JPH0147511B2 - - Google Patents
Info
- Publication number
- JPH0147511B2 JPH0147511B2 JP18082280A JP18082280A JPH0147511B2 JP H0147511 B2 JPH0147511 B2 JP H0147511B2 JP 18082280 A JP18082280 A JP 18082280A JP 18082280 A JP18082280 A JP 18082280A JP H0147511 B2 JPH0147511 B2 JP H0147511B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- sulfochlorinated
- aqueous
- shp
- polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001971 elastomer Polymers 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 37
- -1 polyethylene Polymers 0.000 claims description 37
- 239000005060 rubber Substances 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000002657 fibrous material Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 239000004815 dispersion polymer Substances 0.000 claims 2
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical class C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 25
- 229920002943 EPDM rubber Polymers 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000000835 fiber Substances 0.000 description 18
- 229920000126 latex Polymers 0.000 description 17
- 239000004816 latex Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 9
- 229920005549 butyl rubber Polymers 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 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
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明はゴム類と繊維用材料類との接着方法に
関するものである。
ゴム類の用途にはタイヤ、ベルト、防水シート
などのごとく、補強用繊維類とゴム類の接着が重
視される用途が多い。
天然ゴム（以下NRと略す）やスチレンブタジ
エン共重合ゴム（以下SBRと略す）などと繊維
類との接着には、従来よりレゾルシンホルムアル
デヒド樹脂水性液とNRラテツクス、SBRラテツ
クスあるいはスチレン・ブタジエン・ビニルピリ
ジン三元共重合ゴムラテツクスなどとの組成物が
いわゆるRFL接着剤として使用されている。
ところがエチレンとエチレンより高級なα−オ
レフインと非共役ジオレフインとからなる三元共
重合ゴム（以下EPDMと略す）は耐候性、耐オ
ゾン性、耐熱性などの点で、従来タイヤ、ベルト
などに主として使用されているNR、SBRなどの
高不飽和ゴムよりもはるかにすぐれているにもか
かわらず、繊維類との接着性が小さく上記の
RFL接着剤を使用しても充分な接着強度が得ら
れないため用途が限られている。また、イソブチ
レンイソプレン共重合ゴム（ブチルゴム−以下
IIRと略す）なども同様な事情を有す。
そこで本発明者らはEPDMなどと繊維類の接
着方法について鋭意検討を重ねた結果、レゾルシ
ン・ホルムアルデヒド樹脂水性液（以下RF液と
略す）とスルホハロゲン化ポリマー（以下SHP
と略す）の有機溶剤溶液または水分散液を併用す
ることによりすぐれた接着効果が得られることを
見出した。
さらに本発明の接着方法によればNRやSBRな
どのゴム類に対してもすぐれた接着効果を有する
ことを見出した。
なお本発明の接着方法がSHP類と繊維類との
接着に有効なのは当然である。
本発明によりEPDMやIIRなどの使用を大幅に
拡大するなどその工業的価値は極めて大きい。
RFL系接着剤が強力な接着力を示すためには、
ゴム−接着剤中ポリマ−成分−レゾルシン・ホル
ムアルデヒド樹脂−繊維の間に強い結合力が存在
することが必要であり、通常のRFL接着剤に用
いられるスチレン・ブタジエン・ビニルピリジン
三元共重合体ゴムに比し、本発明で使用する
SHPが各種ゴム類との相溶性がすぐれ、しかも
含有するスルホハロゲン基やハロゲンによる極性
によつてレゾルシン・ホルムアルデヒド樹脂に対
しても相溶性がすぐれているため強固な接着力を
示すものと考えられる。
なおEPDMと繊維類の接着にRF液とEPDMハ
ロゲン化物の水分散液からなる組成物を用いる方
法が提案（特公昭46−22358号）されているが、
後記の実施例などで示すごとく、本発明は接着性
においてすぐれているばかりでなく本発明で使用
するSHPは水分散液の製造が、より容易であり、
かつ、RF液との混合物の安定性がすぐれている
などの利点を有している。
本発明の方法では、まず浸漬、塗布、吹付けロ
ール処理などの適当な方法で、繊維類にRF液を
含浸させ、そのまま、または必要なら適当な乾
燥、熱処理などの工程を経るなどあらかじめレゾ
ルシン・ホルムアルデヒド樹脂で処理された繊維
類に浸漬、塗布、吹付け、ロール処理などの適当
な方法でSHPの有機溶剤溶液や水分散液を含浸
させ、乾燥、熱処理などの工程を経て、各種添加
剤の配合されたEPDMなどのゴム類と接触加硫
処理する方法や、RF液とSHP水分散液をあらか
じめ混合した組成物を浸漬、塗布、吹付け、ロー
ル処理などの適当な方法で、繊維類に浸漬後、乾
燥、熱処理などの工程を経て、各種添加剤の配合
されたEPDMなどのゴム類と接触加硫処理する
方法などによりEPDMなどのゴム類と繊維類と
を強固に接着せしめるものである。
これらの方法のうちRF液とSHP水分散液をあ
らかじめ混合した組成物を用いて繊維類を処理す
る方法は工程が単純化されるなど工業的に有利で
あり、この際使用する組成物はすぐれた接着用組
成物である。
本発明で使用するSHPとは、エチレン、プロ
ピレン、ｎ−ブチレン、イソブチレン、ブタジエ
ン、イソプレン等の単独重合体、これらの任意の
２種以上の相互共重合体およびこれらとエチリデ
ンノルボーネン、５−メチル−２−ノルボーネ
ン、1.4−ヘキサジエン、ジシクロペンタジエン、
1.5−シクロオクタジエン、ジビニルベンゼン等
の非共役ジエン類やスチレン、塩化ビニル、酢酸
ビニル、アクリル酸、メタアクリル酸、各種アク
リル酸エステル類、各種メタアクリル酸エステル
類等との共重合体をハロゲンと二酸化硫黄または
ハロゲン化スルフリルで処理して生成したと考え
られる構造を有するポリマーであり、通常は適当
なポリマーをスルホハロゲン化して製造されたも
のを単独あるいは混合して使用する。
ハロゲンとしては塩素や臭素が通常使用され
る。たとえばEPDMやIIRと繊維類の接着の場合
には、ポリエチレン、ポリプロピレン、エチレン
プロピレン共重合体、EPDMエチレン酢酸ビニ
ル共重合体、IIR等のスルホクロル化物が通常使
用される。この場合、塩素含有量５〜70重量％、
好ましくは10〜50重量％さらに好ましくは18〜45
重量％、硫黄含有量0.1〜10重量％、好ましくは
0.2〜３重量％さらに好ましくは0.5〜2.5重量％の
ものを使用することが多い。
なおSHP中のハロゲン量に関しては、接着力
の点より適当な範囲が存在し、あまり少なかつた
り多かつたりすると充分な接着力が得られないこ
とがある。また硫黄含有量に関しては、あまり少
量では所望の接着力が得難く、またある量以上と
なると一般に熱安定性が低下する。
原料樹脂としてポリエチレンを使用する場合に
は密度が0.94ｇ/cm3以下好ましくは0.934ｇ/cm3以
下のもの、さらにいえばそれらの内溶融指数（以
下MIと略す）が４以上好ましくは５以上のもの、
さらに好ましくは５〜250のもの、ポリプロピレ
ンを使用する場合には密度0.85〜0.93ｇ/cm3さら
にMI3〜300のもの、エチレン酢酸ビニル共重合
体を使用する場合には密度0.92〜0.98ｇ/cm3さら
にMI0.6〜60のものEPDMの場合にはエチレン20
〜75重量％、プロピレンおよび前記の非共役ジエ
ン類からなるものを用いた場合に好結果を得る場
合が多い。
スルホハロゲン化法としては、従来公知の方法
により例えば、上記原料ポリマーを溶媒中に分散
または溶解し、必要なら通常のラジカル開始剤な
どの開始剤の存在下または紫外線照射下に、適当
な温度で、ハロゲンと二酸化硫黄またはハロゲン
化スルフリルを反応させる方法を使用することが
多い。溶媒としては四塩化炭素、四塩化エチレ
ン、四塩化エタン、各種弗素化塩素化炭化水素類
などハロゲン化炭化水素類を使用することが多
い。
これらのSHPを溶液として使用する場合の溶
剤としては種々のものを使用し得るが、通常ベン
ゼン、トルエン、キシレン、エチルベンゼンなど
の芳香族炭化水素類や前記のスルホハロゲン化溶
媒のごときハロゲン化炭化水素類を使用すること
が多く、とくにハロゲン化炭素水素中でスルホハ
ロゲン化反応した生成物は、通常溶液の形で得ら
れるのでこれをそのまま使用することも多い。
SHPの種類、加工等によつて異なるが、種々の
濃度、たとえば１％以下のごとき稀薄溶液や60％
以上のごとき濃厚溶液も場合によつては使用可能
である。
SHPを水分散液として使用する場合の水分散
液は適当な原料ポリマーの水分散液をスルホハロ
ゲン化する方法やSHPを水分散化する方法等に
より得られるが、通常は後者の方法が採用され
る。
SHPを水分散化するには通常SHP溶液を適当
な乳化剤を含有する水と高速撹拌などの方法で
SHP溶液相と水相からなる分散液をつくり、次
に加圧下、常圧下もしくは減圧下などの適当な圧
力下で加熱し、液液相から溶剤の一部または全部
を気化留出させるなどの方法で除去し、さらに必
要なら水の一部を気化留出させたり、遠心力を利
用したりして水を除去するなどの方法で５ないし
70重量％程度の適当な濃度に調整する方法などが
行なわれる。
なおこの場合のSHP溶液としては、前記のご
とき芳香族炭化水素類やハロゲン化炭化水素類の
溶液を使うことが多く、とくにハロゲン化炭化水
素中でスルホハロゲン化反応した生成物をそのま
ま使用する方法が有利である。
また、前記SHP水分散化法の途中の生成物の
ごとき、SHP溶液相と水相からなる分散液が
SHPの水分散液の１種として使用し得るのは当
然である。
SHP水分散液では上記製造法に示したごとく
通常分散安定助剤として乳化剤が使用される。こ
の乳化剤として脂肪酸石鹸類、ロジン酸石鹸類、
アルキルエーテルスルホン酸塩類、アルキルスル
ホン酸塩類、アルキル硫酸塩類、アルケンスルホ
ン酸塩類、アルキルエーテルスルホン酸塩類、ジ
アルキルスルホコハク酸塩類、ポリオキシエチレ
ンアルキルエーテル類、ポリオキシエチレンアル
キルエステル類、ポリオキシエチレンアルキルア
リルエーテル類、ポリオキシエチレンアルキルア
リルエステル類、脂肪酸シヨ糖エステル類、ナフ
タリンスルホン酸ソーダホルマリン縮合物、テト
ラアルキルアンモニウム塩類、アルキルピリジニ
ウム塩類、アルキルベンジルアンモニウム塩類、
ポリエチレンポリアミンテトラ酢酸塩類、アルキ
ルベタイン類など、種々の陰イオン界面活性剤、
非イオン界面活性剤、陽イオン界面活性剤さらに
は両性界面活性剤などが使用されるが、これらの
うち接着力の点より一般に陰イオン界面活性剤が
好ましく、とくにステアリン酸、パルミチン酸、
ミリスチン酸、ラウリン酸、オレイン酸、ロジン
酸などのナトリウムやカリウムなどのアルカリ金
属塩やいわゆる牛脂石鹸、榔子油石鹸などのごと
きカルボン酸のアルカリ金属塩を分子中に含有す
るタイプの乳化剤がすぐれている。これらの乳化
剤の混合物が使用されるのは当然でありカルボン
酸アルカリ金属塩タイプの乳化剤を主体に少量の
非イオンタイプの乳化剤を加えて安定性の向上を
はかるなどの方法も行なわれる。これらの乳化剤
はSHPに対し一般に0.01〜20重量％、好ましくは
0.1〜10重量％使用される。0.01％未満では分散
安定化効果が充分でなく20％をこえて使用しても
20％の場合と効果がほとんど変らない。
また、この水分散化に対し水および有機溶剤の
いずれにも溶解するイソプロパノールのような乳
化助剤などを少量併用することも、可能である。
本発明で使用するRF液としては、一般にホル
ムアルデヒドやパラホルムアルデヒドのごときホ
ルムアルデヒドを簡単に生成する物質とレゾルシ
ンのごときジヒドロキシベンゼン類などのフエノ
ール性化合物を適当な公知の方法で反応させた生
成物を使用する。フエノール性化合物１モルに対
しホルムアルデヒド0.5ないし４モルを、アルカ
リ金属水酸化物存在下、PH8〜９の塩基性条件
下やPH3〜４のごとき酸性条件下など種々のPH
条件下で、室温下や加熱下に反応し、必要に応じ
て反応終了時に中和を実施する。さらに必要に応
じて５ないし40重量％のごとき適当な濃度に調整
する。
本発明で使用するRF液とSHP水分散液からな
る組成物は、通常これら両成分を混合し、必要に
応じて５〜60重量％固形分のごとき濃度に調整す
るなどの方法でつくられる。
勿論、水分散液中でホルムアルデヒド等とフエ
ノール性化合物を反応させる方法で製造すること
も可能である場合が少なくないが再現性の点など
問題点がなお多いのが通常である。
本発明においてはRF液中の固型分１に対し
SHP10〜5000重量％好ましくは50〜2000重量％
使用することが多い。
なお本発明で使用するRF液、SHP溶液、SHP
水分散液やRF液とSHP水分散液からなる組成物
には、粘度調整剤、酸化防止剤など種々の助剤を
添加して使用し得るのは当然である。
本発明の方法では、繊維類にRF液を含浸させ
た後必要に応じて室温〜200℃のごとき適当な温
度で乾燥、熱処理し、さらにSHPの溶液や水分
散液を含浸させて同様に室温〜200℃のごとき適
当な温度で乾燥、熱処理を行なつた後、あるいは
繊維類にRF液とSHP水分散液を順次またはあら
かじめ混合後含浸させ室温200℃のごとき適当な
温度で乾燥、熱処理を行つた後、加硫剤、加硫促
進剤、老化防止剤、補強剤などを混合するなど適
当な加硫配合などの配合を行なつたゴムとはり合
せたり、はさんだ状態でたとえば加圧下130〜160
℃数分〜２時間などのごとき、通常の加硫条件下
で加硫するなどのゴムの仕上げ処理を加えること
により接着が完成される。
なお、接着剤は任意の量を使用し得るが、たと
えばRF液固型分とSHPの合計量で通常繊維に対
し３〜30重量％のごとき量を使用する。
本発明の方法は、NR、イソプレンゴム、
SBR、ブタジエンゴム、アクリロニトリル・ブ
タジエンゴム、IIR、EPDM、エチレンプロピレ
ンゴム、スルホクロル化ポリエチレンゴム（以下
CSMと略す）など種々のゴムと木綿、レーヨン、
アセテート、ナイロン、ポリエステル、ビニロ
ン、アクリル、ポリプロピレンなどの種々の繊
維、とくにEPDM、エチレンプロピレンゴム、
IIR、クロロスルホン化ポリエチレンゴムなどの
ゴムと木綿、レーヨン、ナイロン、ポリエステ
ル、ビニロンなどの繊維の接着に有効である。勿
論、上記繊維材料は狭義の繊維状の場合のみでな
く布などの繊維の形状の場合も含まれるのは当然
である。また、上記繊維材料からなるシートや成
型物と上記ゴムとの接着にも本発明の方法が有効
である。また、CSMと各種ゴム類との混合物を
ゴム類として使用するなど、CSMを併用するこ
とにより好結果を得ることが多く、とくに
EPDMやIIRの場合などその効果が顕著である。
また、本発明の方法や組成物において、NRラ
テツクス、SBRラテツクスあるいはスチレンブ
タジエンビニルピリジン三元共重合体ラテツクス
などのラテツクス類や、従来のRFL接着剤を任
意の方法で併用し得るのは当然であり好結果を得
る場合が少なくない。
以下実施例により本発明を更に詳細に説明す
る。
実施例 １
スルホクロル化ポリエチレンラテツクス
（CSMラテツクス）の調製
低密度ポリエチレン（MI20）より製造したス
ルホクロル化ポリエチレン（塩素含量29％、硫黄
含量１％）40ｇを370ｇのトルエンに溶解した。
ロジン酸カリの25％水溶液4.8ｇを水で370ｇま
で稀釈した液と、上記トルエン溶液を混合し、高
速撹拌機で20分間乳化した。
この乳化液を、温度計、撹拌機、冷却器を備え
た２ガラスフラスコに仕込み、150〜100mmHg
の減圧下、70℃の水浴で加熱し、先ずトルエンを
留去、次いで水を留去することにより内容物が
131ｇになるまで濃縮した。
本方法によりゴム分30.5％の白色ラテツクスを
得た。
RF液の調製
苛性ソーダ0.4ｇを水242ｇに溶解した液に、レ
ゾルシン11ｇと37％ホルマリン水溶液16.2ｇを混
合し、室温で５時間放置、熟成した。
RFL液の調製
前記CSMラテツクス21.1ｇとRF液20ｇを混合
し、室温で２時間放置熟成した。
RF液中の固形分／CSMラテツクス中SHP分の
比は1/5である。
被着ゴムの配合
EPDM※E502 70部
EPDM※E512F 30部
亜鉛華 ５部
ステアリン酸 １部
MAFカーボン 110部
ダイアナプロセスNM280 70部
Ｎ−シクロヘキシル−２−ベンゾチアジル−
スルフエンアミド 1.5部
テトラメチルチウラムジスルフイド 0.5部
ジペンタメチレンチウラムテトラスルフイド
0.7部
ジブチルジチオカルバミン酸亜鉛 1.5部
硫 黄 １部
※ 住友化学工業(株)製エスプレン（エチレンプ
ロピレンエチリデンノルボーネン三元共重
合ゴム）
接着力の測定
1260デニールのナイロンコードを上記RFL液
に浸漬した後150℃の恒温乾燥機中３分間乾燥お
よびベーキングを行なつた。
このようにして調製した処理コードを上記の未
加硫被着ゴム配合物中に埋め込み、150℃で30分
間加硫してＨテスト試験片を作成し、Indian
Rubber World第114巻第213〜217頁（1946）記
載の“Ｈ−プル試験”で接着強度を測定し4.9
Kg／９mmの値を得た。
実施例 ２〜３
CSMラテツクスとRF液の混合割を変更して、
実施例１と同様の測定を行ない第１表の結果を得
た。
The present invention relates to a method of adhering rubber and textile materials. There are many uses for rubber, such as tires, belts, and waterproof sheets, where adhesion between reinforcing fibers and rubber is important. For bonding natural rubber (hereinafter abbreviated as NR) and styrene-butadiene copolymer rubber (hereinafter abbreviated as SBR) to fibers, aqueous resorcin formaldehyde resin and NR latex, SBR latex, or styrene-butadiene-vinylpyridine have traditionally been used. Compositions with ternary copolymer rubber latex and the like are used as so-called RFL adhesives. However, ternary copolymer rubber (hereinafter referred to as EPDM) consisting of ethylene, α-olefin, which is higher than ethylene, and non-conjugated diolefin, has been mainly used in tires, belts, etc. due to its weather resistance, ozone resistance, and heat resistance. Although it is far superior to the highly unsaturated rubbers used, such as NR and SBR, it has poor adhesion to fibers and is
Even if RFL adhesive is used, sufficient adhesive strength cannot be obtained, so its applications are limited. In addition, isobutylene isoprene copolymer rubber (butyl rubber)
(abbreviated as IIR) etc. have similar circumstances. Therefore, the inventors of the present invention have conducted intensive studies on bonding methods between EPDM and other fibers, and have found that aqueous resorcinol-formaldehyde resin liquid (hereinafter referred to as RF liquid) and sulfohalogenated polymer (hereinafter referred to as SHP)
It has been found that an excellent adhesive effect can be obtained by using an organic solvent solution or an aqueous dispersion of . Furthermore, it has been found that the adhesion method of the present invention has an excellent adhesion effect on rubbers such as NR and SBR. It goes without saying that the adhesion method of the present invention is effective in adhering SHPs and fibers. The present invention greatly expands the use of EPDM, IIR, etc., and its industrial value is extremely large. In order for RFL adhesives to exhibit strong adhesive strength,
Rubber - The polymer component in the adhesive - resorcinol/formaldehyde resin - It is necessary to have strong bonding strength between the fibers, and the styrene/butadiene/vinylpyridine terpolymer rubber used in normal RFL adhesives. used in the present invention compared to
It is thought that SHP exhibits strong adhesive strength because it has excellent compatibility with various rubbers, and also with resorcinol and formaldehyde resins due to the polarity of the sulfohalogen groups and halogens it contains. . Note that a method using a composition consisting of an RF liquid and an aqueous dispersion of an EPDM halide for bonding EPDM and fibers has been proposed (Japanese Patent Publication No. 46-22358);
As shown in the examples below, the present invention not only has excellent adhesive properties, but also the SHP used in the present invention is easier to prepare as an aqueous dispersion.
In addition, it has advantages such as excellent stability of the mixture with the RF liquid. In the method of the present invention, fibers are first impregnated with the RF liquid by an appropriate method such as dipping, coating, or spray roll treatment, and then the fibers are treated with resorcinol, either as is or, if necessary, through appropriate drying, heat treatment, etc. Fibers treated with formaldehyde resin are impregnated with an organic solvent solution or aqueous dispersion of SHP using an appropriate method such as dipping, coating, spraying, or roll treatment, and then through processes such as drying and heat treatment, various additives are applied. Fibers can be cured by contact vulcanization with compounded rubber such as EPDM, or by dipping, coating, spraying, or roll treatment with a premixed composition of RF liquid and SHP water dispersion. After dipping, drying, heat treatment, and other processes, rubber such as EPDM and fibers are strongly bonded by contact vulcanization treatment with rubber such as EPDM containing various additives. . Among these methods, the method of treating fibers using a composition in which RF liquid and SHP aqueous dispersion are mixed in advance is industrially advantageous because the process is simplified, and the composition used in this case is of excellent quality. It is an adhesive composition. SHP used in the present invention refers to homopolymers of ethylene, propylene, n-butylene, isobutylene, butadiene, isoprene, etc., copolymers of any two or more of these, and copolymers of these with ethylidenenorbornene, 5-methyl -2-norbornene, 1,4-hexadiene, dicyclopentadiene,
1.5- Copolymers with non-conjugated dienes such as cyclooctadiene and divinylbenzene, styrene, vinyl chloride, vinyl acetate, acrylic acid, methacrylic acid, various acrylic esters, various methacrylic esters, etc. It is a polymer with a structure thought to have been produced by treating it with sulfur dioxide or sulfuryl halide, and it is usually produced by sulfohalogenating an appropriate polymer and is used alone or in combination. Chlorine and bromine are commonly used as halogens. For example, in the case of adhering EPDM or IIR to fibers, polyethylene, polypropylene, ethylene propylene copolymer, EPDM ethylene vinyl acetate copolymer, sulfochloride of IIR, etc. are usually used. In this case, the chlorine content is 5-70% by weight,
Preferably 10-50% by weight, more preferably 18-45%
% by weight, sulfur content 0.1-10% by weight, preferably
0.2 to 3% by weight, more preferably 0.5 to 2.5% by weight, is often used. Regarding the amount of halogen in SHP, there is an appropriate range from the viewpoint of adhesive strength, and if it is too little or too much, sufficient adhesive strength may not be obtained. Regarding the sulfur content, if the content is too small, it is difficult to obtain the desired adhesive strength, and if the content exceeds a certain level, the thermal stability generally decreases. When polyethylene is used as the raw material resin, it must have a density of 0.94 g/cm 3 or less, preferably 0.934 g/cm 3 or less, and more particularly, a melting index (hereinafter abbreviated as MI) of 4 or more, preferably 5 or more. things,
More preferably, it has a density of 5 to 250, and when polypropylene is used, a density of 0.85 to 0.93 g/cm 3 Furthermore, it has a density of 3 to 300, and when an ethylene vinyl acetate copolymer is used, a density of 0.92 to 0.98 g/cm. 3 Furthermore, in the case of EPDM with MI0.6~60, ethylene 20
Good results are often obtained using ~75% by weight of propylene and the non-conjugated dienes mentioned above. As for the sulfohalogenation method, for example, the above-mentioned raw material polymer is dispersed or dissolved in a solvent by a conventionally known method, and if necessary, in the presence of an initiator such as a common radical initiator or under ultraviolet irradiation, at an appropriate temperature. , a method of reacting halogen with sulfur dioxide or sulfuryl halide is often used. As the solvent, halogenated hydrocarbons such as carbon tetrachloride, ethylene tetrachloride, ethane tetrachloride, and various fluorinated chlorinated hydrocarbons are often used. When using these SHPs as a solution, various solvents can be used, but usually aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and halogenated hydrocarbons such as the sulfohalogenated solvents mentioned above are used. In particular, the product of sulfohalogenation reaction in halogenated carbon hydrogen is usually obtained in the form of a solution, so it is often used as it is.
It varies depending on the type of SHP, processing, etc., but various concentrations, such as dilute solutions of 1% or less and 60%
Concentrated solutions such as those mentioned above may also be used in some cases. When using SHP as an aqueous dispersion, the aqueous dispersion can be obtained by sulfohalogenating an aqueous dispersion of an appropriate raw material polymer or by dispersing SHP in water, but the latter method is usually adopted. Ru. To disperse SHP in water, the SHP solution is usually mixed with water containing an appropriate emulsifier and stirred at high speed.
A dispersion consisting of a SHP solution phase and an aqueous phase is prepared, and then heated under an appropriate pressure such as increased pressure, normal pressure, or reduced pressure to vaporize and distill off part or all of the solvent from the liquid-liquid phase. If necessary, some of the water may be distilled off by vaporization or centrifugal force may be used to remove the water.
A method is used to adjust the concentration to an appropriate concentration of about 70% by weight. In this case, as the SHP solution, a solution of aromatic hydrocarbons or halogenated hydrocarbons as mentioned above is often used, and in particular, a method in which the product of a sulfohalogenation reaction in a halogenated hydrocarbon is used as it is is used. is advantageous. In addition, a dispersion consisting of an SHP solution phase and an aqueous phase, such as the product during the SHP water dispersion method described above, is
It goes without saying that it can be used as a type of aqueous dispersion of SHP. In the SHP aqueous dispersion, an emulsifier is usually used as a dispersion stabilizing agent, as shown in the above production method. Fatty acid soaps, rosin acid soaps,
Alkyl ether sulfonates, alkyl sulfonates, alkyl sulfates, alkenesulfonates, alkyl ether sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylaryl Ethers, polyoxyethylene alkylaryl esters, fatty acid sucrose esters, naphthalene sulfonic acid soda formalin condensates, tetraalkylammonium salts, alkylpyridinium salts, alkylbenzylammonium salts,
Various anionic surfactants such as polyethylene polyamine tetraacetates, alkyl betaines,
Nonionic surfactants, cationic surfactants, and even amphoteric surfactants are used, but from the viewpoint of adhesive strength, anionic surfactants are generally preferred, especially stearic acid, palmitic acid,
Emulsifiers containing alkali metal salts such as sodium and potassium salts such as myristic acid, lauric acid, oleic acid, and rosin acid, as well as alkali metal salts of carboxylic acids such as so-called beef tallow soap and bamboo shoot oil soap, are excellent. ing. Naturally, a mixture of these emulsifiers is used, and methods such as using a carboxylic acid alkali metal salt type emulsifier as the main emulsifier and adding a small amount of a nonionic type emulsifier to improve stability are also used. These emulsifiers are generally 0.01 to 20% by weight of SHP, preferably
Used 0.1-10% by weight. If it is less than 0.01%, the dispersion stabilizing effect will not be sufficient, and even if it is used in excess of 20%.
The effect is almost the same as the 20% case. It is also possible to use a small amount of an emulsification aid such as isopropanol, which is soluble in both water and an organic solvent, for this water dispersion. The RF liquid used in the present invention is generally a product obtained by reacting a substance that easily generates formaldehyde, such as formaldehyde or paraformaldehyde, with a phenolic compound, such as dihydroxybenzenes such as resorcinol, by an appropriate known method. do. 0.5 to 4 moles of formaldehyde per mole of phenolic compound in the presence of an alkali metal hydroxide under various pH conditions such as basic conditions of pH 8 to 9 or acidic conditions such as PH 3 to 4.
The reaction is carried out under the following conditions, at room temperature or under heating, and neutralization is carried out at the end of the reaction, if necessary. Further, the concentration is adjusted to an appropriate concentration such as 5 to 40% by weight, if necessary. The composition consisting of the RF liquid and the SHP aqueous dispersion used in the present invention is usually prepared by mixing these two components and adjusting the concentration to 5 to 60% solids by weight as necessary. Of course, it is often possible to produce by reacting formaldehyde or the like with a phenolic compound in an aqueous dispersion, but there are usually still many problems such as reproducibility. In the present invention, for each solid content in the RF liquid,
SHP10~5000wt% preferably 50~2000wt%
Often used. Note that the RF liquid, SHP solution, and SHP used in the present invention
It goes without saying that various auxiliary agents such as viscosity modifiers and antioxidants can be added to the aqueous dispersion or the composition consisting of the RF liquid and the SHP aqueous dispersion. In the method of the present invention, after the fibers are impregnated with the RF liquid, they are dried and heat treated at an appropriate temperature such as room temperature to 200°C as necessary, and then impregnated with an SHP solution or aqueous dispersion, and then heated at room temperature. After drying and heat treatment at an appropriate temperature such as ~200℃, or by impregnating the fibers with RF liquid and SHP water dispersion sequentially or after mixing in advance, drying and heat treatment at an appropriate temperature such as room temperature 200℃. After that, it is laminated or sandwiched with rubber that has been mixed with a suitable vulcanization compound, such as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a reinforcing agent, etc. ~160
The adhesion is completed by finishing the rubber, such as by vulcanizing it under normal vulcanization conditions, such as several minutes to two hours at 0.degree. Note that any amount of adhesive can be used, but for example, the total amount of RF liquid solid content and SHP is usually used in an amount of 3 to 30% by weight based on the fiber. The method of the present invention includes NR, isoprene rubber,
SBR, butadiene rubber, acrylonitrile-butadiene rubber, IIR, EPDM, ethylene propylene rubber, sulfochlorinated polyethylene rubber (hereinafter referred to as
(abbreviated as CSM), various rubber, cotton, rayon,
Various fibers such as acetate, nylon, polyester, vinylon, acrylic, polypropylene, especially EPDM, ethylene propylene rubber,
Effective for adhering rubbers such as IIR and chlorosulfonated polyethylene rubber to fibers such as cotton, rayon, nylon, polyester, and vinylon. Of course, the above-mentioned fibrous material includes not only fibrous materials in the narrow sense, but also fibrous materials such as cloth. Furthermore, the method of the present invention is also effective for adhering sheets or molded products made of the above-mentioned fiber materials and the above-mentioned rubber. In addition, good results are often obtained by using CSM together, such as using a mixture of CSM and various rubbers as the rubber.
The effect is remarkable in the case of EPDM and IIR. Furthermore, in the method and composition of the present invention, latexes such as NR latex, SBR latex, or styrene-butadiene-vinylpyridine terpolymer latex, as well as conventional RFL adhesives, can of course be used in combination in any desired manner. There are many cases where good results are obtained. The present invention will be explained in more detail with reference to Examples below. Example 1 Preparation of sulfochlorinated polyethylene latex (CSM latex) 40 g of sulfochlorinated polyethylene (chlorine content 29%, sulfur content 1%) produced from low density polyethylene (MI20) was dissolved in 370 g of toluene. A solution obtained by diluting 4.8 g of a 25% aqueous solution of potassium rosin acid to 370 g with water and the above toluene solution were mixed and emulsified for 20 minutes using a high-speed stirrer. Pour this emulsion into two glass flasks equipped with a thermometer, a stirrer, and a condenser to maintain a temperature of 150 to 100 mmHg.
The contents were heated in a water bath at 70°C under reduced pressure, and the toluene was first distilled off, then the water was distilled off.
It was concentrated to 131g. A white latex with a rubber content of 30.5% was obtained by this method. Preparation of RF liquid 11 g of resorcinol and 16.2 g of a 37% formalin aqueous solution were mixed with a solution of 0.4 g of caustic soda dissolved in 242 g of water, and the mixture was allowed to stand at room temperature for 5 hours to age. Preparation of RFL liquid 21.1 g of the CSM latex and 20 g of RF liquid were mixed and left to mature at room temperature for 2 hours. The ratio of solid content in the RF liquid/SHP content in the CSM latex was 1/5. Compound of adhered rubber EPDM*E502 70 parts EPDM*E512F 30 parts zinc white 5 parts stearic acid 1 part MAF carbon 110 parts Diana Process NM280 70 parts N-cyclohexyl-2-benzothiazyl-
Sulfenamide 1.5 parts Tetramethylthiuram disulfide 0.5 parts Dipentamethylenethiuram tetrasulfide
0.7 parts Zinc dibutyl dithiocarbamate 1.5 parts Sulfur 1 part * Esprene (ethylene propylene ethylidene norbornene ternary copolymer rubber) manufactured by Sumitomo Chemical Co., Ltd. Measurement of adhesive strength After immersing a 1260 denier nylon cord in the above RFL solution Drying and baking were performed for 3 minutes in a constant temperature dryer at 150°C. The treated cord thus prepared was embedded in the above unvulcanized adhered rubber compound and vulcanized at 150°C for 30 minutes to prepare an H test specimen.
The adhesive strength was measured using the "H-pull test" described in Rubber World, Vol. 114, pp. 213-217 (1946) and was 4.9.
A value of Kg/9mm was obtained. Examples 2 to 3 By changing the mixing ratio of CSM latex and RF liquid,
The same measurements as in Example 1 were carried out, and the results shown in Table 1 were obtained.
【表】
実施例 ４〜６
CSMラテツクス調製用乳化剤の種類および量
を変化させて、実施例１と同様の測定を行ない第
２表の結果を得た。[Table] Examples 4 to 6 The same measurements as in Example 1 were carried out by changing the type and amount of emulsifier for CSM latex preparation, and the results shown in Table 2 were obtained.
【表】
比較例 １
EPDM（住友化学工業(株)製エスプレンE502）よ
りつくつたハロゲン化EPDM（塩素含量15％、臭
素含量２％）60ｇを600ｇのトルエンに溶解した。
ロジン酸カリの25％水溶液12ｇとソルビタンモ
ノラウレート・ポリオキシエチレンエーテル
（HLB16.7）1.2ｇを水で稀釈、分散させ600ｇと
して液に、上記トルエン溶液を混合し、高速撹拌
機で20分間乳化した。この乳化液を実施例１と同
様の方法でハロゲン化EPDM分40％のラテツク
ス150ｇを得た。
このラテツクス16ｇと実施例１のRF液20ｇを
混合し、室温で２時間放置熟成した。RF液中の
固形分／ハロゲン化EPDM分の比は1/5である。
以下実施例１と同様にして接着力を測定し、
1.8Kg／９mmの値を得た。
実施例 ７〜９
SHPの水分散液を第３表に示すごとく変えて、
実施例１と同様の方法で接着力を測定し実施例１
とほぼ同等の値を得た。[Table] Comparative Example 1 60 g of halogenated EPDM (chlorine content 15%, bromine content 2%) made from EPDM (Esplen E502 manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in 600 g of toluene. Dilute and disperse 12 g of a 25% aqueous solution of potassium rosin acid and 1.2 g of sorbitan monolaurate polyoxyethylene ether (HLB16.7) with water to make 600 g. Mix the above toluene solution and use a high-speed stirrer for 20 minutes. Emulsified. This emulsion was treated in the same manner as in Example 1 to obtain 150 g of latex with a halogenated EPDM content of 40%. 16 g of this latex and 20 g of the RF liquid of Example 1 were mixed and left to age at room temperature for 2 hours. The ratio of solid content/halogenated EPDM content in the RF liquid is 1/5. The adhesive strength was measured in the same manner as in Example 1,
A value of 1.8Kg/9mm was obtained. Examples 7 to 9 The aqueous dispersion of SHP was changed as shown in Table 3,
The adhesive strength was measured in the same manner as in Example 1.
Almost the same value was obtained.
【表】
実施例 10
実施例１と同一のスルホクロル化ポリエチレン
15ｇをトルエン85ｇに溶解した。
1260デニールのナイロンコードを実施例１の
RF液に浸漬した後、130℃の恒温乾燥器中で３分
間処理した。次いで上記トルエン溶液を塗布し、
風乾後、実施例１の未加硫被着ゴム配合物を用い
て実施例１と同様の方法で接着力を測定し4.7
Kg／９mmの値を得た。
実施例 11〜13
ナイロンの代りにポリエステル（実施例11）、
ポリプロピレン（実施例12）、アクリル（実施例
13）を用いたこと、恒温乾燥器の温度を130℃と
したことおよび加硫時間を50分としたことを除
き、実施例１と同様に接着力を測定し、実施例１
とほぼ同等の値を得た。
実施例 14
被着ゴム配合を下記のごとく変更して実施例１
と同様の方法で接着力を測定し、実施例１とほぼ
同等の値を得た。
EPDM E502※ 70部
EPDM E512F※ 30部
スルホクロル化ポリエチレン※※ 10部
亜鉛華 ５部
ステアリン酸 １部
MAFカーボン 110部
ダイアナプロセスNM280 70部
Ｎ−シクロヘキシル−２−ベンゾチアジル−ス
ルフエンアミド 1.5部
テトラメチルチウラムジスルフイド 0.5部
ジペンタメチレンチウラムテトラスルフイド
0.7部
ジブチルジチオカルバミン酸亜鉛 1.5部
硫 黄 １部
※ 実施例１参照
※※実施例１のCSMラテツクスに使用したも
の
実施例 15
被着ゴム配合中のスルホクロル化ポリエチレン
を20部と増して実施例14と同様の方法で接着力を
測定した実施例14より若干大きな接着力の値を得
た。
実施例 16
高密度ポリエチレン（MI0.8）よりつくつた塩
素含量34％、硫黄含量1.3％のスルホクロル化ポ
リエチレンを用いて実施例１と同様の方法で接着
力を測定し3.3Kg／９mmの値を得た。
実施例 17
高密度ポリエチレン（MI4）よりつくつた塩素
含量26％、硫黄含量１％のスルホクロル化ポリエ
チレン40ｇをトルエン450ｇに溶解した。
ラウリルアルコール硫酸エステルソーダ溶液を
混合し、高速撹拌で20分間乳化した。この乳化液
を実施例１と同様の方法で処理し、SHP分30％
のラテツクス133ｇを得た。
以下実施例１と同様の方法を実施し、2.6Kg／
９mmの接着力を得た。[Table] Example 10 Sulfochlorinated polyethylene same as Example 1
15g was dissolved in 85g of toluene. 1260 denier nylon cord of Example 1
After being immersed in the RF solution, it was treated in a constant temperature dryer at 130°C for 3 minutes. Then apply the above toluene solution,
After air drying, the adhesion strength was measured in the same manner as in Example 1 using the unvulcanized adhered rubber compound of Example 1.4.7
A value of Kg/9mm was obtained. Examples 11-13 Polyester instead of nylon (Example 11),
Polypropylene (Example 12), Acrylic (Example
13), the temperature of the constant temperature dryer was 130°C, and the vulcanization time was 50 minutes, but the adhesive strength was measured in the same manner as in Example 1.
Almost the same value was obtained. Example 14 Example 1 with the adhered rubber composition changed as follows.
The adhesive strength was measured in the same manner as in Example 1, and a value almost equivalent to that of Example 1 was obtained. EPDM E502 * 70 parts EPDM E512F * 30 parts Sulfochlorinated polyethylene * * 10 parts Zinc white 5 parts Stearic acid 1 part MAF carbon 110 parts Diana Process NM280 70 parts N-cyclohexyl-2-benzothiazyl-sulfenamide 1.5 parts Tetramethylthiuram disulfide 0.5 parts dipentamethylenethiuram tetrasulfide
0.7 parts Zinc dibutyl dithiocarbamate 1.5 parts Sulfur 1 part *See Example 1 * *Used in the CSM latex of Example 1 Example 15 Example 14 by increasing the amount of sulfochlorinated polyethylene in the adherent rubber compound to 20 parts A slightly larger adhesive force value was obtained than in Example 14, in which the adhesive force was measured in the same manner as in Example 14. Example 16 Using sulfochlorinated polyethylene with a chlorine content of 34% and a sulfur content of 1.3% made from high-density polyethylene (MI0.8), the adhesive strength was measured in the same manner as in Example 1, and a value of 3.3Kg/9mm was obtained. Obtained. Example 17 40 g of sulfochlorinated polyethylene made from high-density polyethylene (MI4) with a chlorine content of 26% and a sulfur content of 1% was dissolved in 450 g of toluene. The lauryl alcohol sulfate ester soda solution was mixed and emulsified with high speed stirring for 20 minutes. This emulsion was treated in the same manner as in Example 1, and the SHP content was 30%.
133g of latex was obtained. Below, the same method as in Example 1 was carried out, and 2.6Kg/
An adhesive strength of 9 mm was obtained.
Claims (1)
びスルホハロゲン化ポリマーの有機溶剤溶液また
は水分散液を用いることを特徴とする繊維材料と
ゴム類とを接着する方法。 ２ レゾルシンホルムアルデヒド樹脂水性液とス
ルホハロゲン化ポリマー水分散液を用いる特許請
求の範囲１記載の方法。 ３ 繊維用材料が繊維状ないしは織物状である特
許請求の範囲１および２記載の方法。 ４ ゴム類がエチレンプロピレンジエン共重合ゴ
ム、エチレンプロピレン共重合ゴム、イソブチレ
ンイソプレン共重合ゴム、スルホクロル化ポリエ
チレンゴムまたはそれらの混合物である特許請求
の範囲１記載の方法。 ５ スルホハロゲン化ポリマーがスルホクロル化
ポリエチレン、スルホクロル化ポリプロピレン、
スルホクロル化エチレン酢酸ビニル共重合体、ス
ルホクロル化エチレンプロピレンジエン共重合
体、スルホクロル化エチレンプロピレン共重合
体、スルホクロル化イソブチレンイソプレン共重
合体またはそれらの混合物である特許請求の範囲
１記載の方法。 ６ 密度が0.94ｇ/cm以下のポリエチレンのスル
ホクロル化物をスルホクロル化ポリエチレンとし
て用いる特許請求の範囲５記載の方法。 ７ スルホハロゲン化ポリマー水分散液の乳化剤
としてカルボン酸アルカリ金属塩型乳化剤を用い
る特許請求の範囲１および２記載の方法。[Scope of Claims] 1. A method for bonding a fiber material and rubber, which comprises using an aqueous resorcinol-formaldehyde resin solution and an organic solvent solution or aqueous dispersion of a sulfohalogenated polymer. 2. The method according to claim 1, which uses an aqueous resorcinol formaldehyde resin liquid and an aqueous sulfohalogenated polymer dispersion. 3. The method according to claims 1 and 2, wherein the fiber material is fibrous or woven. 4. The method according to claim 1, wherein the rubber is ethylene propylene diene copolymer rubber, ethylene propylene copolymer rubber, isobutylene isoprene copolymer rubber, sulfochlorinated polyethylene rubber, or a mixture thereof. 5 The sulfohalogenated polymer is sulfochlorinated polyethylene, sulfochlorinated polypropylene,
2. The method of claim 1, which is a sulfochlorinated ethylene vinyl acetate copolymer, a sulfochlorinated ethylene propylene diene copolymer, a sulfochlorinated ethylene propylene copolymer, a sulfochlorinated isobutylene isoprene copolymer, or a mixture thereof. 6. The method according to claim 5, wherein a sulfochlorinated polyethylene having a density of 0.94 g/cm or less is used as the sulfochlorinated polyethylene. 7. The method according to claims 1 and 2, in which a carboxylic acid alkali metal salt type emulsifier is used as an emulsifier for the aqueous sulfohalogenated polymer dispersion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18082280A JPS57105476A (en) | 1980-12-19 | 1980-12-19 | Bonding and adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18082280A JPS57105476A (en) | 1980-12-19 | 1980-12-19 | Bonding and adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57105476A JPS57105476A (en) | 1982-06-30 |
| JPH0147511B2 true JPH0147511B2 (en) | 1989-10-13 |
Family
ID=16089956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18082280A Granted JPS57105476A (en) | 1980-12-19 | 1980-12-19 | Bonding and adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57105476A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6185690B1 (en) * | 2017-02-13 | 2017-08-23 | 日本板硝子株式会社 | Rubber reinforcing cord manufacturing method, rubber reinforcing cord and rubber product |
| JP6247799B1 (en) * | 2017-02-13 | 2017-12-13 | 日本板硝子株式会社 | Rubber reinforcing cord manufacturing method, rubber reinforcing cord and rubber product |
| WO2018146832A1 (en) * | 2017-02-13 | 2018-08-16 | 日本板硝子株式会社 | Production method for rubber-reinforcing cord, rubber-reinforcing cord, and rubber product |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5916566A (en) * | 1982-07-19 | 1984-01-27 | Sumitomo Chem Co Ltd | Flocking method of fiber |
| JPS5918761A (en) * | 1982-07-23 | 1984-01-31 | Sumitomo Chem Co Ltd | Composition containing short fiber |
| JPS60115679A (en) * | 1983-11-26 | 1985-06-22 | Seitetsu Kagaku Co Ltd | Bonding composition |
| JPH0742448B2 (en) * | 1985-03-12 | 1995-05-10 | 日本ゼオン株式会社 | Method of bonding rubber compound and fiber |
| WO1993022390A1 (en) * | 1992-05-01 | 1993-11-11 | Lord Corporation | Acrylonitrile-butadiene copolymer rubber adhesive |
| JP6032039B2 (en) * | 2013-02-08 | 2016-11-24 | 東ソー株式会社 | Adhesive aid, rubber composition-adhesive treatment solution for fiber composite and rubber composition-fiber composite |
| CN103450826B (en) * | 2013-08-23 | 2015-09-30 | 吴江骏达电梯部件有限公司 | A kind of metal pressure sensitive sizing agent and preparation method thereof |
| WO2019103133A1 (en) * | 2017-11-27 | 2019-05-31 | 住友精化株式会社 | Anionic aqueous dispersion, production method therefor, moulded article, adhesive liquid, rubber-reinforcing fibres, and rubber-reinforcing fibre composite |
| CN110698990A (en) * | 2018-07-09 | 2020-01-17 | 科建高分子材料（上海）股份有限公司 | Car door water-retaining film adhesive tape improved by butyl rubber and resin |
-
1980
- 1980-12-19 JP JP18082280A patent/JPS57105476A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6185690B1 (en) * | 2017-02-13 | 2017-08-23 | 日本板硝子株式会社 | Rubber reinforcing cord manufacturing method, rubber reinforcing cord and rubber product |
| JP6247799B1 (en) * | 2017-02-13 | 2017-12-13 | 日本板硝子株式会社 | Rubber reinforcing cord manufacturing method, rubber reinforcing cord and rubber product |
| WO2018146814A1 (en) * | 2017-02-13 | 2018-08-16 | 日本板硝子株式会社 | Production method for rubber-reinforcing cord, rubber-reinforcing cord, and rubber product |
| WO2018146832A1 (en) * | 2017-02-13 | 2018-08-16 | 日本板硝子株式会社 | Production method for rubber-reinforcing cord, rubber-reinforcing cord, and rubber product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57105476A (en) | 1982-06-30 |
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