JP2007046210A - Method of producing fiber for reinforcing rubber - Google Patents
Method of producing fiber for reinforcing rubber Download PDFInfo
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- JP2007046210A JP2007046210A JP2005234180A JP2005234180A JP2007046210A JP 2007046210 A JP2007046210 A JP 2007046210A JP 2005234180 A JP2005234180 A JP 2005234180A JP 2005234180 A JP2005234180 A JP 2005234180A JP 2007046210 A JP2007046210 A JP 2007046210A
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- fiber
- rubber
- treatment liquid
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- fine particles
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 47
- 239000005060 rubber Substances 0.000 title claims abstract description 45
- 239000000835 fiber Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000003014 reinforcing effect Effects 0.000 title claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 230000009477 glass transition Effects 0.000 claims abstract description 19
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 18
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 43
- 239000000853 adhesive Substances 0.000 claims description 34
- 230000001070 adhesive effect Effects 0.000 claims description 34
- 239000010419 fine particle Substances 0.000 claims description 26
- 229920000126 latex Polymers 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- -1 isocyanate compound Chemical class 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- 229960001755 resorcinol Drugs 0.000 claims description 17
- 239000012783 reinforcing fiber Substances 0.000 claims description 15
- 239000004816 latex Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 230000007423 decrease Effects 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
- 125000003118 aryl group Chemical group 0.000 description 5
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 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
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ONBWNNUYXGJKKD-UHFFFAOYSA-N 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC ONBWNNUYXGJKKD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- YQTPPZQYNWOAEV-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hept-4-ene-4-carboxylic acid Chemical compound C1CC(C(=O)O)=CC2OC21 YQTPPZQYNWOAEV-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 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
- 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 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- ULLDRQCJTSHDDT-UHFFFAOYSA-N penta-2,3,4-trienenitrile Chemical compound C=C=C=CC#N ULLDRQCJTSHDDT-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 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
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Abstract
Description
本発明はゴム補強用繊維の製造方法に関し、さらに詳しくはゴムに対する耐熱接着性の極めて高いゴム補強用繊維の製造方法に関する。 The present invention relates to a method for producing rubber reinforcing fibers, and more particularly to a method for producing rubber reinforcing fibers having extremely high heat-resistant adhesion to rubber.
ゴムなどの各種材料の補強用として、繊維材料が広く用いられてきている。このように補強用途に繊維を用いる場合、各種材料と繊維間の接着が重要課題であり、各種接着剤が開発されてきた。しかし、特に優れた物理的特性を有する合成繊維などを使用する場合、まだまだその繊維の強力に比して接着性が不足しているという問題があった。ことに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繊維で代表されるポリエステル繊維や、芳香族ポリアミド繊維等は、高強度、高ヤング率等の優れた物理的特性を有しており、補強用の繊維としては最適であるが、これら繊維はその表面が比較的不活性であるので、通常の接着剤ではゴムや樹脂等のマトリックスとの接着性が不十分となるという問題があった。 Fiber materials have been widely used for reinforcing various materials such as rubber. Thus, when using a fiber for a reinforcement use, adhesion | attachment between various materials and fibers is an important subject, and various adhesive agents have been developed. However, when synthetic fibers having excellent physical properties are used, there is still a problem that adhesiveness is still insufficient as compared with the strength of the fibers. In particular, polyester fibers such as polyethylene terephthalate and polyethylene naphthalate fibers, and aromatic polyamide fibers have excellent physical properties such as high strength and high Young's modulus, making them ideal as reinforcing fibers. However, since the surface of these fibers is relatively inactive, there is a problem that the adhesiveness to a matrix such as rubber or resin becomes insufficient with a normal adhesive.
このため現在では、脂肪族エポキシ化合物や、エチレン尿素、ブロックドイソシアネート化合物等の反応性の強い化学薬品を含む接着剤組成物が各種開発されてきている。例えば、特許文献１には、繊維の表面を種々の薬品を含む接着剤組成物であらかじめ処理し、さらにレゾルシン・ホルマリン・ゴムラテックス（ＲＦＬ）系接着剤で処理する、２浴処理方法が提案され実用化されている。または、特許文献２に開示されているようなＲＦＬ系接着剤にブロックドイソシアネートと芳香族エポキシ化合物を添加した接着剤組成物のみで処理する、１浴処理方法が実用化されている。特に耐熱接着力を向上させるためには例えば特許文献３ではケイ酸アルカリ金属塩を含有することによる耐熱接着性に優れた接着剤組成物が開示されている。 For this reason, at present, various adhesive compositions containing highly reactive chemicals such as aliphatic epoxy compounds, ethylene urea, blocked isocyanate compounds have been developed. For example, Patent Document 1 proposes a two-bath treatment method in which the fiber surface is pretreated with an adhesive composition containing various chemicals and further treated with a resorcin / formalin / rubber latex (RFL) adhesive. It has been put into practical use. Alternatively, a one-bath treatment method in which treatment is performed only with an adhesive composition in which a blocked isocyanate and an aromatic epoxy compound are added to an RFL adhesive as disclosed in Patent Document 2 has been put into practical use. In particular, in order to improve the heat-resistant adhesive force, for example, Patent Document 3 discloses an adhesive composition excellent in heat-resistant adhesive property by containing an alkali metal silicate.
しかし、これらの接着剤組成物を用いた場合であっても、過加硫時等の熱が過剰にかかる条件下等では接着力が低下し、さらには使用によって繊維強度が低下し、繊維の物理的特性を充分に発揮させるにはまだ不十分であるという問題があった。 However, even when these adhesive compositions are used, the adhesive strength is reduced under conditions where excessive heat is applied during overvulcanization or the like, and further, the fiber strength is reduced by use. There has been a problem that it is still insufficient for fully exerting physical properties.
本発明は、ゴムとの耐熱接着力および耐疲労性に優れたゴム補強用繊維の製造方法を提供することにある。 It is an object of the present invention to provide a method for producing a rubber reinforcing fiber having excellent heat-resistant adhesive strength and fatigue resistance with rubber.
本発明のゴム補強用繊維の製造方法は、合成繊維を、樹脂微粒子を含む処理液で処理する方法であって、該樹脂微粒子がコア部とシェル部からなるコアシェル構造を有し、コア部を構成するポリマーのガラス転移点温度が−２０℃以下であり、シェル部を構成するポリマーのガラス転移点温度が６０℃以上であるとともに、合成繊維を該処理液に含浸した後にシェル部を構成するポリマーのガラス転移点以上の温度で加熱処理することを特徴とする。さらには該樹脂微粒子のシェル部を構成するポリマーが水酸基またはカルボキシル基を有することが好ましい。 The method for producing a rubber reinforcing fiber of the present invention is a method of treating synthetic fibers with a treatment liquid containing resin fine particles, wherein the resin fine particles have a core-shell structure comprising a core portion and a shell portion, The glass transition temperature of the constituting polymer is −20 ° C. or lower, the glass transition temperature of the polymer constituting the shell portion is 60 ° C. or higher, and the shell portion is formed after impregnating the synthetic fiber with the treatment liquid. The heat treatment is performed at a temperature higher than the glass transition point of the polymer. Furthermore, the polymer constituting the shell part of the resin fine particles preferably has a hydroxyl group or a carboxyl group.
また処理液が、ゴムラテックスを含有することや、レゾルシン・ホルマリン・ラテックス系接着剤を含有すること、ポリエポキシド化合物及びブロックドイソシアネート化合物を含有することが好ましい。さらには該合成繊維が、ポリエポキシド化合物またはブロックドイソシアネート化合物による前処理糸であることや、ポリエステル繊維または芳香族ポリアミド繊維であることが好ましい。 The treatment liquid preferably contains a rubber latex, contains a resorcin / formalin / latex adhesive, and contains a polyepoxide compound and a blocked isocyanate compound. Furthermore, it is preferable that the synthetic fiber is a pretreated yarn with a polyepoxide compound or a blocked isocyanate compound, or a polyester fiber or an aromatic polyamide fiber.
本発明によれば、ゴムとの耐熱接着力および耐疲労性に優れたゴム補強用繊維の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the fiber for rubber reinforcement excellent in the heat-resistant adhesive force and fatigue resistance with rubber | gum is provided.
本発明は合成繊維をコアシェル構造を有する樹脂微粒子を含む処理液に含浸、加熱処理を行うゴム補強用繊維の製造方法である。
ここで本発明の製造方法で用いられる合成繊維には特に制限は無いが、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレートに代表されるポリエステル、ナイロン６、ナイロン６６に代表される脂肪族ポリアミド、芳香族ポリアミド、およびポリビニルアルコール、ポリエチレンからなるポリマーを紡糸、延伸することにより得られる繊維であることが好ましい。これらの繊維は、高強力化を図るために、高粘度のポリマーを用い、高延伸倍率で延伸されたものであることが望ましい。
The present invention is a method for producing a rubber-reinforcing fiber in which a synthetic fiber is impregnated with a treatment liquid containing resin fine particles having a core-shell structure and subjected to heat treatment.
Here, the synthetic fiber used in the production method of the present invention is not particularly limited. For example, polyethylene terephthalate, polyester typified by polybutylene terephthalate, nylon 6, aliphatic polyamide typified by nylon 66, and aromatic polyamide And a fiber obtained by spinning and stretching a polymer comprising polyvinyl alcohol and polyethylene. These fibers are desirably drawn using a high-viscosity polymer at a high draw ratio in order to increase the strength.
合成繊維の形状は、特に制限されるものではなく、ヤーン、コード、不織布、織編物等種々の繊維集合形態で処理することができ、柔軟に本発明の製造プロセスを実施することが出来る。しかし特にはゴム補強用用途として、マルチフィラメントからなる合成繊維であることが好ましい。特に好ましくは、単糸太さが０．５〜６．０ｄｔｅｘ、フィラメント数が１８０〜１０００フィラメントであるフィラメント糸を使用し、３０〜７０Ｔ／１０ｃｍで下撚りを施し、これを２〜４本あわせて逆方向に３０〜７０Ｔ／１０ｃｍで上撚りを施したものである。また、その合計太さは１０００〜１００００ｄｔｅｘ、特に好ましくは２２００〜６６００ｄｔｅｘであるものが好ましい。断面形状は、強度の点などから円形であることが好ましいが、接着性の観点から異型断面をとることも本方法では可能である。 The shape of the synthetic fiber is not particularly limited, and can be processed in various fiber aggregate forms such as yarn, cord, nonwoven fabric, woven or knitted fabric, and the production process of the present invention can be implemented flexibly. However, a synthetic fiber made of multifilament is particularly preferred for rubber reinforcement. Particularly preferably, a filament yarn having a single yarn thickness of 0.5 to 6.0 dtex and a filament number of 180 to 1000 filaments is used, and a twist is applied at 30 to 70 T / 10 cm. In the reverse direction, the upper twist is applied at 30 to 70 T / 10 cm. The total thickness is preferably 1000 to 10000 dtex, particularly preferably 2200 to 6600 dtex. The cross-sectional shape is preferably circular from the viewpoint of strength, but it is also possible in this method to take an irregular cross-section from the viewpoint of adhesiveness.
本発明で用いられる処理液は樹脂微粒子を含むものであり、樹脂微粒子がコア部とシェル部からなるコアシェル構造を有し、コア部を構成するポリマーのガラス転移点温度が−２０℃以下であり、シェル部を構成するポリマーのガラス転移点温度が６０℃以上であることを必須とする。コア部ポリマーのガラス転移温度としては−３０℃以下であることがさらには−３５〜−７０℃の範囲であることがより好ましい。ガラス転移温度が−２０℃より高い場合には、加熱処理時の繊維に対する含浸性が低下し、耐熱性向上効果を得ることができない。また、シェル部ポリマーのガラス転移温度としては８０〜１３０℃であることがより好ましく、低すぎる場合には加熱処理前の繊維への処理液の含浸時の安定性が低下し、本発明の効果を安定して得ることができない。 The treatment liquid used in the present invention contains resin fine particles, the resin fine particles have a core-shell structure composed of a core part and a shell part, and the glass transition temperature of the polymer constituting the core part is −20 ° C. or lower. In addition, it is essential that the glass transition temperature of the polymer constituting the shell portion is 60 ° C. or higher. The glass transition temperature of the core polymer is preferably −30 ° C. or lower, more preferably −35 to −70 ° C. When the glass transition temperature is higher than −20 ° C., the impregnation property to the fiber during the heat treatment is lowered, and the heat resistance improvement effect cannot be obtained. Further, the glass transition temperature of the shell part polymer is more preferably 80 to 130 ° C. If it is too low, the stability during impregnation of the treatment liquid into the fiber before the heat treatment is lowered, and the effect of the present invention Can not be obtained stably.
本発明で用いられる樹脂微粒子のコア部としては共役ジエンまたはアルキル基の炭素数が２〜８であるアルキルアクリレートあるいはそれらの混合物を重合させて得られたゴム状ポリマーであることが好ましい。ここでコア部の樹脂微粒子に占める割合は重量で５０〜９０重量％の範囲が適当である。 The core part of the resin fine particles used in the present invention is preferably a rubbery polymer obtained by polymerizing a conjugated diene or an alkyl acrylate having 2 to 8 carbon atoms in an alkyl group or a mixture thereof. Here, the ratio of the core part to the resin fine particles is suitably in the range of 50 to 90% by weight.
さらにシェル部を構成するポリマーが水酸基またはカルボキシル基を有することが好ましい。このような基を有することにより、繊維のゴムに対する接着性をより向上させることが可能となる。またこのような樹脂微粒子を処理液中で安定して存在させるためには、水溶液、乳化物として用いることが好ましい。より具体的にはビニル重合性ポリマーなどが好ましく、例えばエチルアクリレート、ブチルアクリレート等のアルキルアクリレート、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート等のアルキルメタクリレート、スチレン、ビニルトルエン、α−メチルスチレン等の芳香族ビニル、芳香族ビニリデン、アクリロニトリル、メタクリロニトリル等のシアン化ビニル、シアン化ビニリデン等のビニル重合性モノマーをあげることができる。 Furthermore, the polymer constituting the shell part preferably has a hydroxyl group or a carboxyl group. By having such a group, it becomes possible to further improve the adhesion of the fibers to the rubber. Moreover, in order to make such resin fine particles exist stably in a processing liquid, it is preferable to use as aqueous solution and an emulsion. More specifically, a vinyl polymerizable polymer is preferable, for example, alkyl acrylate such as ethyl acrylate and butyl acrylate, alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate, aromatic such as styrene, vinyl toluene, and α-methyl styrene. Examples thereof include vinyl polymerizable monomers such as vinyl cyanide, vinyl cyanide such as vinyl, aromatic vinylidene, acrylonitrile, and methacrylonitrile, and vinylidene cyanide.
このようなコアシェル構造を有する樹脂微粒子は従来公知の方法により得ることができ、市販品のコアシェルポリマーの中から適切な物性を有する樹脂微粒子を選択して用いることも可能である。 The resin fine particles having such a core-shell structure can be obtained by a conventionally known method, and resin fine particles having appropriate physical properties can be selected and used from commercially available core-shell polymers.
また、本発明で用いられる処理液はゴム／繊維間の接着力を向上させるために各種成分を含有することが好ましい。ゴムとの接着性を向上させるためには、処理液がゴムラテックスを含有すること、特にはレゾルシン・ホルマリン・ラテックス系の接着剤を含有することが好ましい。一方、繊維のゴム用接着剤との親和性を向上させるためには処理液がポリエポキシド化合物及びブロックドイソシアネート化合物を含有することが好ましい。 Further, the treatment liquid used in the present invention preferably contains various components in order to improve the adhesive force between rubber / fiber. In order to improve the adhesion to rubber, it is preferable that the treatment liquid contains a rubber latex, particularly a resorcin / formalin / latex adhesive. On the other hand, in order to improve the affinity of the fibers with the rubber adhesive, the treatment liquid preferably contains a polyepoxide compound and a blocked isocyanate compound.
本発明で好ましく用いられるゴムラテックスとしては、例えば、天然ゴムラテックス、スチレン・ブタジエン・コポリマーラテックス、ビニルピリジン・スチレン・ブタジエンターポリマーラテックス、ニトリルゴムラテックス、クロロブレンゴムラテックス、エチレン・プロピレン・ジエンモノマーラテックス等であり、これらを単独、又は、併用することができる。なかでも、ビニルピリジン・スチレン・ブタジエンターポリマーラテックスを単独、又は、他のものと併用するものが好ましい。併用使用の場合には、該ビニルピリジン・スチレン・ブタジエンターポリマーラテックスを全ラテックス重量の１／３量以上使用した場合が優れた性能のものが得られる。 Examples of rubber latex preferably used in the present invention include natural rubber latex, styrene / butadiene copolymer latex, vinylpyridine / styrene / butadiene terpolymer latex, nitrile rubber latex, chlorobrene rubber latex, ethylene / propylene / diene monomer latex. These can be used alone or in combination. Especially, what uses vinyl pyridine * styrene * butadiene terpolymer latex individually or in combination with another thing is preferable. When used in combination, excellent performance is obtained when the vinylpyridine / styrene / butadiene terpolymer latex is used in an amount of 1/3 or more of the total latex weight.
また、処理液がレゾルシン・ホルマリン・ラテックス系の接着剤を含有する場合、このようなレゾルシン・ホルマリン・ゴムラテックス系接着剤（ＲＦＬ）としては、レゾルシンとホルムアルデヒドのモル比が、１：０．１〜１：８の範囲にあるものが、より好ましくは１：１〜１：４の範囲であるものであることが好ましい。ホルムアルデヒドの添加量が少なすぎるとレゾルシン・ホルマリンの縮合物の架橋密度が低下すると共に分子量の低下を招くため、接着剤層凝集力が低下することにより、接着性が低下するおそれがある。逆にホルムアルデヒドの添加量が多すぎると架橋密度上昇によりレゾルシン・ホルマリン縮合物が硬くなり、被着体ゴムとの共加硫時にＲＦＬとゴムとの相溶化が阻害され、接着性が低下すると共に処理後の接着剤層の収縮が顕著となり、界面での応力集中による界面剥離による接着力が低下する。 When the treatment solution contains a resorcin / formalin / latex adhesive, the resorcin / formalin / rubber latex adhesive (RFL) has a molar ratio of resorcin / formaldehyde of 1: 0.1. What is in the range of ˜1: 8 is more preferably in the range of 1: 1 to 1: 4. If the amount of formaldehyde added is too small, the crosslink density of the condensate of resorcin / formalin is lowered and the molecular weight is lowered. Therefore, the adhesive layer cohesive force is lowered and the adhesiveness may be lowered. On the other hand, if the amount of formaldehyde added is too large, the resorcin / formalin condensate becomes hard due to an increase in the crosslinking density, and the compatibility between the RFL and the rubber is inhibited at the time of co-vulcanization with the adherend rubber, and the adhesiveness decreases. Shrinkage of the adhesive layer after the treatment becomes remarkable, and the adhesive force due to interface peeling due to stress concentration at the interface is reduced.
レゾルシン・ホルマリンとゴムラテックスとの配合比率は、前記のコアシェルポリマーの添加割合によって変化するが、固形分量比で、レゾルシン・ホルマリン：ゴムラテックス（ＲＦＬ）が１：１〜１：１５の範囲にあるものが好ましく、特に、１：３〜１：１２の範囲にあるものが好ましく使用される。該ゴムラテックスの比率が少なすぎると処理された繊維が硬くなって耐疲労性が低下しやすくなり、また、接着剤組成物中のラテックス及び被着体であるゴムとの共加硫が不十分となり、接着性が低くなるおそれがあり、逆に、該ゴムラテックスの比率が多すぎると接着剤皮膜として充分な強度を得ることが出来ないため、満足な接着力やゴム付着率が得られないおそれがある。 The blending ratio of resorcin / formalin and rubber latex varies depending on the addition ratio of the core-shell polymer, but resorcin / formalin: rubber latex (RFL) is in the range of 1: 1 to 1:15 in the solid content ratio. Those having a range of 1: 3 to 1:12 are particularly preferably used. If the ratio of the rubber latex is too small, the treated fiber becomes hard and the fatigue resistance tends to be lowered, and the latex in the adhesive composition and the rubber as the adherend are not sufficiently vulcanized. In contrast, if the ratio of the rubber latex is too large, sufficient strength as an adhesive film cannot be obtained, so that satisfactory adhesive force and rubber adhesion rate cannot be obtained. There is a fear.
ＲＦＬ系接着剤を主成分とした場合には、総固形分濃度が１〜３０重量％の範囲であることが好適であり、さらには５〜２０重量％の範囲であることであることが好ましい。接着剤組成物の濃度が前記範囲よりも低すぎると接着剤の付着量低下を招き、接着性が低下し、逆に、接着剤組成物の濃度が前記範囲よりも高すぎると固形分付着量が多くなりすぎるため繊維が硬くなって耐疲労性が低下する傾向にある。 When the RFL adhesive is a main component, the total solid content concentration is preferably in the range of 1 to 30% by weight, and more preferably in the range of 5 to 20% by weight. . If the concentration of the adhesive composition is too lower than the above range, the adhesion amount of the adhesive will be reduced and the adhesiveness will be reduced. Conversely, if the concentration of the adhesive composition is too high above the above range, the solid content will be attached. Therefore, the fiber becomes hard and the fatigue resistance tends to decrease.
さらには合成繊維があらかじめポリエポキシド化合物またはブロックイソシアネートによる前処理糸であることが好ましい。そして特に好ましい方法は、合成繊維を、ポリエポキシド化合物及びブロックドイソシアネート化合物を含有する処理液（１）と、レゾルシン・ホルマリン・ラテックス系接着剤を含有する処理液（２）の少なくとも２種の処理液で処理する、いわゆる２浴処理と呼ばれる処理方法であって、処理液（１）、処理液（２）のいずれか一方または両方に、コア部とシェル部からなるコアシェル構造である上記の樹脂微粒子を含有するものを用いることが好ましい。 Furthermore, it is preferable that the synthetic fiber is pretreated yarn with a polyepoxide compound or a blocked isocyanate in advance. A particularly preferable method is that the synthetic fiber is treated with at least two kinds of treatment liquid (1) containing a polyepoxide compound and a blocked isocyanate compound and treatment liquid (2) containing a resorcin / formalin / latex adhesive. The above-mentioned resin fine particles having a core-shell structure consisting of a core portion and a shell portion in one or both of the treatment liquid (1) and the treatment liquid (2). It is preferable to use those containing.
本発明で好ましく用いられるポリエポキシド化合物としては、１分子中に少なくとも２個以上のエポキシ基を有する化合物であり、そのエポキシ基の含有量は、該ポリエポキシド化合物：１００ｇ当り０．２ｇ当量以上を含有する化合物である。このような化合物としては、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ごと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−ヒドロキシフェニル）ジメチルメタン、フェノール・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ェ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化合物を酸化して得られるポリエポキシド化合物、すなわち、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）アジペート等を挙げることができる。これらのうち、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、すなわち、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ことができるので好ましく例示される。 The polyepoxide compound preferably used in the present invention is a compound having at least two epoxy groups in one molecule, and the epoxy group content is 0.2 g equivalent or more per 100 g of the polyepoxide compound. A compound. Such compounds include reaction products of polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene glycol and halogen-containing epoxides such as epichlorohydrin, resorcin, bis (4-hydroxyphenyl) dimethylmethane. Reaction products of polyhydric phenols such as phenol / formaldehyde resin and resorcin / formaldehyde resin with the halogen-containing epoxides, polyepoxide compounds obtained by oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, That is, 3,4-epoxycyclohexylene epoxide, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cyclohexylmedium Le) adipate, and the like can be given. Among these, the reaction product of polyhydric alcohol and epichlorohydrin, that is, the polyglycidyl ether compound of polyhydric alcohol is particularly preferred because it can exhibit excellent performance.
かかるポリエポキシド化合物は、通常は水溶液、若しくは、乳化液として使用するものがよい。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、あるいは、必要に応じて少量の溶剤に溶解したものを、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ナトリウム塩、ノニルフェノールエチレンオキサイド付加物等を用いて乳化、又は溶解することができる。 Such polyepoxide compounds are usually used as an aqueous solution or an emulsion. In order to obtain an emulsified liquid or solution, for example, a polyepoxide compound as it is or dissolved in a small amount of a solvent as necessary is used as a known emulsifier such as sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium. It can be emulsified or dissolved using a salt, nonylphenol ethylene oxide adduct or the like.
また本発明で好ましく用いられるブロックドイソシアネート化合物としては、ポリイソシアネート化合物とブロック化剤との付加化合物であり、加熱によりブロッ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じるものであることが好ましい。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、メタフェニレンジイソシアネート、ジフェ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、トリフェ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、あるいはこれらポリイソシアネートと活性水素原子を２個以上有する化合物、例えばトリメチロールプロパン、ペンタエリスリトール等とをイソシアネート基（−ＮＣＯ）とヒドロキシル基（−ＯＨ）の比が１を超えるモル比で反応させて得られる末端イソシアネート基含有のポリオールアダクトポリイソシアネート等が挙げられる。特にトリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリメチレンポリフ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。ブロックドイソシアネート化合物のブロック化剤としては、例えばフェノール，チオフェノール，クレゾール，レゾルシノール等のフェノール類、ジフェニルアミン、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ある。 The blocked isocyanate compound preferably used in the present invention is an addition compound of a polyisocyanate compound and a blocking agent, and is preferably a compound that liberates a block component by heating to produce an active polyisocyanate compound. Examples of the polyisocyanate compound include polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, or two or more of these polyisocyanates and active hydrogen atoms. Terminal isocyanate group-containing polyol adduct polyisocyanate obtained by reacting a compound having, for example, trimethylolpropane, pentaerythritol, etc. with a molar ratio of isocyanate group (—NCO) to hydroxyl group (—OH) exceeding 1. Is mentioned. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate are preferable because they exhibit excellent performance. Examples of blocking agents for blocked isocyanate compounds include phenols such as phenol, thiophenol, cresol, and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, lactams such as phthalimides, caprolactam, and valerolactam. Oximes such as acetoxime, methyl ethyl ketone oxime, cyclohexane oxime, and acidic sodium sulfite.
本発明は上記のような組成物と樹脂微粒子を含む処理液で合成繊維を処理する方法であるが、処理液の総固形分濃度は１〜３０重量％であることが好ましく、さらに好ましくは、２〜２０重量％の範囲である。総固形分濃度が低すぎると接着剤表面張力が増加し、繊維表面に対する均一付着性が低下すると共に、固形分付着量が低下することにより接着性が低下し、また、一方、該処理剤濃度が高すぎると生産コスト的に不利になるだけでなく、固形分付着量が多くなりすぎるため硬くなり耐疲労性が低下しやすい傾向にある。 The present invention is a method for treating synthetic fibers with a treatment liquid containing the composition and resin fine particles as described above, and the total solid content concentration of the treatment liquid is preferably 1 to 30% by weight, more preferably, It is in the range of 2 to 20% by weight. If the total solid content concentration is too low, the adhesive surface tension increases, the uniform adhesion to the fiber surface decreases, and the adhesion decreases due to a decrease in the solid content, while the treatment agent concentration If it is too high, not only will it be disadvantageous in terms of production cost, but the amount of solid content will increase so much that it will become hard and fatigue resistance will tend to be reduced.
また、処理液中の樹脂微粒子は、処理液中の全固形成分中での樹脂微粒子の含有率が０．５〜１０重量％であることが好ましく、最も好ましくは１〜５重量％であることが好ましい。すなわち樹脂微粒子の繊維に対する付着量は０．００５〜２重量％、さらには０．０１〜1重量％の範囲であることが好ましい。 The resin fine particles in the treatment liquid preferably have a resin fine particle content of 0.5 to 10% by weight, and most preferably 1 to 5% by weight in the total solid components in the treatment liquid. Is preferred. That is, the adhesion amount of the resin fine particles to the fiber is preferably in the range of 0.005 to 2% by weight, more preferably 0.01 to 1% by weight.
本発明の処理液は各種成分を水分散物として用いるために界面活性剤を用いることが好ましく、界面活性剤の含有量としては処理液の全固形分に対し、１５重量％以下であり、好ましくは、１〜１０重量％で用いるものであることが好ましい。界面活性剤の量が多すぎる場合には接着性が低下する傾向にある。 In the treatment liquid of the present invention, it is preferable to use a surfactant in order to use various components as an aqueous dispersion, and the content of the surfactant is preferably 15% by weight or less based on the total solid content of the treatment liquid, preferably Is preferably used at 1 to 10% by weight. When the amount of the surfactant is too large, the adhesiveness tends to decrease.
さらに２浴処理で行う場合には、１浴目の処理液ａの固形分付着量は、０．１〜１０重量％の範囲で使用することが好ましく、より好ましくは、０．３〜７重量％の範囲、さらに好ましくは、０．５〜５重量％の範囲で付着せしめることが好ましい。さらには２浴目の処理液ｂの繊維に対する固形分付着量は、０．１〜２０重量％の範囲で使用する方法が好ましく、さらに好ましくは、０．５〜１０重量％の範囲で付着させる方法である。繊維に対する処理液の付着量を制御するためには、ローラーとの接触、ノズルからの噴霧による塗布、又は溶液への浸漬などの操作を経た後、圧接ローラーによる絞り、スクレバー等によるかき落とし、空気吹きつけによる吹き飛ばし、吸引、ビーターの手段により行うことが出来る。また付着量を上げるため、もしくは均一性を確保するために複数回付着させてもよい。 Furthermore, when performing by 2 bath processing, it is preferable to use the solid content adhesion amount of the processing liquid a of the 1st bath in the range of 0.1-10 weight%, More preferably, 0.3-7 weight %, More preferably 0.5 to 5% by weight. Furthermore, the method of using solid content adhesion amount with respect to the fiber of the processing solution b of the 2nd bath is preferably 0.1 to 20% by weight, and more preferably 0.5 to 10% by weight. Is the method. In order to control the amount of the treatment liquid attached to the fibers, after operations such as contact with a roller, application by spraying from a nozzle, or immersion in a solution, squeezing with a pressure roller, scraping with a scrubber, etc., air blowing It can be carried out by blowing, sucking, or beatering. Moreover, you may make it adhere several times in order to raise the adhesion amount or to ensure uniformity.
本発明の製造方法は、上記のように合成繊維を処理液に含浸した後に、樹脂微粒子のシェル部を構成するポリマーのガラス転移点以上の温度で加熱処理を行う。さらには加熱処理温度としてはガラス転移点温度より５〜５０℃高いことが好ましい。また処理温度としては１０〜２０℃であることが好ましく、時間的には３０〜１８０秒の範囲であることが好ましい。温度は均一にするために熱風乾燥機を用いることが好ましい。 In the production method of the present invention, after impregnating the synthetic fiber with the treatment liquid as described above, the heat treatment is performed at a temperature equal to or higher than the glass transition point of the polymer constituting the shell portion of the resin fine particles. Furthermore, the heat treatment temperature is preferably 5 to 50 ° C. higher than the glass transition temperature. Moreover, it is preferable that it is 10-20 degreeC as process temperature, and it is preferable that it is the range of 30-180 second in time. In order to make the temperature uniform, it is preferable to use a hot air dryer.
本発明では、このようなコアシェル構造を有する樹脂微粒子をそのシェル部を構成するポリマーのガラス転移点以上の温度で加熱処理を行うことにより、処理液中では均一に分散が行われながら、熱処理後には繊維表面に強固に皮膜を形成することができる。 In the present invention, the resin fine particles having such a core-shell structure are subjected to a heat treatment at a temperature equal to or higher than the glass transition point of the polymer constituting the shell portion, so that the resin particles are uniformly dispersed in the treatment liquid. Can form a strong film on the fiber surface.
このような本発明の製造方法によって得られたゴム補強用繊維はコアシェル構造を有する樹脂微粒子が処理剤中に均一に分散することによって、乾燥後の処理液の弾性を向上させ、耐熱接着性及び疲労性を高めることができる。このゴム補強用繊維は、例えばタイヤ、ベルトおよびホースなどの繊維補強されたゴム繊維複合体に用いられ、得られるゴム繊維複合体は高い接着性を有する高品質な特性を発揮するため、繊維補強ゴム製品として極めて有用である。 The rubber reinforcing fiber obtained by such a production method of the present invention improves the elasticity of the treatment liquid after drying by uniformly dispersing resin fine particles having a core-shell structure in the treatment agent. Fatigue can be increased. This rubber reinforcing fiber is used for a fiber reinforced rubber fiber composite such as tires, belts and hoses, for example, and the resulting rubber fiber composite exhibits high quality properties with high adhesiveness. It is extremely useful as a rubber product.
以下、本発明を実施例を用いて説明するが、本発明はこれらの実施例に限定されるものでははない。尚、実施例および比較例において、評価方法は下記の方法により測定した。 EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these Examples. In Examples and Comparative Examples, the evaluation method was measured by the following method.
（１）コード剥離接着力
処理コードとゴムとの接着力を示すものである。天然ゴムを主成分とするカーカス配合の未加硫ゴムシート表層近くに５本のコードを埋め、１５０℃の温度で、３０分間、５０ｋｇ／ｃｍ２のプレス圧力（初期値）、又は、１８０℃の温度で４０分間、５０ｋｇ／ｃｍ２のプレス圧力（耐熱値）で加硫し、次いで、両端のコードを残し３本のコードをゴムシート面に対し９０度の方向へ２００ｍｍ／分の速度で剥離するのに要した力をＮ／３本で示したものである。
(1) Cord peeling adhesive strength This indicates the adhesive strength between the treated cord and rubber. Five cords are buried near the surface layer of an unvulcanized rubber sheet containing carcass containing natural rubber as a main component, at a temperature of 150 ° C. for 30 minutes, a pressing pressure of 50 kg / cm 2 (initial value), or 180 ° C. For 40 minutes at a temperature of 50 kg / cm 2 at a pressing pressure (heat resistance value), and then leaving the cords at both ends and leaving the three cords at a speed of 200 mm / min in the direction of 90 degrees with respect to the rubber sheet surface. The force required for peeling is indicated by N / 3.
（２）コード引抜接着力
処理コードとゴムとの剪断接着力を示すものである。コードを天然ゴムを主成分とするカーカス配合の未加硫ゴムブロック中に埋め込み、１５０℃の温度で、３０分間、５０ｋｇ／ｃｍ２のプレス圧力（初期値）、又は、１８０℃の温度で２０分間、５０ｋｇ／ｃｍ２のプレス圧力（耐熱値）で加硫し、次いで、コードを該ゴムブロックから２００ｍｍ／分の速度で引き抜き、引き抜きに要した力をＮ／７ｍｍで表示したものである。
(2) Cord pull-out adhesive strength This shows the shear adhesive strength between the treated cord and rubber. The cord is embedded in an unvulcanized rubber block containing carcass containing natural rubber as a main component, pressed at a temperature of 150 ° C. for 30 minutes, a press pressure of 50 kg / cm 2 (initial value), or 20 at a temperature of 180 ° C. Vulcanization was performed at a pressing pressure (heat resistance value) of 50 kg / cm 2 for 5 minutes, and then the cord was pulled out from the rubber block at a speed of 200 mm / min, and the force required for the drawing was expressed in N / 7 mm.
（３）コード疲労性（強力保持率）
未加硫ゴムに接着処理コード１本を埋め込み温度１５０℃で３０分、５０ｋｇ／ｃｍ２の条件で加硫すると同時にゴムに接着させた試験片を用い、ＪＩＳ Ｌ−１０１７のディスク疲労（グッドリッチ法）に従って、８０℃雰囲気下、伸張率：＋６．０％、圧縮率：−１８．０、疲労回数：１００万回の条件で行ったときの疲労前後の強力から強力維持率を評価した。
(3) Cord fatigue (strong retention)
An unvulcanized rubber was embeded with an adhesive treatment cord at a temperature of 150 ° C. for 30 minutes and vulcanized under the conditions of 50 kg / cm 2 , and at the same time using a test piece adhered to the rubber, JIS L-1017 disc fatigue (Goodrich The strength retention rate was evaluated from the strength before and after fatigue under the conditions of 80 ° C. atmosphere, elongation rate: + 6.0%, compression rate: −18.0, number of fatigue times: 1 million times.
［実施例１］
各処理液は以下の用にして調液した。
（１）一浴目用の処理液（１）
樹脂微粒子として、コア部がｎ−ブチルアクリレート、アリルメタクリレート、ブチレングリコールジアクリレートを重合させて得られたゴム状ポリマーで、シェル部がメチルメタアクリレート、エチルアクリレートを重合させて得られたガラス状ポリマーであるコアシェルポリマーを用いた。このもののコア部を構成するポリマーのガラス転移点温度は−４０℃であり、シェル部を構成するポリマーのガラス転移点温度は１１０℃であった。またシェル部を構成するポリマーは水酸基とカルボキシル基を有するため乳化物であった。
[Example 1]
Each treatment solution was prepared as follows.
(1) Treatment liquid for the first bath (1)
As a resin fine particle, the core part is a rubbery polymer obtained by polymerizing n-butyl acrylate, allyl methacrylate, butylene glycol diacrylate, and the shell part is a glassy polymer obtained by polymerizing methyl methacrylate and ethyl acrylate. A core-shell polymer was used. The glass transition temperature of the polymer constituting the core portion was −40 ° C., and the glass transition temperature of the polymer constituting the shell portion was 110 ° C. The polymer constituting the shell part was an emulsion because it had a hydroxyl group and a carboxyl group.
一浴目用の処理液としては、ソルビトールポリグリシジルエーテル（固形分濃度１００％）、εカプロラクタムメチレンジフェニルジイソシアネート（ＭＤＩ）（固形分濃度２５％）、コアシェルポリマー（固形分濃度１０％）、ビニルピリジンスチレンブタジエンターポリマーゴムラテックス（固形分濃度４０．５％）を３．０重量部、１３重量部、２．５重量部、８４重量部の割合で混合し、総固形分濃度を１０．０重量％とし、得られた処理液を一浴目用の処理液（１）とした。 As the treatment solution for the first bath, sorbitol polyglycidyl ether (solid content concentration 100%), ε caprolactam methylene diphenyl diisocyanate (MDI) (solid content concentration 25%), core-shell polymer (solid content concentration 10%), vinylpyridine Styrene butadiene terpolymer rubber latex (solid content concentration 40.5%) is mixed in the ratio of 3.0 parts by weight, 13 parts by weight, 2.5 parts by weight, 84 parts by weight, and the total solid content concentration is 10.0 weights. %, And the obtained treatment liquid was designated as treatment liquid (1) for the first bath.
（２）一浴目用の処理液（ａ）
コアシェルポリマーを添加しない以外は処理液（１）と同じ組成とし、濃度調整のために水を添加した以外は同様にして一浴目用の処理液（ａ）を作成した。
(2) Treatment liquid for the first bath (a)
A treatment solution (a) for the first bath was prepared in the same manner as in the treatment solution (1) except that the core-shell polymer was not added, except that water was added to adjust the concentration.
（３）二浴目用の処理液（２）
レゾルシン／ホルマリン（Ｒ／Ｆ）のモル比が１／０．６、固形分濃度が６５重量％であるレゾルシン・ホルマリン初期縮合物をアルカリ条件下溶解し９重量％水溶液とする。この上記９％初期縮合物５０重量部に対し、４０．５％ビニルピリジン・スチレン・ブタジエンターボリマーラテックス水乳化液４２０重量部添加する。この液にホルマリン３重量部、５０重量％クレゾールノボラック型芳香族エポキシ化合物分散体を１８重量部、３３重量％アセトキシムブロックドジフエニルメタンジイソシアネート分散体を１７重量部添加し、４８時間熟成したのち、１０％コアシェルポリマーを２０重量部加え固形分濃度２０重量％を二浴目用の処理液（２）とした。
(3) Treatment liquid for the second bath (2)
A resorcin / formalin initial condensate having a resorcin / formalin (R / F) molar ratio of 1 / 0.6 and a solid concentration of 65% by weight is dissolved under alkaline conditions to obtain a 9% by weight aqueous solution. To 50 parts by weight of the 9% initial condensate, 420 parts by weight of 40.5% vinylpyridine / styrene / butadiene turbolimer latex aqueous emulsion is added. To this solution was added 3 parts by weight of formalin, 18 parts by weight of a 50% by weight cresol novolak type aromatic epoxy compound dispersion, and 17 parts by weight of 33% by weight acetoxime blocked diphenylmethane diisocyanate dispersion, followed by aging for 48 hours. 20 parts by weight of 10% core-shell polymer was added, and a solid content concentration of 20% by weight was used as the treatment liquid (2) for the second bath.
（４）二浴目用の処理液（ｂ）
コアシェルポリマーを添加しない以外は処理液（２）と同じ組成とし、濃度調整のために水を添加した以外は同様にして二浴目用の処理液（ｂ）を作成した。
(4) Treatment liquid for the second bath (b)
A treatment liquid (b) for the second bath was prepared in the same manner as in the treatment liquid (2) except that the core-shell polymer was not added, and water was added to adjust the concentration.
（ゴム補強用繊維の製造）
固有粘度が０．９５のポリエチレンテレフタレートからなる１６７０ｄｔｅｘ／３８４フィラメントのマルチフィラメント糸を使用し、該マルチフィラメント糸に４０Ｔ／１０ｃｍで下撚りを施し、これを２本合わせて４０Ｔ／ｃｍで上撚りを施して３３４０ｄｔｅｘ／７６８フィラメントのコードを得た。
(Manufacture of rubber reinforcing fibers)
A multi-filament yarn of 1670 dtex / 384 filament made of polyethylene terephthalate with an intrinsic viscosity of 0.95 is used. The multi-filament yarn is subjected to a lower twist at 40 T / 10 cm, and two of these are twisted together to give an upper twist at 40 T / cm. To obtain a cord of 3340 dtex / 768 filament.
該コードをコンビュートリーター処理機（ＣＡリッツラー株式会社製、タイヤコード処理機）を用いて、前記の処理液（１）に浸漬した後、１３０℃の温度で２分間乾燥し、引き続き、２４０℃の温度で１分間の熱処理を行い、続いて、処理液（２）に浸漬した後に、１７０℃の温度で２分間乾燥し、引続いて、２４０℃の温度で１分間の熱処理を行った。得られたコードには、処理剤の固形分として、一浴目の処理液（１）が２．０重量％（樹脂微粒子は０．１２％）、二浴目の処理液（２）が１．５重量％（樹脂微粒子は０．０１６％）付着していた。得られた処理コードを天然ゴムを主成分とするカーカス配合の未加硫ゴム中に埋め込み、１５０℃の温度で３０分間、及び、１８０℃の温度で６０分間、加硫し前記の方法により評価した。その結果を表１に示す。 The cord was immersed in the treatment liquid (1) using a contributor processing machine (tire code processing machine manufactured by CA Ritzler Co., Ltd.), then dried at a temperature of 130 ° C. for 2 minutes, and subsequently 240 ° C. Then, after being immersed in the treatment liquid (2), it was dried at a temperature of 170 ° C. for 2 minutes, followed by a heat treatment at a temperature of 240 ° C. for 1 minute. In the obtained cord, the treatment liquid (1) in the first bath was 2.0% by weight (the resin fine particles were 0.12%) and the treatment liquid (2) in the second bath was 1 as the solid content of the treatment agent. 5% by weight (0.06% of resin fine particles) was adhered. The obtained treated cord was embedded in an unvulcanized rubber containing carcass containing natural rubber as a main component, vulcanized at a temperature of 150 ° C. for 30 minutes and at a temperature of 180 ° C. for 60 minutes, and evaluated by the above method. did. The results are shown in Table 1.
［実施例２］
一浴目の処理液（１）の替わりに処理液（ａ）を用いた以外は、実施例１と同様の処理を行った。結果を表１に併せて記す。
[Example 2]
The same treatment as in Example 1 was carried out except that the treatment liquid (a) was used instead of the treatment liquid (1) in the first bath. The results are also shown in Table 1.
［実施例３］
二浴目の処理液（２）の替わりに処理液（ｂ）を用いた以外は、実施例１と同様の処理を行った。結果を表１に併せて記す。
[Example 3]
The same treatment as in Example 1 was performed except that the treatment liquid (b) was used instead of the treatment liquid (2) in the second bath. The results are also shown in Table 1.
［比較例１］
一浴目の処理液（１）の替わりに処理液（ａ）を用い、２浴目の処理液（２）の替わりに処理液（ｂ）を用いた以外は、実施例１と同様の処理を行った。結果を表１に併せて記す。
[Comparative Example 1]
The same treatment as in Example 1 except that the treatment liquid (a) was used instead of the treatment liquid (1) for the first bath and the treatment liquid (b) was used instead of the treatment liquid (2) for the second bath. Went. The results are also shown in Table 1.
Claims (8)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005234180A JP2007046210A (en) | 2005-08-12 | 2005-08-12 | Method of producing fiber for reinforcing rubber |
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| JP2005234180A JP2007046210A (en) | 2005-08-12 | 2005-08-12 | Method of producing fiber for reinforcing rubber |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161872A (en) * | 2007-12-28 | 2009-07-23 | Bridgestone Corp | Adhesive composition for organic fiber cord, and method for producing rubber product using the same adhesive composition |
| JP2009174105A (en) * | 2007-12-25 | 2009-08-06 | Bridgestone Corp | Method for producing adhesive composition for organic fiber cord, adhesive composition for organic fiber cord and method for producing rubber product |
| JP2011241504A (en) * | 2010-05-18 | 2011-12-01 | Teijin Techno Products Ltd | Aromatic polyamide short fiber bundle |
| WO2014091376A1 (en) * | 2012-12-13 | 2014-06-19 | Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi | A dipping material for cord fabrics and a production method thereof |
| US10145034B2 (en) | 2013-04-26 | 2018-12-04 | Kordsa Teknik Tekstil A.S. | RFL-free dipping composition providing high performance for cord fabrics |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6096674A (en) * | 1983-10-31 | 1985-05-30 | Sumitomo Naugatuck Co Ltd | Rubber reinforcement adhesive |
| JPS6381184A (en) * | 1986-09-24 | 1988-04-12 | Sumitomo Naugatuck Co Ltd | Adhesive composition for rubber and fiber |
| JPH05311534A (en) * | 1992-05-07 | 1993-11-22 | Teijin Ltd | Treatment of aromatic polyamide fiber for rubber reinforcement |
| JPH0995599A (en) * | 1995-09-29 | 1997-04-08 | Nippon Zeon Co Ltd | Epoxy resin composition, and prepreg and molded product produced using the same |
| JPH1046475A (en) * | 1996-07-25 | 1998-02-17 | Teijin Ltd | Treatment of polyester fiber |
| JPH10195173A (en) * | 1996-11-18 | 1998-07-28 | Takeda Chem Ind Ltd | Primer composition |
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2005
- 2005-08-12 JP JP2005234180A patent/JP2007046210A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6096674A (en) * | 1983-10-31 | 1985-05-30 | Sumitomo Naugatuck Co Ltd | Rubber reinforcement adhesive |
| JPS6381184A (en) * | 1986-09-24 | 1988-04-12 | Sumitomo Naugatuck Co Ltd | Adhesive composition for rubber and fiber |
| JPH05311534A (en) * | 1992-05-07 | 1993-11-22 | Teijin Ltd | Treatment of aromatic polyamide fiber for rubber reinforcement |
| JPH0995599A (en) * | 1995-09-29 | 1997-04-08 | Nippon Zeon Co Ltd | Epoxy resin composition, and prepreg and molded product produced using the same |
| JPH1046475A (en) * | 1996-07-25 | 1998-02-17 | Teijin Ltd | Treatment of polyester fiber |
| JPH10195173A (en) * | 1996-11-18 | 1998-07-28 | Takeda Chem Ind Ltd | Primer composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009174105A (en) * | 2007-12-25 | 2009-08-06 | Bridgestone Corp | Method for producing adhesive composition for organic fiber cord, adhesive composition for organic fiber cord and method for producing rubber product |
| JP2009161872A (en) * | 2007-12-28 | 2009-07-23 | Bridgestone Corp | Adhesive composition for organic fiber cord, and method for producing rubber product using the same adhesive composition |
| JP2011241504A (en) * | 2010-05-18 | 2011-12-01 | Teijin Techno Products Ltd | Aromatic polyamide short fiber bundle |
| WO2014091376A1 (en) * | 2012-12-13 | 2014-06-19 | Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi | A dipping material for cord fabrics and a production method thereof |
| US10294385B2 (en) | 2012-12-13 | 2019-05-21 | Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi | Dipping material for cord fabrics and a production method thereof |
| US10145034B2 (en) | 2013-04-26 | 2018-12-04 | Kordsa Teknik Tekstil A.S. | RFL-free dipping composition providing high performance for cord fabrics |
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