole-based vulcanization accelerator (trade name "ノクセラー M" available from Dainiji chemical industries, ltd.).
"phr" in the columns of carbon black, oil/plasticizer, and vulcanization system means parts by mass with respect to 100 parts by mass of the polymer.
The BR-based compound 1 in the table is the same as (BR-based compound 1) used in the above < preparation of adherend rubber 1 >.
TABLE 7
< production of adherend rubber 2 >
Each adherend rubber was prepared by using each component (part by mass) shown in the rubber compounding in table 7 in the same manner as in preparation 1 > of the < adherend rubber (the same manner was applied until the surface treatment agent was applied), each adherend rubber 2 sheet prepared as described above was coated with the adhesive composition shown in "used adhesive composition" in table 7, the same kind (compounded) of adherend rubbers was bonded to each other on the surface to which the adhesive composition was applied to prepare a sample, a weight of 10kg in mass was placed on the sample, and the sample was cured for 1 week under conditions of 23 ℃ and 50% rh to prepare each laminate 2.
< evaluation >
Using each laminate 2 prepared as described above, the same evaluation as the above-described < adhesiveness > was performed. The evaluation criteria are the same as described above. The results are shown in Table 7.
According to the results shown in table 7, when the adhesive composition of comparative example 6 containing no polyols 1 and 2 instead of chloroprene rubber was used for vulcanized rubbers containing BR at a high ratio (BR-based compounds 1 to 3), the adhesiveness between the vulcanized rubbers was poor.
In contrast, the adhesive composition of the present invention has excellent adhesion to a vulcanized rubber containing BR at a high proportion such as more than 30 mass% in the vulcanized rubber (for example, a covering rubber of a BR-based compound in a conveyor belt).
The adhesive composition of the present invention is also excellent in adhesion to a vulcanized rubber (for example, a heat-resistant belt or a coating rubber in a conveyor belt) containing no BR or BR in a low proportion (30 mass% or less in the vulcanized rubber).
Description of the symbols
1. 1' band
2a, 2b, 2a ', 2b' are covered with rubber
3. 3' coated rubber
4. 4' end region.
Claims (13)
1. A urethane adhesive composition comprising a polyol component and a polyisocyanate component, wherein the polyol component comprises the following polyol 1 and polyol 2, the urethane adhesive composition being used for bonding a vulcanized rubber,
polyol 1: is a polyhydric alcohol compound having a glass transition temperature of-30 to +60 ℃, a hydroxyl value of 1 to 20KOHmg/g and an ester bond,
polyol 2: the polyol compound has a hydroxyl value of more than 20KOHmg/g and 500KOHmg/g or less and has a skeleton comprising at least 1 selected from the group consisting of polymers of isoprene and/or butadiene, hydrides thereof, polyolefins, ester bonds, and carbonate bonds.
2. The urethane adhesive composition according to claim 1, wherein the proportion of the hydroxyl group of the polyol 1 in all the hydroxyl groups of the polyol component is 10 to 30 mol%.
3. The urethane adhesive composition according to claim 1 or 2, wherein the proportion of the hydroxyl group of the polyol 2 in all the hydroxyl groups of the polyol component is 40 to 70 mol%.
4. The urethane adhesive composition according to any one of claims 1 to 3, wherein the polyol component further comprises polyol 3 having a hydroxyl value of more than 500KOHmg/g and 1300KOHmg/g or less.
5. The urethane adhesive composition according to claim 4, wherein the polyol 3 has a hydroxyl value of 1000 to 1300KOHmg/g.
6. The urethane adhesive composition according to claim 4 or 5, wherein the proportion of the hydroxyl group of the polyol 3 in all the hydroxyl groups of the polyol component is 10 to 40 mol%.
7. The urethane adhesive composition according to any one of claims 1 to 6, wherein a molar ratio of all isocyanate groups of the polyisocyanate component to all hydroxyl groups of the polyol component is 1.0 to 3.0.
8. The urethane adhesive composition according to any one of claims 1 to 7, wherein the glass transition temperature of the polyol 1 is 0 to +50 ℃.
9. The urethane adhesive composition according to any one of claims 1 to 8, wherein the number average molecular weight of the polyol 1 is 6,000 to 23,000.
10. The urethane adhesive composition according to any one of claims 1 to 9, wherein the polyol 2 has at least polyisoprene, polybutadiene, a hydride thereof, or polycarbonate as a skeleton.
11. The urethane adhesive composition according to any one of claims 1 to 10, further comprising a solvent, the solvent containing at least an acetate solvent.
12. A method for bonding vulcanized rubbers, wherein the vulcanized rubbers are bonded to each other using the urethane adhesive composition according to any one of claims 1 to 11.
13. A conveyor belt, wherein the ends of the belt are bonded to each other using the urethane adhesive composition according to any one of claims 1 to 11.
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| JP2021169657A JP2023059569A (en) | 2021-10-15 | 2021-10-15 | Urethane-based adhesive composition, vulcanized rubber bonding method, and conveyor belt |
| JP2021-169657 | 2021-10-15 |
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| CN115975584A true CN115975584A (en) | 2023-04-18 |
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