CN112608525A - Rubber composition for bonding steel cord and conveyor belt - Google Patents
Rubber composition for bonding steel cord and conveyor belt Download PDFInfo
- Publication number
- CN112608525A CN112608525A CN202011001518.9A CN202011001518A CN112608525A CN 112608525 A CN112608525 A CN 112608525A CN 202011001518 A CN202011001518 A CN 202011001518A CN 112608525 A CN112608525 A CN 112608525A
- Authority
- CN
- China
- Prior art keywords
- rubber
- steel cord
- mass
- parts
- phenol
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 168
- 239000005060 rubber Substances 0.000 title claims abstract description 168
- 239000000203 mixture Substances 0.000 title claims abstract description 140
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 77
- 239000010959 steel Substances 0.000 title claims abstract description 77
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 134
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000004073 vulcanization Methods 0.000 claims abstract description 45
- 239000005011 phenolic resin Substances 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- -1 organic acid cobalt salts Chemical class 0.000 claims abstract description 34
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000001424 substituent group Chemical group 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 34
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 13
- 229930003836 cresol Natural products 0.000 claims description 13
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 11
- YJEUJARPQSLENW-UHFFFAOYSA-M B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] Chemical group B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] YJEUJARPQSLENW-UHFFFAOYSA-M 0.000 claims description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 7
- 239000008397 galvanized steel Substances 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 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 41
- 230000000694 effects Effects 0.000 description 40
- 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 36
- 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 36
- 229920003048 styrene butadiene rubber Polymers 0.000 description 32
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 19
- 150000002989 phenols Chemical class 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 15
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 244000043261 Hevea brasiliensis Species 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 229920003052 natural elastomer Polymers 0.000 description 12
- 229920001194 natural rubber Polymers 0.000 description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 150000007524 organic acids Chemical class 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920003049 isoprene rubber Polymers 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- WHCIAGVVOCLXFV-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)-1,3-benzothiazole Chemical group C1=CC=C2SC(SC=3SC4=CC=CC=C4N=3)=NC2=C1 WHCIAGVVOCLXFV-UHFFFAOYSA-N 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- LMWMTSCFTPQVCJ-UHFFFAOYSA-N 2-methylphenol;phenol Chemical compound OC1=CC=CC=C1.CC1=CC=CC=C1O LMWMTSCFTPQVCJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 2
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 2
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 2
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010073 coating (rubber) Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 2
- 229940118781 dehydroabietic acid Drugs 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
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- 239000005077 polysulfide Chemical group 0.000 description 2
- 229920001021 polysulfide Chemical group 0.000 description 2
- 150000008117 polysulfides Chemical group 0.000 description 2
- 238000007586 pull-out test Methods 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
- 125000004434 sulfur atom Chemical group 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- DLTLLZLEJKRETK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n-pentamethoxy-6-n-methyl-1,3,5-triazine-2,4,6-triamine Chemical compound CON(C)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 DLTLLZLEJKRETK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
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- 239000012166 beeswax Substances 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GQWNEBHACPGBIG-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-[2-(1,3-benzothiazol-2-ylsulfanylamino)ethoxy]ethanamine Chemical compound C1=CC=C2SC(SNCCOCCNSC=3SC4=CC=CC=C4N=3)=NC2=C1 GQWNEBHACPGBIG-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
- B65G15/30—Belts or like endless load-carriers
- B65G15/32—Belts or like endless load-carriers made of rubber or plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a rubber composition for bonding a steel cord, which has excellent water-resistant adhesion, and a conveyor belt. The rubber composition for bonding steel cords comprises: a rubber component containing at least a diene rubber; a mixture comprising a phenol having 1 phenolic hydroxyl group and which may further have a substituent (wherein the phenolic hydroxyl group is excluded), and a phenol resin; diethylene glycol; a vulcanization accelerator; organic acid cobalt salts; and sulfur, wherein the content of the mixture is 2.0 to 10.0 parts by mass relative to 100 parts by mass of the rubber component, and the content of the diethylene glycol is 0.3 to 2.5 parts by mass relative to 100 parts by mass of the rubber component.
Description
Technical Field
The present invention relates to a rubber composition for bonding steel cords and a conveyor belt.
Background
Conventionally, various rubber compositions have been proposed for the purpose of improving adhesion to a steel cord and the like.
For example, patent document 1 describes a conveyor belt including a belt body formed by crosslinking rubber,
the belt body comprises a steel cord as a core, the steel cord being embedded in the crosslinked rubber,
the crosslinked rubber forming the portion in contact with the core is formed of a rubber composition containing a base rubber and an organic acid cobalt salt, a part or the whole of the base rubber is a natural rubber or a styrene-butadiene copolymer rubber,
the rubber composition further contains a modified resorcinol/formaldehyde condensate, a modified etherified methylolmelamine resin, diethylene glycol, and silica, and contains, relative to 100 parts by mass of the base rubber, 1 part by mass or more and 10 parts by mass or less of the modified resorcinol/formaldehyde condensate, 0.5 part by mass or more and 7 parts by mass or less of the modified etherified methylolmelamine resin, 1 part by mass or more and 5 parts by mass or less of the diethylene glycol, and 5 parts by mass or more and 45 parts by mass or less of the silica.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015-083746
Disclosure of Invention
Problems to be solved by the invention
In this case, the present inventors have made reference to patent document 1 and evaluated a rubber composition prepared and used as a rubber composition for bonding a steel cord, and as a result, they have found that there is room for improvement in water-resistant adhesion between a rubber obtained from such a rubber composition and a steel cord.
Accordingly, the present invention aims to provide a rubber composition for bonding a steel cord, which has excellent water-resistant adhesion. In the present invention, the water-resistant adhesion includes moisture-resistant adhesion.
The present invention also aims to provide a conveyor belt having excellent water-resistant adhesion.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems and as a result, have found that the water resistant adhesion between the rubber obtained from the rubber composition and the steel cord can be improved if the following rubber composition for steel cord adhesion, which contains: a rubber component containing at least a diene rubber; a mixture comprising a phenol having 1 phenolic hydroxyl group and which may further have a substituent (wherein the phenolic hydroxyl group is excluded), and a phenol resin; diethylene glycol; a vulcanization accelerator; organic acid cobalt salts; and sulfur, wherein the content of the mixture is 2.0 to 10.0 parts by mass relative to 100 parts by mass of the rubber component, and the content of the diethylene glycol is 0.3 to 2.5 parts by mass relative to 100 parts by mass of the rubber component.
The present invention solves the above problems based on the above findings and the like, specifically, with the following configurations.
[1] A rubber composition for bonding a steel cord, comprising:
a rubber component containing at least a diene rubber;
a mixture comprising a phenol having 1 phenolic hydroxyl group and which may further have a substituent (wherein the phenolic hydroxyl group is excluded), and a phenol resin;
diethylene glycol;
a vulcanization accelerator;
organic acid cobalt salts; and
the amount of sulfur is such that,
the content of the mixture is 2.0-10.0 parts by mass relative to 100 parts by mass of the rubber component,
the content of the diethylene glycol is 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the rubber component.
[2] The rubber composition for bonding a steel cord according to [1], wherein the organic acid cobalt salt is cobalt neodecanoate borate.
[3] The rubber composition for bonding a steel cord according to [1] or [2], wherein the phenol resin is an alkylphenol phenol resin.
[4] The rubber composition for bonding a steel cord according to any one of [1] to [3], wherein the phenol contains phenol and/or alkylphenol.
[5] The rubber composition for bonding a steel cord according to any one of [1] to [4], wherein the mixture further contains an aldehyde.
[6] The rubber composition for bonding a steel cord according to any one of [1] to [5], wherein the mixture contains phenol, cresol novolac as the phenol resin, and formaldehyde.
[7] The rubber composition for bonding a steel cord according to any one of [1] to [6], wherein the vulcanization accelerator is a thiazole-based vulcanization accelerator.
[8] The rubber composition for adhesion of steel cord according to any one of [1] to [7], wherein the vulcanization accelerator is 1.50 parts by mass or less with respect to 100 parts by mass of the rubber component.
[9] The rubber composition for bonding a steel cord according to any one of [1] to [8], wherein the softening point of the mixture is 85 ℃ or lower.
[10] The rubber composition for steel cord adhesion according to any one of [1] to [9], which is used for adhesion of a galvanized steel cord.
[11] A conveyor belt formed by using the rubber composition for bonding steel cords according to any one of [1] to [10 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The rubber composition for bonding a steel cord of the present invention has excellent water-resistant adhesion.
The conveyor belt of the present invention is excellent in water-resistant adhesion.
Drawings
Fig. 1 is a sectional perspective view schematically showing an example of a conveyor belt according to the present invention.
Detailed Description
The present invention will be described in detail below.
In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value.
In the present specification, unless otherwise specified, each component may be used alone or in combination with 2 or more kinds of the substances corresponding to the component. When the component contains 2 or more substances, the content of the component means the total content of the 2 or more substances.
In the present specification, the method for producing each component is not particularly limited as long as it is not particularly specified. For example, a conventionally known method can be used.
In the present specification, the more excellent water-resistant adhesion is sometimes referred to as the more excellent effect of the present invention.
[ rubber composition for adhesion of Steel cord ]
The rubber composition for bonding a steel cord of the present invention (the composition of the present invention) contains:
a rubber component containing at least a diene rubber;
a mixture comprising a phenol having 1 phenolic hydroxyl group and which may further have a substituent (wherein the phenolic hydroxyl group is excluded), and a phenol resin;
diethylene glycol;
a vulcanization accelerator;
organic acid cobalt salts; as well as sulfur, and the like, and,
the content of the mixture is 2.0-10.0 parts by mass relative to 100 parts by mass of the rubber component,
the content of the diethylene glycol is 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the rubber component.
It is considered that the composition of the present invention has the above-described structure, and therefore, the desired effects can be obtained. The reason for this is not clear, but is presumed to be as follows.
The present inventors considered that, when a rubber composition containing a diene rubber, an organic acid cobalt salt, a phenol resin, sulfur, a vulcanization accelerator, and the like is adhered to a steel cord and vulcanized to obtain a composite, the adhesiveness between the vulcanized rubber and the steel cord is deteriorated with time by water and the like in the composite.
The phenol resin in the rubber composition may have a function of coating the surface of the steel cord to enhance the adhesion between the rubber composition and the steel cord.
In this regard, it is presumed that the above functions are higher than those of the case of the phenol resin alone by including diethylene glycol and a mixture of phenols (specific phenols) having 1 phenolic hydroxyl group and optionally further having a substituent (not including the phenolic hydroxyl group).
Further, it is considered that in the case of containing a mixture containing a specific phenol and a phenol resin and diethylene glycol, the performance of removing the metal oxide on the surface of the steel cord is higher than that in the case of only the phenol resin.
For the above reasons, the present inventors speculate that the composition of the present invention, even if containing a vulcanization accelerator, can suppress the influence on the adhesion due to the deterioration of the vulcanization accelerator by containing a mixture containing a specific phenol and a phenol resin and diethylene glycol, and thus the rubber composition has excellent water-resistant adhesion to a steel cord.
The components contained in the composition of the present invention will be described in detail below.
< rubber component >
The composition of the present invention contains a rubber component containing at least a diene rubber.
< diene rubber >
The diene rubber contained in the composition of the present invention is not particularly limited as long as it is a polymer obtained by polymerizing a diene monomer.
Examples of the diene rubber include natural rubber, Isoprene Rubber (IR), aromatic vinyl compound-conjugated diene copolymer rubber (e.g., styrene butadiene copolymer rubber), nitrile rubber (NBR), butyl rubber (IIR), halogenated butyl rubber, and Chloroprene Rubber (CR).
The diene rubber is preferably natural rubber, Isoprene Rubber (IR), or an aromatic vinyl compound-conjugated diene copolymer rubber (for example, styrene butadiene copolymer rubber), and more preferably a combination of natural rubber and an aromatic vinyl compound-conjugated diene copolymer rubber (particularly, styrene butadiene copolymer rubber), or Isoprene Rubber (IR), from the viewpoint of further improving the effects of the present invention and excellent durability.
Natural rubber
The Natural Rubber (NR) is not particularly limited. Examples thereof include those conventionally known.
Isoprene rubber
The isoprene rubber is not particularly limited as long as it is a homopolymer of isoprene. Examples thereof include those conventionally known.
Styrene butadiene copolymer rubber
The styrene-butadiene copolymer rubber is not particularly limited as long as it is a copolymer of styrene and butadiene.
(bound styrene amount of styrene butadiene copolymer rubber)
From the viewpoint of further improving the effect of the present invention and lowering the glass transition temperature of the styrene-butadiene copolymer rubber described later, the amount of bound styrene in the styrene-butadiene copolymer rubber is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass, based on the total amount of the styrene-butadiene copolymer rubber.
(vinyl amount of styrene butadiene copolymer rubber)
From the viewpoint of further improving the effect of the present invention and lowering the glass transition temperature of the styrene-butadiene copolymer rubber described later, the amount of vinyl groups (1, 2-vinyl bond amount) derived from butadiene in the styrene-butadiene copolymer rubber is preferably 5 to 30% by mass, more preferably 5 to 20% by mass, based on the total amount of repeating units derived from butadiene in the styrene-butadiene copolymer rubber.
In the present invention, the amount of the bound styrene and the amount of the vinyl group in the styrene-butadiene copolymer rubber may be determined by1H-NMR measurement.
(weight average molecular weight of styrene butadiene copolymer rubber)
The weight average molecular weight of the styrene butadiene copolymer rubber is not particularly limited. And may be, for example, 20 to 300 ten thousand.
In the present invention, the weight average molecular weight of the styrene butadiene copolymer rubber is a standard polystyrene equivalent value based on a measurement value obtained by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent.
(S-SBR)
The method for producing the styrene-butadiene copolymer rubber is not particularly limited. Examples thereof include styrene butadiene copolymer rubber (S-SBR) obtained by solution polymerization and styrene butadiene copolymer rubber (E-SBR) obtained by emulsion polymerization. Among these, the styrene-butadiene copolymer rubber preferably contains S-SBR, from the viewpoint that the effect of the present invention is more excellent.
The S-SBR is not particularly limited as long as it is produced by copolymerizing styrene and butadiene in an organic solvent in the presence of a catalyst. Further, the above solution polymerization is not particularly limited. Examples of S-SBR and solution polymerization are those conventionally known.
So long as all or a part of the rubber component is a diene rubber. One preferable embodiment is one in which all of the rubber components are diene rubbers.
The content of the diene rubber is preferably 70 to 100 parts by mass per 100 parts by mass of the rubber component.
In the case where the rubber component contains the natural rubber and the styrene-butadiene copolymer rubber, the content of the natural rubber is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 60 parts by mass with respect to 100 parts by mass of the rubber component, from the viewpoint that the effect of the present invention is more excellent.
The content of the styrene-butadiene copolymer rubber may be an amount excluding the content of the natural rubber from 100 parts by mass of the rubber component.
When the rubber component contains a rubber other than a diene rubber, examples of the rubber other than a diene rubber include non-diene rubbers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM).
< mixture >
The composition of the present invention contains a mixture comprising a phenol having 1 phenolic hydroxyl group and may further have a substituent (wherein the phenolic hydroxyl group is excluded), and a phenol resin.
In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic ring (e.g., benzene ring).
< phenols >
The above mixture contains a phenol having 1 phenolic hydroxyl group and may further have a substituent (wherein the phenolic hydroxyl group is excluded).
In the present specification, the above-mentioned phenols may be referred to as "specific phenols".
The above specific phenols have 1 phenolic hydroxyl group per 1 molecule.
The specific phenol may further have a substituent in addition to the 1 phenolic hydroxyl group. However, the above substituents do not include phenolic hydroxyl groups.
Examples of the substituent which the specific phenol may further have include a hydrocarbon group such as an alkyl group.
Examples of the specific phenol include phenol (a phenol having 1 phenolic hydroxyl group and not further having the substituent);
phenols having 1 phenolic hydroxyl group and further having the above-mentioned substituent, such as alkylphenols having an alkyl group and 1 phenolic hydroxyl group, e.g., cresol and xylenol.
From the viewpoint of further improving the effect of the present invention, the specific phenol is preferably phenol and/or alkylphenol, and more preferably phenol and alkylphenol are used in combination.
(phenol)
The phenol that can be contained as the specific phenol is a compound in which 1 phenolic hydroxyl group is directly bonded to a benzene ring. In the present invention, the phenol is unsubstituted.
(alkylphenol)
The alkylphenol that can be contained as the specific phenol is a compound having an alkyl group and 1 phenolic hydroxyl group, and the phenolic hydroxyl group is directly bonded to a benzene ring.
Alkyl radical
Examples of the alkyl group of the alkylphenol include an alkyl group having 1 to 10 carbon atoms.
The alkyl group may be linear, branched, cyclic, or a combination thereof.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Among them, the above alkyl group is preferably a methyl group.
The number of the above alkyl groups which the above alkylphenol has per 1 molecule is not particularly limited. The number is preferably 1.
In the above alkylphenol, the position of the above alkyl group is not particularly limited. It is preferably meta-position to the phenolic hydroxyl group of the alkylphenol.
From the viewpoint of further improving the effect of the present invention, the alkylphenol is preferably cresol, and more preferably m-cresol.
< phenolic resin >
The phenolic resin contained in the above mixture is not particularly limited as long as it is a condensate of a phenol and an aldehyde, or a modified product thereof.
From the viewpoint of further improving the effect of the present invention, the phenol resin is preferably a polycondensate of a phenol (raw phenol) and an aldehyde.
(phenols)
Examples of the phenols that can constitute the phenol resin (hereinafter, these may be referred to as "raw material phenols") include, for example, phenol;
alkylphenols having an alkyl group and 1 phenolic hydroxyl group such as cresol and xylenol;
phenols having a plurality of phenolic hydroxyl groups such as resorcinol.
One of the preferable embodiments is that the raw material phenols contain at least phenols other than phenol. In this case, the raw material phenol may further contain phenol in addition to phenol.
Among these, from the viewpoint of further improving the effect of the present invention, the raw phenol is preferably an alkylphenol or a phenol having a plurality of phenolic hydroxyl groups, more preferably an alkylphenol, still more preferably cresol, and still more preferably m-cresol.
(aldehydes)
Examples of the aldehyde that can constitute the phenol resin include formaldehyde, acetaldehyde, and furfural.
Among them, formaldehyde is preferable from the viewpoint of further improving the effect of the present invention.
From the viewpoint of further improving the effect of the present invention, the phenol resin is preferably an alkylphenol phenol resin, more preferably a cresol phenol resin, and still more preferably a cresol/formaldehyde resin.
The above phenol resin is preferably an unmodified phenol resin.
(relationship between specific phenols and phenol resin)
When the specific phenol contains an alkylphenol and the phenol (the raw phenol) capable of constituting the phenol resin contains an alkylphenol, it is preferable that both of the alkylphenols are the same kind of alkylphenol.
(aldehyde)
From the viewpoint of further improving the effect of the present invention, the mixture preferably further contains an aldehyde.
The above mixture further contains an aldehyde which can be condensed with the above specific phenol and/or the above phenol resin when the composition of the present invention is, for example, vulcanized.
Examples of the aldehyde include formaldehyde, acetaldehyde, and furfural.
Among them, formaldehyde is preferable from the viewpoint of further improving the effect of the present invention.
The aldehyde may be derived from a methylene donor.
Examples of the methylene donor include a curing agent for a general phenol resin, and specific examples thereof include polymers of hexamethylenetetramine, hexamethoxymethylmelamine, hexamethoxymethylolmelamine, pentamethoxymethylmelamine, hexaethoxymethylmelamine, and p-formaldehyde.
From the viewpoint of further excellence in the effect of the present invention, the above mixture preferably contains phenol, alkylphenol-phenol resin, and aldehyde,
more preferably contains the above phenol, cresol novolac resin (as the above novolac resin), and formaldehyde.
(total content of phenol resin and alkylphenol as specific phenol)
In the case where the specific phenol as a component of the mixture contains phenol and an alkylphenol (e.g., cresol), and the mixture further contains an aldehyde (e.g., formaldehyde), the total content of the phenol resin (e.g., cresol phenol resin) and the alkylphenol (e.g., cresol) is preferably 80 to 98% by mass, and more preferably 90 to 98% by mass, based on the total amount of the mixture, from the viewpoint that the effect of the present invention is more excellent.
(total content of phenol and aldehyde as specific phenols)
In addition, in the case where the specific phenol contains phenol and an alkylphenol (e.g., cresol), and the mixture further contains an aldehyde (e.g., formaldehyde), the total content of the phenol and the aldehyde may be a value obtained by removing the total content of the phenol resin (e.g., cresol phenol resin) and the alkylphenol (e.g., cresol) from the total amount of the mixture.
The softening point of the mixture is preferably 85 ℃ or less, more preferably 50 to 80 ℃ from the viewpoints that the rubber composition is more excellent in the effect of the present invention, is easily dispersed in the rubber composition, has higher performance of removing metal oxides on the surface of a steel cord, and is advantageous in adhesion to the surface of a steel cord (metal).
In the present invention, the softening point of the above mixture can be measured in accordance with JIS K5601.
< content of mixture >
In the present invention, the content of the mixture is 2.0 to 10.0 parts by mass with respect to 100 parts by mass of the rubber component.
From the viewpoint of the excellent effect and durability of the present invention, the content of the mixture is preferably 2 to 8 parts by mass, more preferably 5 to 7 parts by mass, per 100 parts by mass of the rubber component.
< diethylene glycol >
The compositions of the present invention contain diethylene glycol.
The diethylene glycol contained in the composition of the present invention is not particularly limited. The diethylene glycol may be a monomer such as diethylene glycol, or may be a mixture of diethylene glycol and silica (a blend of the two which has been mixed in advance).
Content of diethylene glycol
In the present invention, the content of diethylene glycol is 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the rubber component.
When the content of diethylene glycol is in the above range, the water resistant adhesion is excellent.
If the content of diethylene glycol exceeds 2.5 parts by mass relative to 100 parts by mass of the rubber component, the water-resistant adhesion becomes low.
From the viewpoint of the excellent effects and durability of the present invention, the content of diethylene glycol is preferably 0.4 to 2.0 parts by mass, and more preferably 0.4 to less than 1.0 part by mass, per 100 parts by mass of the rubber component.
< vulcanization accelerator >
The vulcanization accelerator contained in the composition of the present invention is not particularly limited as long as it can be used for a rubber composition vulcanized by sulfur.
Examples of the vulcanization accelerator include aldehyde-ammonia type, aldehyde-amine type, thiourea type, guanidine type, thiazole type, sulfenamide type, thiuram type, dithiocarbamate type, xanthate type, and a mixture thereof.
In the present specification, the above-described vulcanization accelerator is classified as a thiazole-based vulcanization accelerator, in the case where the vulcanization accelerator generally classified as a vulcanization accelerator other than thiazole-based vulcanization accelerators has a thiazole skeleton.
The vulcanization accelerator is preferably a thiazole-based vulcanization accelerator from the viewpoint of further improving the water resistant adhesion.
The thiazole-based vulcanization accelerator is not particularly limited as long as it is a vulcanization accelerator having a thiazole skeleton. Examples of the thiazole-based vulcanization accelerator include a benzothiazole-based vulcanization accelerator having a benzothiazole skeleton.
Vulcanization accelerators having a benzothiazolylthioether group
Examples of the benzothiazole-based vulcanization accelerator include a vulcanization accelerator having a benzothiazyl sulfide group.
The benzothiazolyl sulfide group can be represented by the following structure, for example. In the following structures, a hydrogen atom in the benzothiazolyl ring may be substituted with a substituent. The substituent in the benzothiazole ring group is not particularly limited.
In the benzothiazolyl sulfide group represented by the above structure, a sulfur atom not constituting a ring structure may constitute, for example, -SH (mercapto); a linker (e.g., a 2-or 3-valent linker) such as a (poly) sulfide bond or a sulfonamide bond (e.g., -S-NH-, -S-N <); the salt is formed with a metal such as zinc or an alkali metal such as sodium.
In the case where the benzothiazolyl sulfide group has the above-mentioned linking group, a group to be further bonded to the above-mentioned linking group is not particularly limited. Examples thereof include hydrocarbon groups which may have hetero atoms such as oxygen, nitrogen and sulfur. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including linear, branched, and cyclic), an aromatic hydrocarbon group, a heterocyclic ring, and a combination thereof.
Examples of the benzothiazolyl sulfide group in which a sulfur atom not constituting a ring structure constitutes a sulfenamide bond (a benzothiazole-based vulcanization accelerator having a sulfenamide bond) include N-cyclohexyl-2-benzothiazolyl sulfenamide, N-tert-butyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide, N-diisopropyl-2-benzothiazolyl sulfenamide, and N, N-dicyclohexyl-2-benzothiazyl sulfenamide.
From the viewpoint of more excellent water-resistant adhesion, the vulcanization accelerator (or the benzothiazole-based vulcanization accelerator) preferably contains benzothiazole having a mercapto group or a polysulfide bond, or mercaptobenzothiazole which forms a salt with a metal or an alkali metal.
Examples of the benzothiazole having a mercapto group include 2-mercaptobenzothiazole (the following structure).
Examples of the benzothiazole having a polysulfide bond include benzothiazoles having a disulfide bond such as bis-2-benzothiazolylthiodisulfide (the following structure).
Examples of mercaptobenzothiazoles which form salts with metals or alkali metals include zinc salts of 2-mercaptobenzothiazole (the following structure),
Sodium salt of 2-mercaptobenzothiazole (structure below).
From the viewpoint of more excellent water-resistant adhesion, the vulcanization accelerator (or the benzothiazole-based vulcanization accelerator) is preferably at least 1 selected from the group consisting of 2-mercaptobenzothiazole, di-2-benzothiazyl disulfide, and zinc salts of 2-mercaptobenzothiazole, and more preferably di-2-benzothiazyl disulfide.
(content of vulcanization accelerator)
From the viewpoint of more excellent water-resistant adhesion, the content of the vulcanization accelerator in the composition of the present invention is preferably more than 0.0 part by mass and 1.5 parts by mass or less, preferably 0.1 to 0.7 part by mass, and more preferably 0.3 to 0.7 part by mass, per 100 parts by mass of the rubber component.
Organic acid cobalt salt
The organic acid cobalt salt contained in the composition of the present invention is not particularly limited as long as it is a salt formed from an organic acid and cobalt.
(organic acid)
Examples of the organic acid constituting the organic acid cobalt salt include compounds having a carboxyl group. The above carboxyl group may be combined with an organic group. The organic group is not particularly limited. Examples thereof include hydrocarbon groups. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
Examples of the aliphatic hydrocarbon group include straight chain, branched chain, cyclic, and combinations thereof. The aliphatic hydrocarbon group may have an unsaturated bond.
(Carboxylic acid ion)
When the organic acid forming the organic acid cobalt salt is a compound having a carboxyl group, the organic acid cobalt salt has a carboxyl ion (-COO)-) May be derived from the carboxyl group of the organic acid.
(cobalt ion)
In the organic acid cobalt salt, the counter ion of the anion (derived from the acid) such as the carboxyl ion is a cobalt ion (e.g., Co) contained in the organic acid cobalt salt2+、Co3+)。
Examples of the organic acid cobalt salt include organic acid cobalt salts containing no boron, such as cobalt naphthenate, cobalt stearate, cobalt octylate, and cobalt neodecanoate; cobalt salts of organic acids containing boron.
From the viewpoint of further improving the effect and durability of the present invention, the organic acid cobalt salt preferably contains boron.
Examples of the organic acid cobalt salt containing boron include a complex salt in which a part of an organic acid is substituted with boric acid or the like.
Specific examples of the organic acid cobalt salt include, for example, a cobalt boron complex compound such as cobalt neodecanoate borate represented by the following formula (1).
From the viewpoint of further improving the effect and durability of the present invention, the organic acid cobalt salt is preferably cobalt neodecanoate borate.
(cobalt content in organic acid cobalt salt)
The content of cobalt in the organic acid cobalt salt contained in the composition of the present invention is preferably 0.22 to 1.20 parts by mass, and more preferably 0.25 to 0.80 part by mass, per 100 parts by mass of the rubber component.
< Sulfur >
The composition of the present invention contains sulfur. The above sulfur is not particularly limited. For example, elemental sulfur may be mentioned.
(content of sulfur)
From the viewpoint of the excellent effects and durability of the present invention, the content of sulfur in the composition of the present invention is preferably 2.1 to 6.0 parts by mass, more preferably 3.5 to 5.0 parts by mass, per 100 parts by mass of the rubber component.
(Compound A)
The composition of the present invention preferably further contains at least 1 compound a selected from rosins, phenol resins and chloroparaffins.
The composition of the present invention further contains compound a, and therefore has more excellent water-resistant adhesion.
(rosins)
The composition of the present invention may further contain a rosin.
Examples of the rosin include rosin and rosin derivatives.
Rosin (R)
Rosin is generally a natural resin obtained by distilling rosin or the like.
When rosin is exemplified from the viewpoint of the production as described above, examples of the rosin include gum rosin, wood rosin, and tall oil rosin.
The rosin (among gum rosin, wood rosin, and tall oil rosin) is preferably gum rosin, from the viewpoint of further improving the effect of the present invention.
Furthermore, rosin generally comprises resin acids.
Examples of the resin acid include abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, and dehydroabietic acid.
The various resin acids described above are common in that they have a carboxyl group as a functional group.
The rosin may contain at least 1 selected from abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, and dehydroabietic acid. Further, the rosin may be a mixture containing at least 2 or more selected from the above group.
The ratio of the resin acid component generally varies depending on the kind of rosin such as gum rosin.
Rosin derivatives
Examples of the rosin derivative (modified rosin) include compounds obtained by acid-modifying, disproportionating (double-bonding), hydrogenating, dimerizing, or esterifying the resin acid.
The rosin preferably contains rosin from the viewpoint of further improving the effect of the present invention.
Softening point of rosins
The softening point of the rosin is preferably 40 to 130 ℃, and more preferably 50 to 100 ℃ from the viewpoint of further enhancing the effect of the present invention.
The softening point of the rosin can be measured according to JIS K5902-1969.
Acid value of rosins
The acid value of the rosin may be 50mgKOH/g or more.
From the viewpoint of further improving the effect of the present invention, the acid value of the rosin is preferably 50 to 200mgKOH/g, and more preferably 80 to 180 mgKOH/g.
The acid value of the rosin can be determined in accordance with JIS K2501: 2003.
Molecular weight of rosins
The molecular weight of the rosin is preferably 200 to 1000, more preferably 250 to 400, from the viewpoint of further improving the effect of the present invention.
The molecular weight of rosins can be determined by Gel Permeation Chromatography (GPC).
Since rosins are generally a mixture, the molecular weights of the rosins may be average values.
From the viewpoint of further improving the effect of the present invention and the durability, the content of the rosin is preferably 3 to 10 parts by mass per 100 parts by mass of the rubber component.
Chlorinated alkane
The chlorinated paraffin is not particularly limited as long as it is a paraffin having chlorine. Examples thereof include, on average, a chain-like saturated hydrocarbon compound having 26 carbon atoms, in which all or a part of hydrogen atoms are substituted with chlorine atoms.
The amount of chlorine contained in the chlorinated paraffin is preferably, for example, 40 to 80% by mass based on the total amount of chlorinated paraffin.
From the viewpoint of further improving the effect of the present invention and the durability, the content of the chloroparaffin is preferably 3 to 8 parts by mass per 100 parts by mass of the rubber component.
From the viewpoint of further improving the effects of the present invention and improving the durability, the compound a preferably contains rosin or the rosin derivative and chloroparaffin.
(carbon Black)
The composition of the present invention may further contain carbon black.
The carbon black is not particularly limited.
Among these, the carbon black is preferably an HAF-grade carbon black or an ISAF-grade carbon black, and more preferably an HAF-grade carbon black, from the viewpoint of further improving the effect of the present invention.
(nitrogen adsorption specific surface area of carbon Black)
From the viewpoint that the effect of the present invention is more excellent, the nitrogen adsorption specific surface area (N) of the carbon black is2SA) is preferably 60 to 120m2A concentration of 65 to 95m is more preferable2/g。
The nitrogen adsorption specific surface area of carbon black can be determined in accordance with JIS K6217-2: 2017 "(2 nd: determination of specific surface area-nitrogen adsorption method-single point method)'.
(content of carbon Black)
From the viewpoint of further improving the effect of the present invention, the content of the carbon black is preferably 35 to 75 parts by mass, and more preferably 40 to 70 parts by mass, based on 100 parts by mass of the rubber component.
(anti-aging agent)
The composition of the present invention may further contain an antioxidant.
The antioxidant is not particularly limited. Examples thereof include conventionally known antioxidants.
From the viewpoint of further improving the effect of the present invention, the content of the antioxidant is preferably 1.0 part by mass or more per 100 parts by mass of the rubber component.
The upper limit of the content of the antioxidant may be 5.0 parts by mass or less with respect to 100 parts by mass of the rubber component.
(Zinc oxide)
The composition of the present invention may further contain zinc oxide. The zinc oxide is not particularly limited.
(content of Zinc oxide)
From the viewpoint of further improving the effect of the present invention, the content of the zinc oxide is preferably 5.0 parts by mass or more per 100 parts by mass of the rubber component.
The upper limit of the content of the zinc oxide may be 20 parts by mass or less with respect to 100 parts by mass of the rubber component.
The composition of the present invention may further contain, in addition to the above-mentioned essential components, additives such as phenols other than the above-mentioned specific phenols, metal salts other than organic acid cobalt salts, stearic acid, fillers other than carbon black, and oils, as necessary, within a range not to impair the object of the present invention.
The composition of the present invention can be produced by mixing the above-mentioned essential components and, if necessary, the above-mentioned carbon black and the like with a roll mill, a banbury mixer or the like.
The composition of the present invention can be used for example for bonding steel cords (specifically, for example, galvanized steel cords).
By using the composition of the present invention together with a steel cord (e.g., a galvanized steel cord), for example, vulcanization is performed, a composite body having a vulcanized rubber and a steel cord can be obtained. The vulcanized rubber and the steel cord may be bonded to each other in the composite.
Examples of the steel cord include a steel cord; a steel cord galvanized with zinc.
The steel cord is preferably galvanized from the viewpoint of further excellent effects and excellent rust prevention properties of the present invention.
The wire diameter, the cord diameter, and the like of the steel cord (including galvanized steel cord, the same applies hereinafter) can be appropriately selected. The steel cord may be a surface-untreated one.
The temperature at which the composition of the present invention is vulcanized may be, for example, about 140 to 160 ℃.
The composition of the present invention can be suitably used for, for example, the production of a conveyor belt. In the case where the composition of the present invention is used for the production of a conveyor belt, the composition of the present invention is preferably formed into a coating rubber layer (e.g., cushion rubber and/or joint rubber) coating a steel cord, for example, as a member constituting the conveyor belt. The 1 coating rubber layer coating the steel cord may have functions of both cushion rubber and joint rubber.
As the cushion rubber, for example, when the conveyor belt has a cover rubber layer, there can be mentioned a rubber adjacent to the cover rubber layer.
Examples of the joint rubber include rubbers capable of connecting the conveyor belt to the end portion, for example. The conveyor belt may be lengthened and/or looped by attachment using a joint rubber.
[ conveyor belt ]
Next, the conveyor belt of the present invention will be explained below.
The conveyor belt of the present invention is formed using the rubber composition for bonding steel cords of the present invention.
It is preferable that the conveyor belt of the present invention has a steel cord. From the viewpoint of further improving the effect of the present invention, it is preferable that the steel cord is obtained by galvanizing a steel cord.
The rubber composition for bonding a steel cord used for the conveyor belt of the present invention is not particularly limited as long as it is the composition of the present invention.
From the viewpoint that the effect of the present invention is more excellent, it is preferable that the composition of the present invention forms a coating rubber layer (e.g., cushion rubber and/or joint rubber) coating the steel cord.
The conveyor belt of the present invention may preferably further include a rubber coating layer. The rubber composition capable of forming the cover rubber layer is not particularly limited.
When the coating rubber layer formed from the composition of the present invention is a tie rubber, the cover rubber layer may or may not be adjacent to the coating rubber layer.
The conveyor belt according to the present invention will be described below with reference to the drawings. The conveyor belt of the present invention is not limited to the drawings.
Fig. 1 is a sectional perspective view schematically showing an example of a conveyor belt according to the present invention.
In fig. 1, the conveyor belt 1 has cover rubber layers 6 on both surfaces, and has steel cords 2 and a coating rubber layer 4 between the cover rubber layers 6. The coating rubber layer 4 coats the steel cord 2. The coating rubber layer 4 is preferably formed of the rubber composition for bonding steel cords of the present invention.
Examples
The following examples illustrate the present invention in detail. However, the present invention is not limited thereto.
< production of composition >
The components shown in table 1 below were used in the compositions (parts by mass) shown in the table.
First, the components shown in the following table 1 except sulfur and vulcanization accelerator were mixed with a banbury mixer, then, the amount shown in table 1 was added to the mixture, and they were mixed with a roller to prepare each composition.
[ evaluation ]
The following evaluations were made using each composition produced as described above. The results are shown in table 1.
< Water-resistant adhesion >
The water-resistant adhesion was evaluated by the rubber adhesion rate.
Evaluation method
Each of the compositions prepared as described above was applied to a galvanized steel cord having a diameter of 4.1mm, which was stored in a dryer and subjected to dust-proof and moisture-proof treatment, at a thickness of 15mm to prepare a composite of each composition and the steel cord (a state in which the steel cord was embedded in the composition), and the composite was press-vulcanized for 20 minutes at 153 ℃ and a surface pressure of 2.0MPa using a press molding machine to prepare a test piece (rubber/galvanized steel cord composite). In the test piece, the boundary between the rubber and the steel cord at the position where the steel cord protrudes from the rubber surface was sealed with beeswax, and the test piece was placed in a constant temperature and humidity bath at a temperature of 50 ℃ and a relative humidity of 95% for 3 weeks. Then, a steel cord pulling test was performed at room temperature (23 ℃ C.) to pull out the steel cord from each test piece. The above-mentioned pull-out test was carried out in accordance with DIN 22131.
After the pull-out test, the state of the pulled-out steel cord was confirmed, and the ratio of the coated area of the rubber remaining on the surface of the steel cord after the pull-out to the initial surface area of the steel cord (rubber coating percentage,%) was calculated. The rubber coverage calculated as described above is shown in table 1 as the rubber adhesion.
Evaluation criteria
In the present invention, when the rubber adhesion rate (rubber coverage) exceeds 60%, the water resistant adhesion is evaluated to be excellent.
When the rubber adhesion rate was 60% or less, the water-resistant adhesion was evaluated to be poor.
The larger the rubber adhesion rate, the more excellent the water-resistant adhesion was evaluated to be, the more 60%.
[ Table 1]
The details of each component shown in table 1 are as follows.
(diene rubber)
Diene rubber 1 (NR): natural rubber. TSR20
Diene rubber 2 (SBR): styrene butadiene copolymer rubber was solution polymerized. Trade name タフデン 2000R (manufactured by Asahi Kasei corporation). Glass transition temperature-70 ℃. Weight average molecular weight 32 ten thousand, bound styrene amount 27 mass%, vinyl amount 9 mass%
(mixture)
Mixture: comprising a mixture of m-cresol novolac resin, phenol, m-cresol and formaldehyde. In the above mixture, the content of cresol novolac resin was 95 mass%, the content of cresol was 1.5 mass%, and the remainder contained phenol and formaldehyde. Trade name スミライトレジン PR-175, manufactured by Sumitomo デュレズ. The softening point of the mixture is 55-70 ℃.
(comparative) Resorcinol resin: trade name スミカノ - ル 620, manufactured by Taoka chemical industries, Ltd. The resorcinol resin does not contain phenols having 1 phenolic hydroxyl group and may further have a substituent (wherein the phenolic hydroxyl group is not included). Instead, resorcinol (having 2 phenolic hydroxyl groups per 1 molecule) is included.
Curing agent for the above (comparative) resorcinol resin: trade name スミカノ ー ル 507AP, manufactured by Taoka chemical industries, Ltd. Polymethylolmelamine derivatives
(Compound A)
Rosins (gum rosins): china rosin WW, manufactured by Mitsui chemical industries, Inc. Softening point: 65 ℃, acid value: 162mgKOH/g, molecular weight: 289
Chlorinated alkane: chloroparaffins (chlorine content 70 mass%). エンパラ 70S, manufactured by Meizizhisu ファインテクノ.
(cobalt salt of organic acid)
Organic acid cobalt salt 1 (cobalt naphthenate 10%): cobalt naphthenate. The cobalt naphthenate contained 10 mass% of cobalt. The product was named "ナフテン acid コバルト 10%", manufactured by DIC CORPORATION.
Organic acid cobalt salt 2 (cobalt neodecanoate borate): cobalt neodecanoate borate represented by the following formula (1). DICNATE NBC-II (cobalt content in cobalt neodecanoate borate: 22.2% by mass) produced by DIC CORPORATION
HAF grade carbon black: シヨウブラック N330T (nitrogen adsorption specific surface area 74m, manufactured by キャボットジャパン K.K.)2/g)
Anti-aging agent (OD-3): p, p' -dioctyldiphenylamine represented by the following formula. ノンフレックス OD-3, available from Seiko chemical Co., Ltd. The antioxidant does not function as a vulcanization accelerator.
Zinc oxide: 3 kinds of zinc oxide produced by the same chemical industry society
Stearic acid: stearic acid YR (manufactured by Nichisu)
(diethylene glycol)
Diethylene glycol: as diethylene glycol, a product name DST パウダー 1.6.6 (a blend of diethylene glycol and silica 60: 40 (mass ratio)) manufactured by japan ピグメント co. The amount shown in the diethylene glycol column in table 1 is the amount of diethylene glycol contained in the DST powder used.
(vulcanization accelerators)
Vulcanization accelerator 1 (DM): a thiazole-based vulcanization accelerator. Dibenzothiazyl disulfide (structure below). サンセラー DM-PO, (manufactured by Sanxin chemical industry Co., Ltd.)
Vulcanization accelerator 2 (sulfenamide): n, N-dicyclohexyl-2-benzothiazylsulfenamide (structure: below), ノクセラー DZ, a product of Dainiji chemical industries, Ltd
Sulfur: jinhua stamp-pad ink into micropowder sulfur (Crane manufactured by chemical industry Co., Ltd.)
As is clear from the results shown in Table 1, comparative example 1 containing no diethylene glycol had poor water-resistant adhesion.
Comparative example 2, which contained (comparative) resorcinol resin and its curing agent instead of the specified mixture, was inferior in water-resistant adhesion.
In contrast, the composition of the present invention is excellent in water-resistant adhesion.
Description of the symbols
1 conveyor belt
2 steel cord
4 coating rubber layer
6 covering the rubber layer.
Claims (11)
1. A rubber composition for bonding a steel cord, comprising:
a rubber component containing at least a diene rubber;
a mixture comprising a phenol having 1 phenolic hydroxyl group and which may further have a substituent excluding the phenolic hydroxyl group, and a phenol resin;
diethylene glycol;
a vulcanization accelerator;
organic acid cobalt salts; and
the amount of sulfur is such that,
the content of the mixture is 2.0-10.0 parts by mass relative to 100 parts by mass of the rubber component,
the content of the diethylene glycol is 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the rubber component.
2. A rubber composition for adhesion of steel cord according to claim 1, wherein said organic acid cobalt salt is cobalt neodecanoate borate.
3. The rubber composition for adhesion of steel cord according to claim 1 or 2, wherein the phenol resin is alkylphenol phenol resin.
4. A rubber composition for adhesion of steel cord according to any one of claims 1 to 3, wherein said phenol comprises phenol and/or alkylphenol.
5. A rubber composition for adhesion of steel cord according to any one of claims 1 to 4, said mixture further comprising aldehyde.
6. A rubber composition for steel cord adhesion according to any one of claims 1 to 5, said mixture comprising phenol, cresol novolac as said novolac resin, and formaldehyde.
7. The rubber composition for adhesion of steel cord according to any one of claims 1 to 6, wherein the vulcanization accelerator is a thiazole-based vulcanization accelerator.
8. The rubber composition for adhesion of steel cord according to any one of claims 1 to 7, wherein the vulcanization accelerator is 1.50 parts by mass or less with respect to 100 parts by mass of the rubber component.
9. The rubber composition for bonding a steel cord according to any one of claims 1 to 8, wherein the softening point of the mixture is 85 ℃ or lower.
10. A rubber composition for steel cord adhesion according to any one of claims 1 to 9, which is used for adhesion of a galvanized steel cord.
11. A conveyor belt comprising the rubber composition for bonding steel cord according to any one of claims 1 to 10.
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|---|---|
| JP7372529B2 (en) | 2023-11-01 |
| JP2021059624A (en) | 2021-04-15 |
| CN112608525B (en) | 2023-04-11 |
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