JPS6224551B2 - - Google Patents
Info
- Publication number
- JPS6224551B2 JPS6224551B2 JP56046347A JP4634781A JPS6224551B2 JP S6224551 B2 JPS6224551 B2 JP S6224551B2 JP 56046347 A JP56046347 A JP 56046347A JP 4634781 A JP4634781 A JP 4634781A JP S6224551 B2 JPS6224551 B2 JP S6224551B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- rubber
- fiber material
- treated
- agent
- 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
- 239000000853 adhesive Substances 0.000 claims description 50
- 230000001070 adhesive effect Effects 0.000 claims description 50
- 229920001971 elastomer Polymers 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 239000002657 fibrous material Substances 0.000 claims description 23
- 229920000126 latex Polymers 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 18
- 238000009499 grossing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000004816 latex Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 10
- 239000012783 reinforcing fiber Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 2
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 2
- -1 polyethylene terephthalate Polymers 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 26
- 239000005056 polyisocyanate Substances 0.000 description 20
- 229920001228 polyisocyanate Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 7
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920005749 polyurethane resin Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 229960001755 resorcinol Drugs 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 3
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- BARWIPMJPCRCTP-UHFFFAOYSA-N oleic acid oleyl ester Natural products CCCCCCCCC=CCCCCCCCCOC(=O)CCCCCCCC=CCCCCCCCC BARWIPMJPCRCTP-UHFFFAOYSA-N 0.000 description 3
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 2
- UQDDVIGJWPTDNJ-UHFFFAOYSA-N 2-(chloromethyl)oxirane;propane-1,2,3-triol Chemical compound ClCC1CO1.OCC(O)CO UQDDVIGJWPTDNJ-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- QNLWQRKKNCGZNS-UHFFFAOYSA-N benzylbenzene;ethene;urea Chemical compound C=C.C=C.NC(N)=O.C=1C=CC=CC=1CC1=CC=CC=C1 QNLWQRKKNCGZNS-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 150000003509 tertiary alcohols Chemical class 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- BBBHAOOLZKQYKX-QXMHVHEDSA-N 16-methylheptadecyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCCCCCCCCCCCCCC(C)C BBBHAOOLZKQYKX-QXMHVHEDSA-N 0.000 description 1
- SAMYFBLRCRWESN-UHFFFAOYSA-N 16-methylheptadecyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCCCCC(C)C SAMYFBLRCRWESN-UHFFFAOYSA-N 0.000 description 1
- IPRSYPLQDZLFFB-UHFFFAOYSA-N 2-(butylamino)ethanesulfonic acid Chemical compound CCCCNCCS(O)(=O)=O IPRSYPLQDZLFFB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- NZXZINXFUSKTPH-UHFFFAOYSA-N 4-[4-(4-butylcyclohexyl)cyclohexyl]-1,2-difluorobenzene Chemical compound C1CC(CCCC)CCC1C1CCC(C=2C=C(F)C(F)=CC=2)CC1 NZXZINXFUSKTPH-UHFFFAOYSA-N 0.000 description 1
- AOYQDLJWKKUFEG-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]hept-4-ene-4-carboxylate Chemical compound C=1C2OC2CCC=1C(=O)OCC1CC2OC2CC1 AOYQDLJWKKUFEG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920013646 Hycar Polymers 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
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QTIMEBJTEBWHOB-PMDAXIHYSA-N [3-[(z)-octadec-9-enoyl]oxy-2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COC(=O)CCCCCCC\C=C/CCCCCCCC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC QTIMEBJTEBWHOB-PMDAXIHYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- QZULIRBSQUIUTA-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] hexanedioate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC\C=C/CCCCCCCC QZULIRBSQUIUTA-CLFAGFIQSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- DNWILILLQPIREP-UHFFFAOYSA-N ditridecyl decanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCCCCCCC DNWILILLQPIREP-UHFFFAOYSA-N 0.000 description 1
- VVTGHWARMCSPKY-UHFFFAOYSA-N dodecan-1-amine;oxirane Chemical compound C1CO1.CCCCCCCCCCCCN VVTGHWARMCSPKY-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 229940113915 isostearyl palmitate Drugs 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- WRPMUZXHQKAAIC-CZIZESTLSA-N octadecyl (e)-octadec-9-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCC\C=C\CCCCCCCC WRPMUZXHQKAAIC-CZIZESTLSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Description
本発明はゴム補強用繊維材料の処理方法に関し
その目的とするところは接着剤処理を実施された
コード又は織物の平滑性を向上させ、かつ高強
力、高接着力を有するゴム補強用繊維材料を提供
することにある。
ポリエステル繊維、ナイロン繊維、全芳香族ポ
リアミド繊維等の繊維材料は、寸法安定性、耐熱
性、耐疲労性などに優れ、ベルト、タイヤなどの
ゴム補強材として使用される。一般にゴム補強材
は、製糸された繊維束(ヤーン)に下撚を施した
後2本ないし数本を集め上撚を施しコードとした
ものをスダレ織物等に織編成し、その後接着剤処
理を施し、ゴムに埋め込み、加硫処理を行うこと
により、その補強効果を発揮する。従つてゴム補
強材としての効果を最大限に発揮するには、接着
剤処理を施されたスダレ織物(以下処理スダレと
いう)が高強力であるばかりでなく、ゴムとの接
着力が十分になければならない。
又、近年工程合理化を企図し、接着剤処理され
たコードを織編成しゴムに埋め込んで加硫熱処理
しゴム補強材となす方法も汎用されつつある。し
かしながら、かかる方法は、処理コードが粘着性
を有するため織編成し難い。従つて、前記特性に
加え、生産性向上の面から、処理コードが平滑性
を有し取り扱いやすいことが要求されつつある。
処理コード、スダレの強力を向上させるにはヤ
ーンの段階で出来るだけ引き延ばし高強力にする
だけでなく、これに続く撚糸、製織、接着剤処理
の工程での強力低下を防止する必要がある。因み
に、これらの段階での強力低下の原因は、主とし
てヤーンを撚り合わせること及び接着剤により、
ヤーン間、単糸間が固定され、初期ヤーンの全強
力が発揮されないことに依るものと考えられてい
る。撚糸の際の撚数は、補強を必要とするゴム製
品の種類により、強力、耐疲労性などの観点から
決定され、ゴム製品メーカーにより決定される。
一方接着剤による単糸間の固定化の条件は、接着
剤を付着する段階で接着剤がコード内部にどの程
度入るかという問題と、その後のベーキング条件
とで決定される。これらの条件は、続いて行われ
る加硫工程でのゴムとの接着及び加硫中の寸法安
定性を高めるのに好適なように決められる。接着
力向上、熱収縮率の減少のためには、十分な熱が
加えられなければならないが、このような処理に
より、一方では強力は低下する一方、処理コード
の粘着性も未だ改善されていない。
本発明者らは高接着性、高強力でかつ平滑性の
ある処理スダレあるいはコードを繊維材料の処理
剤を変更するだけで得ることを鋭意研究の結果、
驚くべきことに、特定の成分を使用することによ
り、従来考えられなかつた効果が奏されることを
見い出し、本発明に到達したものである。
即ち、本発明は、繊維材料をレゾルシン・ホル
マリン・ラテツクスを含む接着剤で処理した後、
分子量250〜1200の常温液状の平滑剤を主体とす
る処理剤で処理することを特徴とするゴム補強用
繊維材料の処理方法である。
本発明において使用する繊維材料はポリエチレ
ンテレフタレート、ポリエチレンナフタレートの
如き芳香族又はナフタレン環含有線状ポリエステ
ルの繊維、ナイロン6、ナイロン6、6の如き脂
肪族ポリアミドの繊維、又はポリメタフエニレン
イソフタラミド、ポリパラフエニレンテレフタラ
ミド等の全芳香族ポリアミドの繊維からなるヤー
ン、コード又は織布状のものを意味する。ここで
該繊維材料の形態は用途によつて夫々異なること
は勿論であるが、本発明の処理は任意の形態の繊
維材料に施すことができる。例えば、コートの形
態で接着剤処理を施し、次いで織編成して処理剤
で処理してもよいし、コードの形態で接着剤、処
理剤で順次処理し織編成してもよいし、更にコー
ドを織編成後得られたスダレ等に順次接着剤、処
理剤で処理してもよい。
本発明の接着剤に使用するレゾルシン・ホルマ
リン・ラテツクス(RFL)はレゾルシン−ホル
ムアルデヒドをアルカリ又は酸性触媒下で反応さ
せて得られる初期縮合物とゴムラテツクスの混合
物であり、レゾルシンとホルムアルデヒドのモル
比は1/0.1〜1/8の範囲が使用され好ましく
は1/0.5〜1/5の範囲である。更に好ましく
は1/1〜1/4の範囲である。
ゴムラテツクスとはブタジエン−スチレン−ビ
ニルピリジンラテツクス(VPラテツクスと称
す)、ブタジエン−スチレンラテツクス(SPRラ
テツクスと称す)、ブタジエンビニルピリジンラ
テツクス、アクリロニトリルラテツクス、アクリ
ロニトリル−ブタジエンラテツクス、天然ゴムラ
テツクス等であり単独又は混合物が使用できる。
特にVP−ラテツクス単独又はVP−ラテツクスと
他のラテツクスの混合系で用いるのが望ましい。
レゾルシン−ホルムアルデヒド初期縮合物とゴ
ムラテツクスとの混合比は後述の第2成分の添加
率にもよるが1/1〜1/15(重量比)で好まし
くは1/3〜1/12である。ゴムラテツクスの比
率が少ないと処理コードが硬くなるし多すぎると
満足すべき接着力が得られず著しく粘着性が増す
ために好ましくない。
かかるRFLを主体とする接着剤は、固形分と
してRFLを10〜25重量%含むように調整され
る。
なお、本発明に適用される接着剤は、前記の如
くRFLを含む組成物よりなるが、該接着剤には
さらに必要に応じポリエポキシド化合物、エチレ
ン尿素化合物、ブロツクドポリイソシアネート及
び水溶性ポリウレタン樹脂よりなる群から選ばれ
た少くとも1種の化合物を第2成分として含有せ
しめてもよい。
かかる第2成分は、上記RFLに対して0.5〜30
重量%、好ましくは1.0〜2.0重量%添加される。
第2成分の添加量が少なすぎると良好な接着力、
ゴム付着率が得られない。一方添加量が多すぎる
と接着剤の粘度が著しく上昇して繊維材料の処理
操作が困難となり、そのうえ接着力、ゴム付着率
は飽和に達して、第2成分の添加量を多くしただ
けの効果が上らずコストが上昇するだけであり、
更には処理繊維材料が著しく硬くなり強力も低下
してくるという欠点が生ずる。
本発明の接着剤に第2成分として含まれるポリ
エポキシド化合物は1分子中に少くとも2個以上
のエポキシ基を該化合物100g当り0.2g当量以上
含有する化合物であり、エチレングリコール、グ
リセロール、ソルビトール、ペンタエリスリトー
ル、ポリエチレングリコール等の多価アルコール
類とエピクロルヒドリンの如きハロゲン含有エポ
キシド類との反応生成物、レゾルシン、ビス(4
−ヒドロキシフエニル)ジメチルメタン、フエノ
ール・ホルムアルデヒド樹脂、レゾルシン・ホル
ムアルデヒド樹脂等の多価フエノール類と前記ハ
ロゲン含有エポキシド類との反応生成物、過酢酸
又は過酸化水素等で不飽和結合部を酸化して得ら
れるポリエポキシド化合物、即ち、3・4−エポ
キシシクロヘキセンエポキシド、3・4−エポキ
シシクロヘキシルメチル−3・4−エポキシシク
ロヘキセンカルボキシレート、ビス(3・4−エ
ポキシ−6−メチル−シクロヘキシルメチル)ア
ジペートなどを挙げることができる。これらの
内、特に多価アルコールとエピクロルヒドリンと
の反応生成物、即ち多価アルコールのポリグリシ
ジルエーテル化合物が優れた性能を発現するので
好ましい。かかるポリエポキシド化合物は通常乳
化液又は溶液として使用に供するのがよい。乳化
液又は溶液にするには、例えばかかるポリエポキ
シド化合物をそのまま、或は必要に応じて少量の
溶媒に溶解したものを、公知の乳化剤、例えばア
ルキルベンゼンスルホン酸ソーダ、ジオクチルス
ルホサクシネートNa塩、ノニルフエノールエチ
レンオキサイド付加物等を用いて乳化又は溶解
し、接着剤に添加する。
本発明で第2成分として用いる前記エチレン尿
素化合物は次に示す一般式で表わされるもので、
R′は芳香族又は脂肪族の炭化水素残基であり、
n′は0ないし2の整数である。
代表的な化合物としては、オクタデシルイソシ
アネート、ヘキサメチレンジイソシアネート、イ
ソホロンジイソシアネート、トリレンジイソシア
ネート、メタキシリレンジイソシアネート、ジフ
エニルメタンジイソシアネート、ナフチレンジイ
ソシアネート、トリフエニルメタントリイソシア
ネート等の芳香族、脂肪族イソシアネートとエチ
レンイミンとの反応生成物があげられ、特にジフ
エニルメタンジエチレン尿素等の芳香族エチレン
尿素化合物が良好な結果を与える。
本発明において接着剤に第2成分として含まれ
る前記エチレン尿素化合物は、加熱によつてエチ
レンイミン環が開環して反応し、接着性を高める
のである。かかるエチレン尿素化合物を接着剤に
添加して処理すると、接着性、柔軟性共に優れた
ゴム補強用繊維材料が得られ、更にブロツクドイ
ソシアネート化合物の場合のように、加熱時にブ
ロツク成分が遊離して環境を汚染するようなこと
もない。
また接着剤に併用するブロツクドポリイソシア
ネート化合物はポリイソシアネート化合物とブロ
ツク化剤との付加化合物であり、加熱によりブロ
ツク成分が遊離して活用なポリイソシアネート化
合物を生ぜしめるものである。ポリイソシアネー
ト化合物としては、例えばトリレンジイソシアネ
ート、メタフエニレンジイソシアネート、ジフエ
ニルメタンジイソシアネート、ヘキサメチレンジ
イソシアネート、ポリメチレンポリフエニルイソ
シアネート、トリフエニルメタントリイソシアネ
ート等のポリイソシアネート、或はこれらのポリ
イソシアネートと、トリメチロールプロパン、ペ
ンタエリスリトール等の活性水素原子を2個以上
有する化合物とを、NCO/OH>1となるモル比
で反応させて得られる末端NCO基含有のポリア
ルキレングリコールアダクトポリイソシアネート
が挙げられる。特にトリレンジイソシアネート、
メタキシレンジイソシアネート、ジフエニルメタ
ンジイソシアネート、ポリメチレンポリフエニル
イソシアネートの如き芳香族ポリイソシアネート
が優れた性能を発現するので好ましい。
ブロツク化剤としては、例えばフエノール、チ
オフエノール、クレゾール、レゾルシノール等の
フエノール類、t−ブタノール、t−ペンタノー
ル等の第3級アルコール類、ジフエニルアミン、
キシリジン等の芳香族第2級アミン類、フタル酸
イミド等のイミド類、カプロラクタム、バレロラ
クタム等のラクタム類、アセトキシム、メチルエ
チルケトンオキシム、シクロヘキサンオキシム等
のオキシム類、及び酸性亜硫酸ソーダがある。
かかるブロツクドポリイソシアネート化合物は
特に一般式
R″(NHCOX)n″
〔R″は芳香族、芳香脂肪族、脂肪族からなる群よ
り選ばれた有機残基、Xは熱処理によつて遊離す
るブロツク剤残基、n″は2以上の整数〕で表わ
されるブロツクドポリイソシアネート化合物を用
いるのが好ましい。
かかる場合、接着剤を調整するにはRFL液に
ブロツクドポリイソシアネート化合物を添加した
後熟成して使用することもできるし、又RFL液
を熟成した後、繊維材料の処理直前にブロツクド
ポリイソシアネート化合物を添加して使用するこ
ともできる。RFL液の熟成は通常、15〜25℃で
15時間以上行なわれる。
ブロツクドポリイソシアネート化合物及び
RFLを含む接着剤は、通常、固形分を10〜25重
量%含有するように調整される。
このようにRFLおよびブロツクドポリイソシ
アネート化合物を含む接着剤では該化合物が加熱
されてブロツク成分が遊離し活性なイソシアネー
ト基が再成されて、レゾルシン・ホルマリンと反
応しRFLの擬集力を著しく高めると共に、接着
剤付与による処理で繊維材料に付着した接着成分
とも反応し、更に加硫時にゴムとも反応して繊維
材料の硬化をともなわずに総合的に接着力を高め
る結果となる。
さらに本発明では接着剤としてRFLの他に必
要に応じ下記一般式で示される水溶性ポリウレタ
ン樹脂を第2成分として含有させることができ
る。
〔A:有機ポリイソシアネート残基
R:芳香族、脂肪族、芳香脂肪族からなる群より
選ばれた有機残基
X:熱処理によつて遊離するブロツク化剤残基
Y:炭素数2〜6のアミノスルホン酸または炭素
数1〜6のアミノカルボン酸の残基
n:5〜30の整数
l、m:1〜5の整数
l+m:2〜6の整数〕
前記水溶性ポリウレタン樹脂は、前記一般式で
示されるように親水性基としてポリオキシエチレ
ン基(−CH2CH2O−)を10〜50重量%含むイソシア
ネート基含有のウレタンプレポリマーの遊離イソ
シアネート基をブロツク化剤によつてブロツク化
したブロツクドイソシアネート(RXCONH−)並
びにイソシアネート基と反応性の水素原子を少な
くとも1ケ及びアニオン形成性基を少なくとも1
ケ含有する化合物とを反応させたもの(YCONH
−)より構成される。
更に詳言するならポリオキシエチレン基(−
CH2CH2O−)oは、得られるポリウレタン樹脂が安
定な水溶性を得るために必須の成分でありそのn
数は5〜30、ポリエチレングリコールの分子量に
換算して約200〜1300である。
また有機ポリイソシアネート残基Aは、官能数
3〜7の有機ポリイソシアネートを対象とし、例
えば、トリフエニルメタントリイソシアネート、
ポリメチレンポリフエニルイソシアネート並びに
ヘキサメチレンジイソシアネート、キシリレンジ
イソシアネート、イソホロンジイソシアネート、
トリレンジイソシアネート、ジフエニルメタンジ
イソシアネート等とトリメチロールプロパン等低
分子量ポリオールとを予め反応させて得られたポ
リイソシアネート、ヘキサメチレンジイソシアネ
ートの3量体化物等があげられる。
またブロツクドイソシアネート(RXCONH−)l
は前記イソシアネート基とブロツク化剤との付加
化合物であり、加熱によりブロツク成分が遊離し
て活性なポリイソシアネート化合物を生ぜしめる
ものである。ブロツク化剤としては、例えばフエ
ノール、チオフエノール、クレゾール、レゾルシ
ノール等のフエノール類、t−ブタノール、t−
ペンタノール等の第3級アルコール類、ジフエニ
ルアミン、キシリジン等の芳香族第2級アミン
類、フタル酸イミド等のイミド類、カプロラクタ
ム、バレロラクタム等のラクタム類、アセトキシ
ム、メチルエチルケトンオキシム、シクロヘキサ
ンオキシム等のオキシム類及び酸性亜硫酸ソーダ
等が挙げられるが、特にフエノール、クレゾー
ル、ノニルフエノールの如きアルキルフエノール
が好ましい。即ちブロツクドイソシアネート(−
RXCONH−)lとしては、好ましくは
The present invention relates to a method for treating a rubber reinforcing fiber material, and its purpose is to improve the smoothness of a cord or fabric treated with an adhesive, and to produce a rubber reinforcing fiber material having high strength and adhesive strength. It is about providing. Fiber materials such as polyester fibers, nylon fibers, and wholly aromatic polyamide fibers have excellent dimensional stability, heat resistance, and fatigue resistance, and are used as rubber reinforcing materials for belts, tires, and the like. In general, rubber reinforcing materials are made by first twisting a spun fiber bundle (yarn), then collecting two or several yarns and giving them a second twist to form a cord, which is then woven into a sudare fabric or the like, and then treated with an adhesive. Its reinforcing effect is achieved by applying it, embedding it in rubber, and vulcanizing it. Therefore, in order to maximize its effectiveness as a rubber reinforcing material, the adhesive-treated sudare fabric (hereinafter referred to as treated sudare) must not only be highly strong, but also have sufficient adhesive strength with the rubber. Must be. In addition, in recent years, with the aim of streamlining the process, a method of weaving and knitting adhesive-treated cords, embedding them in rubber, and subjecting them to vulcanization heat treatment to form rubber reinforcing materials has become widely used. However, this method is difficult to weave and knit because the treated cord is sticky. Therefore, in addition to the above-mentioned characteristics, from the viewpoint of improving productivity, it is increasingly required that the treated cord be smooth and easy to handle. In order to improve the strength of treated cords and threads, it is necessary not only to stretch the yarn as much as possible to make it as strong as possible, but also to prevent a decrease in strength during the subsequent processes of twisting, weaving, and adhesive treatment. Incidentally, the cause of the decrease in strength at these stages is mainly due to the twisting of the yarns and the adhesive.
It is believed that this is due to the fact that the yarns and single yarns are fixed and the full strength of the initial yarn is not exerted. The number of twists during twisting is determined from the viewpoints of strength, fatigue resistance, etc., depending on the type of rubber product that requires reinforcement, and is determined by the rubber product manufacturer.
On the other hand, the conditions for fixing the single yarns with the adhesive are determined by the issue of how much the adhesive enters inside the cord at the stage of adhering the adhesive, and the subsequent baking conditions. These conditions are determined to be suitable for improving adhesion to rubber in the subsequent vulcanization step and dimensional stability during vulcanization. Sufficient heat must be applied to improve adhesion and reduce heat shrinkage, but on the one hand, such treatments reduce strength, and on the other hand, the tackiness of treated cords has not yet been improved. . As a result of intensive research, the present inventors have discovered that it is possible to obtain treated cords or cords with high adhesiveness, high strength, and smoothness by simply changing the treatment agent for fiber materials.
Surprisingly, the present invention was achieved by discovering that by using specific components, effects previously unimaginable can be achieved. That is, in the present invention, after treating a fiber material with an adhesive containing resorcinol formalin latex,
This is a method for treating a rubber reinforcing fiber material, which is characterized in that it is treated with a treatment agent that is mainly a smoothing agent that is liquid at room temperature and has a molecular weight of 250 to 1200. The fiber materials used in the present invention are fibers of aromatic or linear polyesters containing aromatic or naphthalene rings such as polyethylene terephthalate and polyethylene naphthalate, fibers of aliphatic polyamides such as nylon 6, nylon 6, 6, or polymethaphenylene isophthalate. It means a yarn, cord, or woven fabric made of fibers of wholly aromatic polyamide such as ramid and polyparaphenylene terephthalamide. It goes without saying that the form of the fiber material differs depending on the use, but the treatment of the present invention can be applied to any form of fiber material. For example, a coat may be treated with an adhesive, then woven and knitted, and treated with a treatment agent, or a cord may be sequentially treated with an adhesive and a treatment agent and woven, or the cord may be further treated with an adhesive and a treatment agent. After weaving and knitting, the sag etc. obtained may be sequentially treated with an adhesive and a treatment agent. The resorcinol formalin latex (RFL) used in the adhesive of the present invention is a mixture of rubber latex and an initial condensate obtained by reacting resorcinol-formaldehyde under an alkali or acidic catalyst, and the molar ratio of resorcinol and formaldehyde is 1. A range of /0.1 to 1/8 is used, preferably a range of 1/0.5 to 1/5. More preferably, it is in the range of 1/1 to 1/4. Rubber latex includes butadiene-styrene-vinylpyridine latex (referred to as VP latex), butadiene-styrene latex (referred to as SPR latex), butadiene-vinylpyridine latex, acrylonitrile latex, acrylonitrile-butadiene latex, natural rubber latex, etc. Can be used alone or in combination.
In particular, it is desirable to use VP-latex alone or in a mixed system of VP-latex and other latexes. The mixing ratio of the resorcinol-formaldehyde initial condensate and the rubber latex is 1/1 to 1/15 (weight ratio), preferably 1/3 to 1/12, although it depends on the addition rate of the second component described later. If the proportion of rubber latex is too small, the treated cord becomes hard, and if it is too large, satisfactory adhesion cannot be obtained and the tackiness increases significantly, which is not preferable. Such an adhesive mainly composed of RFL is adjusted to contain 10 to 25% by weight of RFL as a solid content. The adhesive applied to the present invention is made of a composition containing RFL as described above, but if necessary, the adhesive may further contain a polyepoxide compound, an ethylene urea compound, a blocked polyisocyanate, and a water-soluble polyurethane resin. At least one compound selected from the group consisting of: may be contained as a second component. The second component has a ratio of 0.5 to 30 with respect to the above RFL.
It is added in weight percent, preferably 1.0 to 2.0 weight percent.
If the amount of the second component added is too small, good adhesion
Rubber adhesion rate cannot be obtained. On the other hand, if the amount added is too large, the viscosity of the adhesive increases significantly, making it difficult to process the fiber material, and in addition, the adhesive strength and rubber adhesion rate reach saturation, resulting in the effect of increasing the amount of the second component added. The cost will only increase without increasing the
A further disadvantage is that the treated fiber material becomes extremely hard and its strength decreases. The polyepoxide compound contained as a second component in the adhesive of the present invention is a compound containing at least two or more epoxy groups in one molecule in an equivalent amount of 0.2 g or more per 100 g of the compound, such as ethylene glycol, glycerol, sorbitol, pentoxide, etc. Reaction products of polyhydric alcohols such as erythritol and polyethylene glycol and halogen-containing epoxides such as epichlorohydrin, resorcinol, bis(4
-Hydroxyphenyl)dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin, and other reaction products of polyhydric phenols and the above-mentioned halogen-containing epoxides, peracetic acid, hydrogen peroxide, etc. to oxidize unsaturated bonds. 3,4-epoxycyclohexene epoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl) adipate, etc. can be mentioned. Among these, reaction products of polyhydric alcohols and epichlorohydrin, ie, polyglycidyl ether compounds of polyhydric alcohols, are particularly preferred because they exhibit excellent performance. Such polyepoxide compounds are usually used as emulsions or solutions. To make an emulsion or solution, for example, such a polyepoxide compound as it is or dissolved in a small amount of a solvent as necessary may be mixed with a known emulsifier such as sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol. It is emulsified or dissolved using an ethylene oxide adduct and added to the adhesive. The ethylene urea compound used as the second component in the present invention is represented by the following general formula,
R′ is an aromatic or aliphatic hydrocarbon residue;
n' is an integer from 0 to 2. Typical compounds include aromatic and aliphatic isocyanates such as octadecyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, metaxylylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, triphenylmethane triisocyanate, and ethylene. Reaction products with imines are mentioned, and in particular aromatic ethylene urea compounds such as diphenylmethane diethylene urea give good results. In the ethylene urea compound contained in the adhesive as a second component in the present invention, the ethylene imine ring opens and reacts with heating, thereby improving adhesiveness. When such an ethylene urea compound is added to an adhesive and processed, a rubber reinforcing fiber material with excellent adhesion and flexibility can be obtained, and furthermore, as in the case of blocked isocyanate compounds, the blocking component is not liberated upon heating. It does not pollute the environment. Further, the blocked polyisocyanate compound used in combination with the adhesive is an addition compound of a polyisocyanate compound and a blocking agent, and the blocking component is liberated by heating to produce a useful polyisocyanate compound. Examples of the polyisocyanate compound include polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, and triphenylmethane triisocyanate; Examples include polyalkylene glycol adduct polyisocyanates containing terminal NCO groups obtained by reacting compounds having two or more active hydrogen atoms such as methylolpropane and pentaerythritol at a molar ratio of NCO/OH>1. Especially tolylene diisocyanate,
Aromatic polyisocyanates such as meta-xylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate are preferred because they exhibit excellent performance. Examples of blocking agents include phenols such as phenol, thiophenol, cresol and resorcinol, tertiary alcohols such as t-butanol and t-pentanol, diphenylamine,
These include aromatic secondary amines such as xylidine, imides such as phthalic acid imide, lactams such as caprolactam and valerolactam, oximes such as acetoxime, methyl ethyl ketone oxime, and cyclohexane oxime, and acidic sodium sulfite. Such blocked polyisocyanate compounds are particularly formulated with the general formula R″(NHCOX)n″ [R″ is an organic residue selected from the group consisting of aromatic, araliphatic, and aliphatic, and X is a block that is liberated by heat treatment. It is preferable to use a blocked polyisocyanate compound represented by the following formula: where n'' is an integer of 2 or more. In such cases, the adhesive can be prepared by adding a blocked polyisocyanate compound to the RFL liquid and then aging it, or after aging the RFL liquid, adding a blocked polyisocyanate compound immediately before processing the textile material. It can also be used by adding a compound. RFL liquid is usually aged at 15-25℃.
It lasts over 15 hours. Blocked polyisocyanate compounds and
Adhesives containing RFL are typically adjusted to contain 10-25% solids by weight. In this way, in adhesives containing RFL and blocked polyisocyanate compounds, when the compound is heated, the blocking component is liberated and active isocyanate groups are regenerated, reacting with resorcinol and formalin, and significantly increasing the gathering power of RFL. At the same time, it also reacts with the adhesive component attached to the fiber material during the adhesive application process, and further reacts with the rubber during vulcanization, resulting in an overall increase in adhesive strength without curing the fiber material. Furthermore, in the present invention, in addition to RFL, a water-soluble polyurethane resin represented by the following general formula can be contained as a second component as an adhesive, if necessary. [A: organic polyisocyanate residue R: organic residue selected from the group consisting of aromatic, aliphatic, and araliphatic X: blocking agent residue released by heat treatment Y: carbon number 2-6 residue of aminosulfonic acid or aminocarboxylic acid having 1 to 6 carbon atoms n: an integer l of 5 to 30, m: an integer l of 1 to 5 + m: an integer of 2 to 6] The water-soluble polyurethane resin has the general formula The free isocyanate groups of the isocyanate group-containing urethane prepolymer containing 10 to 50% by weight of polyoxyethylene groups (-CH 2 CH 2 O-) as hydrophilic groups were blocked with a blocking agent as shown in Blocked isocyanate (RXCONH-) and at least one hydrogen atom reactive with the isocyanate group and at least one anion-forming group.
(YCONH)
−). To be more specific, polyoxyethylene group (-
CH 2 CH 2 O−) o is an essential component in order for the obtained polyurethane resin to have stable water solubility, and its n
The number is 5 to 30, which is approximately 200 to 1300 in terms of the molecular weight of polyethylene glycol. Further, the organic polyisocyanate residue A targets organic polyisocyanates having a functional number of 3 to 7, such as triphenylmethane triisocyanate,
Polymethylene polyphenyl isocyanate as well as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate,
Examples include polyisocyanates obtained by reacting tolylene diisocyanate, diphenylmethane diisocyanate, etc. with low molecular weight polyols such as trimethylolpropane, trimers of hexamethylene diisocyanate, and the like. Also blocked isocyanate (RXCONH−) l
is an addition compound of the above-mentioned isocyanate group and a blocking agent, and the blocking component is liberated by heating to produce an active polyisocyanate compound. Examples of blocking agents include phenols such as phenol, thiophenol, cresol, and resorcinol, t-butanol, and t-butanol.
Tertiary alcohols such as pentanol, aromatic secondary amines such as diphenylamine and xylidine, imides such as phthalic acid imide, lactams such as caprolactam and valerolactam, oximes such as acetoxime, methyl ethyl ketone oxime, and cyclohexane oxime. and acidic sodium sulfite, among which alkylphenols such as phenol, cresol, and nonylphenol are particularly preferred. That is, blocked isocyanate (-
RXCONH−) l is preferably
【式】(Rは炭素数1〜9の
アルキル基または水素原子)を挙げることができ
る。
さらに前記の如くイソシアネート基と反応性の
水素原子を少なくとも1ケ及びアニオン形成性基
を少なくとも1ケ含有する化合物としては炭素数
2〜6のアミノスルホン酸、例えばタウリン、N
−メチルタウリン、もしくはN−ブチルタウリン
等、または炭素数1〜6のアミノカルボン酸、例
えばグリシン、もしくはアラニン等を挙げること
ができる。
この際l+mは有機ポリイソシアネートの官能
数3〜7より1を減じた価であるから2〜6とな
り、mは得られるポリウレタン樹脂の水溶性を確
保するため少なくとも1は必要であり、従つてl
は5以下、l、mはそれぞれ1〜5である。
このように水溶性ポリウレタン樹脂を含む接着
剤の場合は、該ポリウレタン樹脂が水溶性である
ためRFLと均一に混合しており、該接着剤溶液
の経時安定性、工程安定性がよく、タイヤコート
とゴムとの接着性が優れている。そして後工程に
おける熱処理によつてRF樹脂さらにはゴムラテ
ツクスと強力に反応し、より強い相互作用が働く
のである。更には熱処理によつて、かかるポリウ
レタンプレ樹脂より解離したイソシアネート化合
物が自己重合し接着剤層の凝集力を著しく高め且
つゴム成分との間にも相互作用が働き接着力、ゴ
ム付着率が飛躍的に向上する。
次に本発明では、繊維材料に前記接着剤を付与
した後、分子量250〜1200、常温で液状、好まし
くは分子量300〜1000の平滑剤を主体とする処理
剤で処理する。かかる処理は、得られるゴム補強
用繊維材料のゴムとの接着性を向上させると共に
該材料の平滑性を確保するために必要の構成要件
である。
本発明で用いられる「分子量250〜1200の常温
液状平滑剤」とは疎水性を有する分子量250〜
1200の常温液状有機化合物であり、常温液状とは
通常使用温度18〜25℃で液状を呈することであ
り、従来繊維や機械の潤滑性向上のために使用さ
れている成分である。例えば一塩基酸の一価アル
コールのエステルとしてメチルオレート、ブチル
ステアレート、オレイルオレート、イソステアリ
ルパルミテート、イソステアリルオレートなど、
二塩基酸の一価アルコールエステルとしてジオレ
イルアジペート、ジオクチルアセレート、ジトリ
デシルセバケート、ジオレイルジチオプロピオネ
ートなど、三塩基酸の一価アルコースエステルと
して、トリデシルトルメリテート、トリオレイル
トリメリテートなど、二価アルコールの脂肪酸エ
ステルとして、ネオペンチルグリコールジオレー
ト、1・6ヘキサンジオールジオレート、4・
4′イソプロピリデンビスフエノキシエチルラウレ
ートなど、多価アルコールの脂肪酸全エステルと
してグリセリントリオレート、ペンタエリスリト
ールテトラオレートなど、その他2価アルコール
と2塩基酸のポリエステルの末端を一価アルコー
ル又は一塩基酸で封鎖して分子量1200以下にした
もの、ジフエニルメタンジイソシアネートとオレ
イルアルコールのウレタンなどをあげることがで
きる。更に個々の成分が分子量250〜1200であれ
ば、これらを混合して得られる平滑剤混合物も、
この混合物自体が常温液状であれば、本発明の成
分として用いることができる。例えばオレイルオ
レエートの部分水添により発生する少量のオレイ
ルステアレート、ステアリールオレートを含むオ
レイルオレエートでも常温でそれらが相溶し液状
を呈していれば使用できる。
本発明に用いられる平滑剤は常温液状で且つ分
子量250以上1200以下でなければならない。もし
この平滑剤が常温固体になると、撥水性が生じ接
着性が低下するし、又分子量が250未満あるいは
1200を越えると平滑性が低下する。かかる処理剤
は平滑剤を主体とするが、本発明の効果をより一
層発揮させるには平滑剤の配合比率を出来るだけ
高め、70重量%以上含有させる方が望ましい。
本発明における接着剤処理後に付与する処理剤
はトリクレン、パークレン等の有機溶剤に溶解し
たり水性エマルジヨンの状態でも付与できるが、
平滑剤比率を上げるためにはそのままストレート
で付与するのが好ましい。
接着剤および処理剤を繊維材料に付着せしめる
にはローラーとの接着若しくはノズルからの噴霧
による塗布又は液浴への浸漬等任意の方法を採用
することが出来る。
繊維材料に対する固形分付着量は、接着剤とし
ては0.5〜10重量%、好ましくは1〜5重量%、
処理剤としては0.05〜5重量%、好ましくは0.1
〜3重量%付着せしめるのが好適である。該繊維
材料に対する固形分付着量を制御する為に、圧接
ローラによる絞り、スクレーバー等によるかきお
とし、空気吹き付けによる吹飛ばし、吸引、吸
収、ヒーターによる叩打等の手段を用いても良
い。
次いで、平滑剤を主体とする処理剤を付与する
がストレートだとそのまま使用できるが、水性エ
マルジヨン溶液で付与する場合には、水、又は溶
媒が蒸発する温度即ち沸点以上で例えば水性エマ
ルジヨンの場合105〜120℃で乾燥すれば良い。
このようにして処理された繊維材料はゴム補強
用として優れた抗張力、寸法安定性等の一般的諸
性能を有し、特に平滑性が大で、成形加工性が良
好で耐疲労性に優れ、又配合ゴムに埋没加硫した
後の繊維材料のゴム付着率が高く極めて高い接着
力を示す。
本発明により平滑でしかも極めて接着性の高い
処理繊維材料で得られる理由は明らかではない
が、平滑剤が接着剤層を被覆しているため得られ
る処理コード、スダレ等のゴム補強用繊維材料の
平滑性が著しく大となり、又他方RFL(接着
剤)上の平滑剤がRFL自体を膨潤させある程度
可溶化させると共に被着体である未加硫ゴムをも
膨潤させ、両者の濡れを良好にし且つ可溶化させ
る働きをしているものと推定される。
以下本発明を実施例により更に詳細に説明す
る。実施例中%は重量基準で示す。
尚、実施例においてプライ間剥離力とは繊維材
料とゴムとの接着力を示すもので2plyの処理コー
ドを90度の角度を成す様にしてクロスプライ(コ
ード密度27endo/25cm)として自動車タイヤ用
カーカス配合ゴム中に埋め込み160℃で20分間プ
レスにより加硫した後、両プライを200m/m1
分の引張り速度で剥させるに要する力をKg/3cm
で表わしたものである。
又、ゴム付着率も繊維材料に対するゴムの接着
性を示す尺度で上記のプラス間剥離力測定の際に
ゴムから剥離されたコードを肉眼で観察し、コー
ド表面の中ゴムが付着している部分を百分率であ
らわしたものである。
コードの曲げ硬さはガーレー式で測定したもの
で測定値が大きいほど硬いことを示す。更に強力
保持率は耐疲労度をあらわす尺度でクツドリツチ
式疲労試験機によりコードに回転デイスク盤間で
設定、伸度6%、圧縮18%の繰返し疲労を350万
回与えた後強力がいくら残存しているかを百分率
で表わしたものである。
平滑性は処理コードを直径60m/mφ、粗度
3Sの梨地加工ピンに180゜の接触角で接触しなが
ら2m/minで巻取る時ピンへの入側張力(T1)
とし、出側張力(T2)を測定し、摩擦力(F)を
F=T2−T1として算出し、Fが小さいほど平滑
性が良好と判断される。
実施例 1
10%苛性ソーダ水溶液10gr、28%アンモニア水
溶液30grを水260grに加えよく撹拌しこの水溶液
の中に予じめ酸性触媒で縮合せしめたレゾルシン
−ホルムアルデヒド初期縮合物(アセトン40%溶
液)60grを添加して十分に分散せしめる。
次にHycar2518FS(日本ゼオン(社)製40%
分散液Vpラテツクス)240grをHycar LX−112
(日本ゼオン(社)製40%分散液SBRラテツク
ス)100gr、ジフエニルメタンジエチレン尿素水
分散液(25%分散液)80grをH2O200grに添加
し、充分にかきまぜながら加えていき、更にホル
ムアルデヒド(37%)20grを添加し水性接着液を
得た。
次いで予めエチレングリコールジグリシジルエ
ーテル及び該エチレングリコールジグリシジルエ
ーテルに対して10重量%のラウリルアミンエチレ
ンオキサイド10モル付加物
を混合分散せしめ、溶融紡糸されたポリエチレン
テレフタレート繊維にエチレングリコールシグリ
シジルエーテルの付着品が0.5重量%となるよう
に付着させ、延伸後200℃で熱処理し1000de/
250filの延伸糸を得た。
得られたエポキシ処理ポリエチレンテレフタレ
ート延伸糸を3本撚り合わせて(撚数40×40T/
10cm)コードとしコンピユートリーター処理機
(CAリツツラー社製タイヤコード処理機を用いて
前記接着液を浸漬通過させ、次いで100℃120秒乾
燥させた後、230℃で120秒間熱処理した。
得られた処理コードを更に第1表に示す各種の
平滑剤で処理した(平滑剤をエマルジヨン、もし
くは溶液にしたものは110℃で120秒間乾燥し
た)。
平滑剤処理コードは平滑性を測定し、更に天然
ゴムを主成分としたカーカス配合の未加硫ゴム中
に埋込み150℃で30分間加硫後、プライ間剥離力
およびゴム付着率の測定を行つた。
結果を第1表にまとめて示す。
第1表から明らかなように、分子量250〜1200
の平滑剤で処理したコードはマサツ力、ゴム付が
改良されていることがわかる。[Formula] (R is an alkyl group having 1 to 9 carbon atoms or a hydrogen atom) can be mentioned. Furthermore, as mentioned above, examples of compounds containing at least one hydrogen atom reactive with an isocyanate group and at least one anion-forming group include aminosulfonic acids having 2 to 6 carbon atoms, such as taurine, N
-methyltaurine or N-butyltaurine, or aminocarboxylic acids having 1 to 6 carbon atoms, such as glycine or alanine. In this case, l + m is the value obtained by subtracting 1 from the functional number of 3 to 7 of the organic polyisocyanate, so it is 2 to 6, and m is required to be at least 1 to ensure the water solubility of the polyurethane resin obtained, so l
is 5 or less, and l and m are each from 1 to 5. In the case of adhesives containing water-soluble polyurethane resin, since the polyurethane resin is water-soluble, it is uniformly mixed with RFL, and the adhesive solution has good stability over time and process stability, and is suitable for tire coating. and has excellent adhesion to rubber. Then, through heat treatment in the post-process, it reacts strongly with the RF resin and even the rubber latex, creating an even stronger interaction. Furthermore, by heat treatment, the isocyanate compound dissociated from the polyurethane pre-resin self-polymerizes, significantly increasing the cohesive force of the adhesive layer, and interacting with the rubber component, dramatically increasing the adhesive force and rubber adhesion rate. improve. Next, in the present invention, after applying the adhesive to the fiber material, the fiber material is treated with a treatment agent mainly composed of a smoothing agent having a molecular weight of 250 to 1,200, which is liquid at room temperature, and preferably having a molecular weight of 300 to 1,000. Such a treatment is a necessary component in order to improve the adhesion of the resulting rubber reinforcing fiber material to rubber and to ensure the smoothness of the material. The "room-temperature liquid leveling agent with a molecular weight of 250 to 1200" used in the present invention is a hydrophobic molecular weight of 250 to 1200.
1200 is an organic compound that is liquid at room temperature. Liquid at room temperature means that it is liquid at a normal operating temperature of 18 to 25°C, and is a component that has been conventionally used to improve the lubricity of textiles and machinery. For example, esters of monohydric alcohols of monobasic acids such as methyl oleate, butyl stearate, oleyl oleate, isostearyl palmitate, isostearyl oleate, etc.
Monohydric alcohol esters of dibasic acids include dioleyl adipate, dioctyl acelate, ditridecyl sebacate, and dioleyl dithiopropionate; monohydric alcohol esters of tribasic acids include tridecyl tourmelitate and trioleyl trimelli. As fatty acid esters of dihydric alcohols such as tate, neopentyl glycol diolate, 1.6 hexanediol diolate, 4.
4' Isopropylidene bisphenoxyethyl laurate, etc., glycerin triolate, pentaerythritol tetraoleate, etc. as a whole fatty acid ester of a polyhydric alcohol, etc. Other polyesters of a dihydric alcohol and a dibasic acid are connected at the end with a monohydric alcohol or a monobasic acid. Examples include those whose molecular weight is reduced to 1200 or less by blocking with acid, and urethane made from diphenylmethane diisocyanate and oleyl alcohol. Furthermore, if the individual components have a molecular weight of 250 to 1200, the smoothing agent mixture obtained by mixing them can also be
If this mixture itself is liquid at room temperature, it can be used as a component of the present invention. For example, oleyl oleate containing a small amount of oleyl stearate or stearyl oleate generated by partial hydrogenation of oleyl oleate can be used as long as they are compatible and liquid at room temperature. The smoothing agent used in the present invention must be liquid at room temperature and have a molecular weight of 250 or more and 1200 or less. If this smoothing agent becomes a solid at room temperature, it will become water repellent and its adhesion will decrease, and if its molecular weight is less than 250 or
When it exceeds 1200, smoothness decreases. Such a processing agent is mainly composed of a smoothing agent, but in order to further exhibit the effects of the present invention, it is preferable to increase the blending ratio of the smoothing agent to 70% by weight or more. The treatment agent applied after the adhesive treatment in the present invention can be dissolved in an organic solvent such as trichlene or percrene, or can be applied in the form of an aqueous emulsion.
In order to increase the leveling agent ratio, it is preferable to apply it straight. Any method can be used to attach the adhesive and treatment agent to the fiber material, such as adhesion with a roller, application by spraying from a nozzle, or immersion in a liquid bath. The amount of solid content attached to the fiber material is 0.5 to 10% by weight, preferably 1 to 5% by weight as an adhesive.
As a treatment agent, it is 0.05 to 5% by weight, preferably 0.1
It is preferred that the amount is 3 to 3% by weight. In order to control the amount of solid content attached to the fiber material, means such as squeezing with a pressure roller, scraping with a scraper, blowing off with air, suction, absorption, and beating with a heater may be used. Next, a treatment agent mainly composed of a smoothing agent is applied.If it is straight, it can be used as is, but if it is applied as an aqueous emulsion solution, it can be applied at a temperature above the boiling point of the water or solvent, for example, in the case of an aqueous emulsion105 It is sufficient to dry at ~120℃. The fiber material treated in this way has general properties such as excellent tensile strength and dimensional stability for rubber reinforcement, and is especially smooth, has good moldability, and has excellent fatigue resistance. Furthermore, the rubber adhesion rate of the fiber material after vulcanization by embedding in compounded rubber is high, and it exhibits extremely high adhesive strength. Although it is not clear why the present invention allows smooth and highly adhesive treated fiber materials to be obtained, the smoothing agent coats the adhesive layer, resulting in improved rubber reinforcing fiber materials such as treated cords and sag. The smoothness is significantly increased, and on the other hand, the smoothing agent on the RFL (adhesive) swells the RFL itself and makes it solubilized to some extent, and also swells the unvulcanized rubber that is the adherend, improving wetting of both. It is presumed that it has a solubilizing function. The present invention will be explained in more detail below with reference to Examples. In the examples, percentages are given on a weight basis. In addition, in the examples, the inter-ply peel force indicates the adhesive force between the fiber material and the rubber, and 2 ply treated cords were made into a cross ply (cord density 27endo/25 cm) at a 90 degree angle for automobile tires. After embedding the carcass in compound rubber and vulcanizing it by pressing at 160℃ for 20 minutes, both plies were separated at 200m/m1.
The force required to peel it off at a pulling speed of 1 kg/3 cm
It is expressed as In addition, the rubber adhesion rate is a measure that indicates the adhesion of rubber to fiber materials, and when measuring the above-mentioned positive peel force, the cord that has been peeled off from the rubber is observed with the naked eye, and the middle part of the cord surface where the rubber is attached is determined. is expressed as a percentage. The bending hardness of the cord is measured using the Gurley method, and the higher the measured value, the harder it is. Furthermore, the strength retention rate is a measure of the degree of fatigue resistance, and measures how much strength remains after the cord is subjected to repeated fatigue of 6% elongation and 18% compression 3.5 million times using a Kutsdritsu fatigue testing machine between rotating disks. It is expressed as a percentage. The smoothness of the treated cord is 60m/mφ in diameter, and the roughness is
When winding at 2 m/min while contacting a 3S matte finish pin at a contact angle of 180°, the tension at the entrance to the pin (T 1 )
Then, the exit tension (T 2 ) is measured, and the frictional force (F) is calculated as F=T 2 -T 1. It is judged that the smaller F is, the better the smoothness is. Example 1 Add 10g of a 10% aqueous sodium hydroxide solution and 30g of a 28% aqueous ammonia solution to 260g of water, stir well, and add 60g of a resorcin-formaldehyde initial condensate (40% acetone solution) that has been condensed in advance with an acidic catalyst into this aqueous solution. Add and disperse thoroughly. Next, Hycar2518FS (40% manufactured by Nippon Zeon Co., Ltd.)
Dispersion Vp Latex) 240gr Hycar LX−112
Add 100 gr of (40% dispersion SBR latex manufactured by Nippon Zeon Co., Ltd.) and 80 gr of diphenylmethane diethylene urea aqueous dispersion (25% dispersion) to 200 gr of H 2 O, add while stirring thoroughly, and add formaldehyde ( 37%) 20gr was added to obtain an aqueous adhesive solution. Next, ethylene glycol diglycidyl ether and a 10 mole adduct of laurylamine ethylene oxide at a concentration of 10% by weight to the ethylene glycol diglycidyl ether were added in advance. The mixture was mixed and dispersed, and the ethylene glycol siglycidyl ether was attached to the melt-spun polyethylene terephthalate fiber so that the amount of adhesion was 0.5% by weight, and after stretching, it was heat-treated at 200°C for 1000 de//
A drawn yarn of 250fil was obtained. Three of the obtained epoxy-treated polyethylene terephthalate drawn yarns were twisted together (number of twists 40×40T/
A 10 cm) cord was passed through the adhesive solution by immersion using a computer treater processing machine (tire cord processing machine manufactured by CA Ritzler), then dried at 100°C for 120 seconds, and then heat treated at 230°C for 120 seconds. The treated cords were further treated with various smoothing agents shown in Table 1 (the emulsion or solution of the smoothing agent was dried at 110°C for 120 seconds). After embedding it in unvulcanized rubber with a carcass composition mainly composed of rubber and vulcanizing it at 150°C for 30 minutes, the inter-ply peeling force and rubber adhesion rate were measured.The results are summarized in Table 1. As is clear from Table 1, the molecular weight is 250 to 1200.
It can be seen that the cord treated with the smoothing agent has improved stiffness and rubber attachment.
【表】
実施例 2
10%苛性ソーダ水溶液4grを水63grに加えかき
まぜ、次いでレゾルシン12.5grを加え溶解し更に
ホルマリン(37%)を加え25℃で3時間熟成す
る。
熟成後予じめ水443.5grに苛性ソーダ水溶液
3.0gr、ニポール2518FS(日本ゼオン(社)製40
%)293grニポールLX−112(日本ゼオン(社)
製40%)126grを加え調製した液に、熟成したレ
ゾルシンホルムアルデヒド初期縮合物の水溶液を
ゆつくり加えていき、25℃で16時間熟成し水性接
着液を得た。
ナイロン6タイヤコード(1260/238×38T/
10cm)を前記接着剤に浸漬し100℃で120秒乾燥後
200℃で120秒熱処理した。次いで、前記第1表の
処理剤で処理した。
結果を第3表に示す。ポリエステルと同様にポ
リアミド繊維もゴム付、平滑性が改良されること
がわかる。[Table] Example 2 Add 4g of 10% caustic soda aqueous solution to 63g of water and stir. Next, add 12.5g of resorcin and dissolve. Further, formalin (37%) is added and aged at 25°C for 3 hours. After aging, add a caustic soda solution to 443.5gr of water in advance.
3.0gr, Nipole 2518FS (40 manufactured by Nippon Zeon Co., Ltd.)
%) 293gr Nipole LX-112 (Nippon Zeon Co., Ltd.)
An aqueous solution of an aged resorcinol formaldehyde initial condensate was slowly added to the solution prepared by adding 126 gr of 40% of the product, and the mixture was aged at 25°C for 16 hours to obtain an aqueous adhesive solution. Nylon 6 tire cord (1260/238×38T/
10cm) in the adhesive and dried at 100℃ for 120 seconds.
Heat treatment was performed at 200°C for 120 seconds. Then, it was treated with the treatment agent shown in Table 1 above. The results are shown in Table 3. It can be seen that, similar to polyester, polyamide fiber also has improved rubber adhesion and smoothness.
Claims (1)
クスを含む接着剤で処理した後、分子量250〜
1200の常温液状の平滑剤を主体とする処理剤で処
理することを特徴とするゴム補強用繊維材料の処
理方法。 2 繊維材料が、ポリエステル繊維、又は脂肪族
ポリアミド又は全芳香族ポリアミド繊維よりなる
特許請求の範囲第1項記載のゴム補強用繊維材料
の処理方法。 3 平滑剤が、分子量300〜1000である特許請求
の範囲第1項又は第2項記載のゴム補強用繊維材
料の処理方法。 4 処理剤が、平滑剤を70重量%以上含んでなる
特許請求の範囲第1項、第2項又は第3項記載の
ゴム補強用繊維材料の処理方法。[Claims] 1. After treating a fiber material with an adhesive containing resorcinol, formalin, and latex,
1200 A method for processing fiber materials for rubber reinforcement, characterized by processing with a processing agent mainly consisting of a smoothing agent that is liquid at room temperature. 2. The method for treating a rubber reinforcing fiber material according to claim 1, wherein the fiber material is made of polyester fiber, aliphatic polyamide or wholly aromatic polyamide fiber. 3. The method for treating a rubber reinforcing fiber material according to claim 1 or 2, wherein the smoothing agent has a molecular weight of 300 to 1000. 4. The method for treating a rubber reinforcing fiber material according to claim 1, 2 or 3, wherein the treatment agent contains 70% by weight or more of a smoothing agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56046347A JPS57161167A (en) | 1981-03-31 | 1981-03-31 | Treatment of fiber material for reinforcing rubber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56046347A JPS57161167A (en) | 1981-03-31 | 1981-03-31 | Treatment of fiber material for reinforcing rubber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57161167A JPS57161167A (en) | 1982-10-04 |
JPS6224551B2 true JPS6224551B2 (en) | 1987-05-28 |
Family
ID=12744601
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56046347A Granted JPS57161167A (en) | 1981-03-31 | 1981-03-31 | Treatment of fiber material for reinforcing rubber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57161167A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017090270A1 (en) * | 2015-11-24 | 2017-06-01 | 株式会社サンライン | Thread and method for production of same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0781234B2 (en) * | 1988-08-30 | 1995-08-30 | 帝人株式会社 | Surface modified wholly aromatic polyamide fiber |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54138687A (en) * | 1978-03-20 | 1979-10-27 | Teijin Ltd | Production of polyester synthetic fiber for enforcing rubber |
-
1981
- 1981-03-31 JP JP56046347A patent/JPS57161167A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54138687A (en) * | 1978-03-20 | 1979-10-27 | Teijin Ltd | Production of polyester synthetic fiber for enforcing rubber |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017090270A1 (en) * | 2015-11-24 | 2017-06-01 | 株式会社サンライン | Thread and method for production of same |
JPWO2017090270A1 (en) * | 2015-11-24 | 2018-09-13 | 株式会社サンライン | Yarn and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JPS57161167A (en) | 1982-10-04 |
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