TWI816956B - 橡膠補強用纖維之製造方法 - Google Patents
橡膠補強用纖維之製造方法 Download PDFInfo
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- TWI816956B TWI816956B TW108146557A TW108146557A TWI816956B TW I816956 B TWI816956 B TW I816956B TW 108146557 A TW108146557 A TW 108146557A TW 108146557 A TW108146557 A TW 108146557A TW I816956 B TWI816956 B TW I816956B
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- Prior art keywords
- treatment liquid
- rubber
- thermoplastic elastomer
- adhesion
- aqueous dispersion
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 54
- 239000005060 rubber Substances 0.000 title claims abstract description 46
- 239000012783 reinforcing fiber Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 25
- 239000007788 liquid Substances 0.000 claims abstract description 118
- 239000006185 dispersion Substances 0.000 claims abstract description 77
- 239000000835 fiber Substances 0.000 claims abstract description 67
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 53
- 229920000126 latex Polymers 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 42
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 31
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 66
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 45
- 239000007787 solid Substances 0.000 description 37
- 229960001755 resorcinol Drugs 0.000 description 29
- 239000004816 latex Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 229920002994 synthetic fiber Polymers 0.000 description 11
- 239000012209 synthetic fiber Substances 0.000 description 11
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- 238000011156 evaluation Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- -1 acetone oxime, methyl ethylamine Oximes Chemical class 0.000 description 8
- 239000012784 inorganic fiber Substances 0.000 description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 238000002203 pretreatment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920006231 aramid fiber Polymers 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 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 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- YJMZHIMVTRDHND-UHFFFAOYSA-N 2-oxoazepane-3-carboxamide Chemical compound NC(=O)C1CCCCNC1=O YJMZHIMVTRDHND-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 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
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 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 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N N-ethyl-N-methylamine Natural products CCNC LIWAQLJGPBVORC-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
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- DFCSFNUXZBPPTD-UHFFFAOYSA-N benzene-1,3-dicarbonyl isocyanate Chemical compound O=C=NC(=O)C1=CC=CC(C(=O)N=C=O)=C1 DFCSFNUXZBPPTD-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical class NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 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 1
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
本發明之橡膠補強用纖維之製造方法之特徵係將包含熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠之易接著化處理液對纖維芯線進行附著處理而獲得橡膠補強用纖維者,其中易接著化處理液中之熱塑性彈性體係作為水分散液而調配,該水分散液中之熱塑性彈性體粒子之平均粒徑為0.01~1.0μm。
Description
本發明有關橡膠補強用纖維之製造方法,詳言之,有關於製造步驟不使用間苯二酚、甲醛及間苯二酚與甲醛之縮合化合物之任一者之橡膠補強用纖維之製造方法。
合成纖維或無機纖維係高強度、高楊氏模數,且具有優異物性特性。因此,無機纖維廣泛使用於橡膠製之輪胎或水管、皮帶之補強用途。畢竟合成纖維或無機纖維由於其表面大多比較不活性,故將合成纖維或無機纖維直接使用時,與作為基質而使用之橡膠或樹脂等之接著性不充分,無法充分發揮合成纖維或無機纖維本來具有之優異物理特性。
因此已提案將纖維表面以間苯二酚・甲醛・橡膠乳膠(RFL)處理之所謂單浴接著處理方法或首先以聚環氧化物處理,接著以間苯二酚・甲醛・橡膠乳膠(RFL)處理之所謂二浴接著處理方法並已實用化。該方法中所用之間苯二酚或甲醛於近幾年來開始有對環境及人體不良影響之顧慮。
[發明欲解決之課題]
本發明之課題在於提供儘管於製造步驟不使用間苯二酚、甲醛及間苯二酚與甲醛之縮合化合物之任一者,接著力亦優異之橡膠補強用纖維。
[用以解決課題之手段]
亦即本發明係一種橡膠補強用纖維之製造方法,其特徵係將包含熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠之易接著化處理液對纖維芯線進行附著處理而獲得橡膠補強用纖維者,其中易接著化處理液中之熱塑性彈性體係作為水分散液而調配,該水分散液中之熱塑性彈性體粒子之平均粒徑為0.01~1.0μm。
[發明效果]
依據本發明,可提供儘管於製造步驟不使用間苯二酚、甲醛及間苯二酚與甲醛之縮合化合物之任一者,接著力亦優異之橡膠補強用纖維。
[熱塑性彈性體]
熱塑性彈性體係包含硬鏈段及軟鏈段之熱塑性樹脂。作為熱塑性彈性體,舉例為例如苯乙烯系彈性體、烯烴系彈性體、氯乙烯系彈性體、胺基甲酸酯系彈性體、酯系彈性體、醯胺系彈性體。其中較佳為胺基甲酸酯彈性體,又更佳為以聚胺基甲酸酯為硬鏈段,以脂肪族聚酯、脂肪族聚醚或聚烯烴為軟鏈段者。
熱塑性彈性體,基於獲得與橡膠或纖維上之反應性官能基之良好反應性之觀點,較佳於硬鏈段具有酚基、羥基、胺基、羧基之任一基作為取代基。
硬鏈段使用聚胺基甲酸酯時,聚胺基甲酸酯較佳具有酚性羥基、羥基、胺基及羧基之任一基作為取代基。該情況下,該等取代基由於與嵌段聚異氰酸酯之異氰酸酯基反應,故可獲得更高接著性。
作為軟鏈段較佳為聚烯烴,其中較佳為丁二烯、異戊二烯,又更佳為丁二烯。若為此軟鏈段,則可與橡膠成分共硫化,可獲得強固之接著力。
本發明之熱塑性彈性體特佳為聚胺基甲酸酯與聚丁二烯之共聚物。
熱塑性彈性體係作為分散液調配於易接著化處理液中。
該水分散液中之熱塑性彈性體之粒子平均粒徑為0.01~1.0μm,較佳為0.02~0.8μm。未達0.01μm時,被膜凝集力降低,超過1.0μm時,水分散液變不安定。
調配於易接著化處理液之熱塑性彈性體水分散液之pH較佳為6~8。pH未達6時,水分散液變不安定而欠佳,超過8時水分散液亦不安定而欠佳。
調配於易接著化處理液之熱塑性彈性體水分散液之黏度較佳為100~800MPa・s(20℃),更佳為200~ 750MPa・s(20℃)。未達100MPa・s(20℃)時,對纖維之附著量降低而欠佳,超過800MPa・s(20℃)時,分散液之安定性變差而欠佳。
[嵌段聚異氰酸酯]
作為嵌段聚異氰酸酯,係使用聚異氰酸酯化合物與嵌段化劑之加成反應生成物。其係藉由加熱而使嵌段成分游離,產生活性聚異氰酸酯化合物者。
作為聚異氰酸酯化合物可舉例為甲苯二異氰酸酯、間苯二異氰酸酯、二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、三(六亞甲基二異氰酸酯)、使用三(六亞甲基二異氰酸酯)之異氰酸酯基鏈狀鍵結之聚縮合物、聚亞甲基聚苯基異氰酸酯、三苯基甲烷三異氰酸酯等之聚異氰酸酯。
作為嵌段化劑可舉例為具有1個以上活性氫原子之嵌段劑,例如酚、硫酚、甲酚、間苯二酚等之酚類,二苯基胺、二甲苯胺等之芳香族2級胺類、吡唑、二甲基吡唑等之環狀胺類,鄰苯二甲酸醯胺類,己內醯胺、戊內醯胺等之內醯胺類,丙酮肟、甲基乙基酮肟、環己酮肟等之肟類及酸性亞硫酸鈉。
嵌段聚異氰酸酯較佳1分子中具有2個以上經嵌段之異氰酸酯成份。
嵌段聚異氰酸酯係作為水分散液調配於易接著化處理液中。
[橡膠乳膠]
作為橡膠乳膠,可舉例例如天然橡膠乳膠、苯乙烯・丁二烯・共聚物乳膠、乙烯基吡啶・苯乙烯・丁二烯・聚合物乳膠(以下有時稱為「Vp乳膠」)、腈橡膠、氯丁二烯橡膠乳膠、乙烯・丙烯・二烯單體乳膠。該等可單獨使用亦可併用。為了更提高與橡膠之接著性,亦可使用以官能基改質之橡膠乳膠。進而為了提高橡膠乳膠之耐熱性,亦可使用加成氫原子之橡膠乳膠。
橡膠乳膠係作為水分散液調配於易接著化處理液中。
該水分散液中之橡膠乳膠粒子之平均粒徑較佳為0.01~1.0μm,更佳為0.02~0.8μm。實施本發明時,橡膠乳膠粒子之平均粒徑越小越好,但減小平均粒徑技術上有困難,且製造成本變高,故實用上較佳為0.01μm以上。另一方面,超過1.0μm時,橡膠乳膠成分於易接著化處理液中會凝集,使易接著化處理液變不均一,且會損及纖維芯線表面之藉由易接著化處理液之被膜均一性而欠佳。
本發明中,調配於易接著化處理液中之橡膠乳膠之水分散液中之橡膠乳膠之粒子平均粒徑較佳與調配於易接著化處理液中之熱塑性彈性體之水分散液中之熱塑性彈性體之粒子平均粒徑相等。此處所謂「平均粒徑相等」意指水分散液中之橡膠彈性體之平均粒徑相對於水分散液中之熱塑性彈性體之平均粒徑較佳為0.5~1.5倍,更佳為0.5~1.4倍,特佳為0.6~1.3倍。藉由使平均粒徑相等,可獲得高的耐熱接著力或高溫時接著力。
[易接著化處理液]
易接著化處理液係包含上述熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠作為固形分之水分散液。該易接著化處理液中上述熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠之總固形分濃度較佳為1~35重量%,更佳為2~30重量%,特佳為5~25重量%。若未達1重量%,則導致附著處理之附著量降低,接著性降低而欠佳。另一方面,超過35重量%時,附著處理中附著於纖維芯線之固形分過多,而使纖維變硬而有耐疲勞性降低之傾向而欠佳。
本發明所用之易接著化處理液不包含間苯二酚、甲醛及間苯二酚與甲醛之縮合化合物之任一者。
[纖維芯線]
本發明之纖維芯線係將合成纖維或無機纖維加撚而得,較佳將合成纖維加撚而得。例如將合成纖維或無機纖維之絲條以期望根數對齊,對其施加下撚,其次將經下撚之纖維以期望根數集束,於與下撚相反方向賦予上撚,可獲得纖維芯線。撚數為任意,但一般下撚撚數多於上撚。
作為合成纖維,可例示聚酯纖維、聚醯胺纖維、芳香族聚醯胺纖維、縲縈纖維、維尼龍纖維,特佳為聚酯纖維、芳香族聚醯胺纖維。
作為聚酯纖維較佳維以對苯二甲酸或萘二羧酸為主要酸成分,以乙二醇、1,3-丙二醇或四亞甲二醇為主要二醇成分之聚酯所成之纖維。
作為芳香族聚醯胺纖維較佳為由聚對胺基苯甲醯胺、聚對伸苯基對苯二甲醯胺、聚對胺基苯甲醯肼對苯二甲醯胺、聚對苯二甲酸醯肼、聚偏伸苯基間苯二甲醯胺、或該等之共聚物所成之所為芳醯胺纖維。其中較佳為強力較高之對位型芳醯胺。合成纖維之丹尼爾(denier)、纖絲數及剖面形狀為任意。
作為無機纖維可舉例例如碳纖維、玻璃纖維,較佳使用碳纖維。
[附著處理]
藉由易接著處理液對纖維芯線之附著處理,使熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠附著於纖維芯線。易接著處理液對纖維芯線之附著處理可藉由例如將塗佈有易接著處理液之輥與纖維芯線接觸、自噴嘴對纖維芯線噴霧易接著處理液、纖維芯線對易接著處理液之浸漬而進行。
易接著處理液對纖維芯線之附著量,以附著後之纖維芯線重量為基準,作為熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠之合計固形分附著量計,較佳為0.1~20重量%,更佳為0.3~18重量%,特佳為0.5~16重量%。控制對纖維芯線之固形分附著量時,可應用壓接輥之擠壓、刮除板等之刮落、吹附空氣之吹除、抽吸等之手段。
纖維芯線之合成纖維為聚酯纖維或芳醯胺纖維時,較佳以包含聚環氧化合物之前處理劑對纖維芯線進行前處理。
[實施例]
以下藉由實施例進一步詳細說明本發明。又,實施例中之芯線剝離接著力係藉由下述測定方法進行。
(1)芯線剝離接著力(初期接著力、耐熱接著力、高溫時接著力)
(1-1)芯線為合成纖維時之芯線剝離接著力
芯線剝離接著力表示纖維芯線與橡膠之接著力。
對以天然橡膠為主成分之調配附碳層纖維線(Carcass)之未硫化橡膠薄片(22cm×2.5cm,厚0.4cm),以將纖維芯線之表面被橡膠薄片表面隱蔽之方式嵌埋評價對象之纖維芯線3根(長22cm),於150℃之溫度施加30分鐘之50kg/cm2
之加壓壓力而硫化,製作初期接著力評價用之試驗片。進而於180℃之溫度施加40分鐘之50kg/cm2
之加壓壓力而硫化,製作耐熱接著力評價用之試驗片。針對初期接著力評價用之試驗片及耐熱接著力評價用之試驗片,分別進行於20℃環境下之剝離試驗,測定初期接著力與耐熱接著力。且,將初期接著力評價用之試驗片於恆溫槽中150℃之環境下進行剝離試驗,測定高溫時接著力。
又,剝離試驗係使用INSTRON公司製萬能材料試驗機,以平板夾具握持評價對象之纖維芯線之3根的一端,測定將橡膠薄片與纖維芯線之角度成為90°之方式剝離所需之力。此時,將剝離距離16cm量之剝離力之平均值設為剝離力。
(1-2)芯線為碳纖維時之芯線剝離接著力
上述(1-1)中,替代未硫化橡膠薄片而使用以胺基甲酸酯為主成分之未硫化橡膠以外,與(1-1)同樣方法測定。
(2)水分散液中粒子平均粒徑
(2-1)利用MICROTRAC粒徑分佈測定裝置之測定
使用Leeds&Northrup公司製MICROTRAC粒徑分佈測定裝置進行測定。
(2-2)利用雷射繞射・散射粒徑分佈測定裝置之測定
使用MICROTRAC BEL公司製雷射繞射・散射粒徑分佈測定裝置進行測定。該測定係將固形分濃度以水稀釋為為5重量%之水分散液供於測定。
(3)水分散液之黏度
使用A&D公司製音叉型振動式黏度計於溫度20℃進行測定。
[實施例1]
將具有山梨糖醇聚縮水甘油醚構造之聚環氧化合物(DENACOL EX-614B,NAGASE CHEMTEX公司製)溶解於鹼水溶液中,其次,將Vp乳膠(日本A&L公司製,商品名PIRATEX)、嵌段聚異氰酸酯(第一工業製藥公司製,商品名F8894ENB)以該等之固形分重量比為10:75:50依序進行調配,製作總固形分濃度4重量%之調配液。將其作為第一浴處理用之前處理液(處理液1)。
將聚丁二烯與聚胺基甲酸酯之共聚物的熱塑性彈性體(第一工業製藥公司製,F2471D-2,水分散液)、嵌段聚異氰酸酯(明成化學工業公司製,DM6400,以二苯基甲烷雙-4,4’-胺基甲醯基-ε-己內醯胺為成分之水分散液)、Vp乳膠(日本ZEON製,商品名2518FS,水分散液),以該等之固形分重量比為50:15:50進行混合,製作總固形分濃度20重量%之易接著化處理液(處理液2)。又,熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑為0.11μm(以2-1之測定方法之測定值)及0.14μm(以2-2之測定方法之測定值),水分散液之黏度為500 MPa・s(20℃),pH為6.6。Vp乳膠之水分散液中之Vp乳膠之平均粒徑為0.10 μm(以2-2之方法之測定值)。
使用1670dtex/384纖絲之多纖絲作為聚酯纖維(PET,帝人公司製),以40T/10cm實施下撚,其次以40T/cm實施上撚,獲得纖維芯線。使用電腦讀取處理機(CA LITZLER,輪胎塗佈處理機)將該纖維芯線浸漬於前述前處理液(處理液1)之後,於150℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,接著浸漬於易接著化處理液(處理液2)之後,於170℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,獲得橡膠補強用纖維。
對所得橡膠補強用纖維附著以固形分計合計為5重量%(以附著後之橡膠補強纖維之總重量為基準)之易接著化處理液之熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠。評價所得橡膠補強用纖維之芯線剝離接著力。結果示於表1。
[實施例2]
前處理液(處理液1)及易接著化處理液(處理液2)係使用與實施例1相同者。使用1680dtex/1000纖絲之多纖絲作為芳醯胺纖維(帝人芳醯胺公司製,商品名TOWARON),以30T/10cm實施下撚,其次以30T/cm實施上撚,獲得纖維芯線。
使用電腦讀取處理機(CA LITZLER,輪胎塗佈處理機)將該纖維芯線浸漬於前述前處理液(處理液1)之後,於150℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,接著浸漬於易接著化處理液(處理液2)之後,於170℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理。
對所得橡膠補強用纖維附著以固形分計合計為5重量%(以附著後之橡膠補強纖維之總重量為基準)之易接著化處理液之熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠。評價所得橡膠補強用纖維之芯線剝離接著力。結果示於表1。
[比較例1]
前處理液(處理液1)係使用與實施例1相同者。將間苯二酚/甲醛(R/F)之莫耳比為1/0.6,固形分濃度為65重量%之初期縮合物於鹼條件下溶解作成9重量%之水分散液。對於乙烯吡啶・苯乙烯・丁二烯三元聚物乳膠之40重量%水分散液180重量份添加該水分散液109重量份。於該液體中添加甲醛5重量份、33重量%之甲基乙基酮肟嵌段苯基甲烷二異氰酸酯分散液(分散介質為水)23重量份,熟成48小時獲得總固形分濃度18重量%之調配液,使用作為易接著化處理液(處理液2)。除了使用該易接著化處理液(處理液2)以外,與實施例1同樣實施。評價所得橡膠補強用纖維之芯線剝離接著力。評價結果示於表1。
若將比較例1與實施例1進行比對,則判知實施例1中儘管未使用間苯二酚與甲醛之縮合化合物,亦具有與使用間苯二酚與甲醛之縮合化合物之比較例1同樣程度之接著力。
[比較例2]
此例係使用含有間苯二酚與甲醛之縮合化合物之處理液作為易接著化處理液(處理液2)之例。
前處理液(處理液1)及易接著化處理液(處理液2)係使用與比較例1相同者。除了使用與實施例2相同之芳醯胺纖維作為纖維以外,與實施例1同樣實施。評價結果示於表1。若將比較例2與實施例2進行比對,則判知實施例2中儘管未使用間苯二酚與甲醛之縮合化合物,亦具有與使用間苯二酚與甲醛之縮合化合物之比較例2同樣程度之接著力。
[比較例3]
前處理液(處理液1)係使用與實施例1相同者。將聚丁二烯與聚胺基甲酸酯之共聚物的熱塑性彈性體(水分散液)、嵌段聚異氰酸酯(明成化學工業公司製,DM6400,以二苯基甲烷雙-4,4’-胺基甲醯基-ε-己內醯胺為成分之水分散液)、Vp乳膠(日本ZEON製,商品名2518FS,水分散液),以該等之固形分重量比為50:15:50進行混合,製作總固形分濃度20重量%之易接著化處理液(處理液2)。又,熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑為1.2μm(以2-2之方法之測定值),水分散液之黏度為500 MPa・s(20℃),pH為6.6。Vp乳膠之水分散液中之Vp乳膠之平均粒徑為0.10μm(以2-2之方法之測定值)。
使用1670dtex/384纖絲之多纖絲作為聚酯纖維(PET,帝人公司製),以40T/10cm實施下撚,其次以40T/cm實施上撚,獲得纖維芯線。
使用電腦讀取處理機(CA LITZLER,輪胎塗佈處理機)將該纖維芯線浸漬於前處理液(處理液1)之後,於150℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,接著浸漬於易接著化處理液(處理液2)之後,於170℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,獲得橡膠補強用纖維。
對所得橡膠補強用纖維附著以固形分計合計為5重量%(以附著後之橡膠補強纖維之總重量為基準)之易接著化處理液之熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠。評價所得橡膠補強用纖維之芯線剝離接著力。結果示於表1。
[比較例4]
前處理液(處理液1)係使用與實施例1相同者。將聚丁二烯與聚胺基甲酸酯之共聚物的熱塑性彈性體(水分散液)、嵌段聚異氰酸酯(明成化學工業公司製,DM6400,以二苯基甲烷雙-4,4’-胺基甲醯基-ε-己內醯胺為成分之水分散液)、Vp乳膠(日本ZEON製,商品名2518FS,水分散液),以該等之固形分重量比為50:15:50進行混合,製作總固形分濃度20重量%之易接著化處理液(處理液2)。又,熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑為0.11μm(以2-2之方法之測定值),水分散液之黏度為900MPa・s(20℃),pH為6.6。Vp乳膠之水分散液中之Vp乳膠之平均粒徑為0.10μm(以2-2之方法之測定值)。
使用1670dtex/384纖絲之多纖絲作為聚酯纖維(PET,帝人公司製),以40T/10cm實施下撚,其次以40T/cm實施上撚,獲得纖維芯線。
使用電腦讀取處理機(CA LITZLER,輪胎塗佈處理機)將該纖維芯線浸漬於前處理液(處理液1)之後,於150℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,接著浸漬於易接著化處理液(處理液2)之後,於170℃之溫度乾燥2分鐘,接著於240℃之溫度進行1分鐘熱處理,獲得橡膠補強用纖維。
對所得橡膠補強用纖維附著以固形分計合計為5重量%(以附著後之橡膠補強纖維之總重量為基準)之易接著化處理液之熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠。評價所得橡膠補強用纖維之芯線剝離接著力。結果示於表1。
[比較例5]
除了將易接著化處理液(處理液2)中所用之熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑設為1.2μm(以2-2之方法之測定值)以外,與實施例2同樣實施。
[實施例3]
將聚丁二烯與聚胺基甲酸酯之共聚物的熱塑性彈性體(第一工業製藥公司製,F2471D-2,水分散液)、嵌段聚異氰酸酯(明成化學工業公司製,DM6400,以二苯基甲烷雙-4,4’-胺基甲醯基-ε-己內醯胺為成分之水分散液)、Vp乳膠(日本ZEON製,商品名2518FS,水分散液),以該等之固形分重量比為50:15:50進行混合,製作總固形分濃度20重量%之處理液A。又,熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑為0.14μm(以2-2之方法之測定值),水分散液之黏度為500 MPa・s(20℃),pH為6.6。又,Vp乳膠之水分散液中之Vp乳膠之平均粒徑為0.10μm(以2-2之方法之測定值)。
其次使用攪拌機將具有山梨糖醇聚縮水甘油醚構造之聚環氧化合物(DENACOL EX-614B,NAGASE CHEMTEX公司製)溶解於水中,其次調配嵌段聚異氰酸酯(第一工業製藥公司製,商品名F8894ENB,水分散液),製作總固形分濃度16重量%之調配液(聚環氧化合物與嵌段聚異氰酸酯之固形分重量比為1:1.8)。該調配液緩緩添加於前述處理液A中,調整為最終總固形分濃度25重量%,獲得易接著化處理液B。
使用1400dtex之多纖絲(旭化成纖維公司製)作為尼龍纖維,以40T/10cm實施下撚,其次以40T/cm實施上撚,獲得纖維芯線。使用電腦讀取處理機(CA LITZLER,輪胎塗佈處理機)將該纖維芯線浸漬於前述易接著化處理液B之後,於150℃之溫度乾燥2分鐘,接著於230℃之溫度進行1分鐘熱處理,獲得橡膠補強用纖維。
對所得橡膠補強用纖維附著以固形分計合計為5重量%(以附著後之橡膠補強纖維之總重量為基準)之易接著化處理液B之熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠。評價所得橡膠補強用纖維之芯線剝離接著力。結果示於表1。
[實施例4]
上述實施例3之處理液A使用作為易接著化處理液A。
使用1840dtex之多纖絲(Cordenka公司製)作為縲縈纖維,以40T/10cm實施下撚,其次以40T/cm實施上撚,獲得纖維芯線。使用電腦讀取處理機(CA LITZLER,輪胎塗佈處理機)將該纖維芯線浸漬於前述易接著化處理液A之後,於150℃之溫度乾燥2分鐘,接著於180℃之溫度進行2分鐘熱處理,獲得橡膠補強用纖維。
對所得橡膠補強用纖維附著以固形分計合計為5重量%(以附著後之橡膠補強纖維之總重量為基準)之易接著化處理液A之熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠。評價所得橡膠補強用纖維之芯線剝離接著力。結果示於表1。
[比較例6]
此例係使用含有間苯二酚與甲醛之縮合化合物之處理液作為易接著化處理液之例。
將間苯二酚/甲醛(R/F)之莫耳比為1/2之方式,於鹼條件下使間苯二酚與甲醛反應24小時,獲得固形分濃度5.7重量%之間苯二酚/甲醛樹脂之水分散液。對於乙烯吡啶・苯乙烯・丁二烯三元聚物乳膠40重量%水分散液331重量份添加該水分散液427重量份。攪拌30分鐘後進而添加水調整總固形分濃度為17重量%,獲得含有間苯二酚與甲醛之縮合化合物之易接著化處理液。除了使用該易接著化處理液作為易接著化處理液B以外,與實施例3同樣實施。
[比較例7]
此例係使用含有間苯二酚與甲醛之縮合化合物之處理液作為易接著化處理液之例。
將間苯二酚/甲醛(R/F)之莫耳比為1/2之方式,於鹼條件下使間苯二酚與甲醛反應24小時,獲得固形分濃度5.4重量%之間苯二酚/甲醛樹脂之水分散液。對於乙烯吡啶・苯乙烯・丁二烯三元聚物乳膠40重量%水分散液410重量份添加該水分散液590重量份。靜置4小時後進而添加水調整總固形分濃度為15重量%,獲得含有間苯二酚與甲醛之縮合化合物之易接著化處理液。除了使用該易接著化處理液作為易接著化處理液A以外,與實施例4同樣實施。
[比較例8]
將易接著化處理液B中所用之熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑設為1.2μm(以2-2之方法之測定值)以外,與實施例3同樣實施。
[比較例9]
將易接著化處理液A中所用之熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑設為1.2μm(以2-2之方法之測定值)以外,與實施例4同樣實施。
[實施例5]
將具有山梨糖醇聚縮水甘油醚構造之聚環氧化合物(DENACOL EX-614B,NAGASE CHEMTEX公司製)溶解於鹼水溶液中,其次,將Vp乳膠(日本A&L公司製,商品名PIRATEX)、嵌段聚異氰酸酯(第一工業製藥公司製,商品名F8894ENB)以該等之固形分重量比為10:75:50依序進行調配,製作總固形分濃度4重量%之調配液。將其作為第一浴處理用之前處理液(處理液1)。
將聚丁二烯與聚胺基甲酸酯之共聚物的熱塑性彈性體(第一工業製藥公司製,F2471D-2,水分散液)、嵌段聚異氰酸酯(明成化學工業公司製,DM6400,以二苯基甲烷雙-4,4’-胺基甲醯基-ε-己內醯胺為成分之水分散液)、Vp乳膠(日本ZEON製,商品名2518FS,水分散液),以該等之固形分重量比為50:15:50進行混合,製作總固形分濃度20重量%之易接著化處理液(處理液2)。又,熱塑性彈性體之水分散液中之熱塑性彈性體之平均粒徑為0.11μm(以2-1之測定方法之測定值)及0.14μm(以2-2之測定方法之測定值),水分散液之黏度為500MPa・s(20℃),pH為6.6。Vp乳膠之水分散液中之Vp乳膠之平均粒徑為0.10 μm(以2-2之方法之測定值)。
使用8000dtex/12000纖絲之多纖絲(TENAX,帝人公司製)作為碳纖維,以6T/10cm施撚,獲得纖維芯線。使用板加熱器將該纖維芯線浸漬於前述前處理液(處理液1)之後,於200℃之溫度乾燥2分鐘,接著浸漬於易接著化處理液(處理液2)之後,於240℃之溫度乾燥2分鐘,獲得橡膠補強用纖維。評價所得橡膠補強用纖維之芯線剝離接著力之結果示於表1。
[比較例10]
前處理液(處理液1)係使用與實施例1相同者。將間苯二酚/甲醛(R/F)之莫耳比為1/0.6,固形分濃度為65重量%之初期縮合物於鹼條件下溶解作成9重量%之水分散液。對於乙烯吡啶・苯乙烯・丁二烯三元聚物乳膠之40重量%水分散液180重量份添加該水分散液109重量份。於該液體中添加甲醛5重量份、33重量%之甲基乙基酮肟嵌段苯基甲烷二異氰酸酯分散液(分散介質為水)23重量份,熟成48小時獲得總固形分濃度18重量%之調配液,使用作為易接著化處理液(處理液2)。除了使用該易接著化處理液(處理液2)以外,與實施例5同樣實施。評價所得橡膠補強用纖維之芯線剝離接著力。評價結果示於表1。
[產業上之可利用性]
藉由本發明之橡膠補強用纖維之製造方法所得之橡膠補強用纖維可使用於橡膠製之輪胎或水管、皮帶等之補強。
Claims (3)
- 一種橡膠補強用纖維之製造方法,其特徵係將包含熱塑性彈性體、嵌段聚異氰酸酯及橡膠乳膠之易接著化處理液對纖維芯線進行附著處理而獲得橡膠補強用纖維者,其中易接著化處理液中之熱塑性彈性體係作為水分散液而調配,該水分散液中之熱塑性彈性體粒子之平均粒徑為0.01~1.0μm,該水分散液中之橡膠彈性體之平均粒徑相對於該水分散液中之熱塑性彈性體之平均粒徑為0.5~1.5倍。
- 如請求項1之橡膠補強用纖維之製造方法,其中水分散液之pH為6~8且黏度為100~800mPa.s(20℃)。
- 如請求項1或2之橡膠補強用纖維之製造方法,其中熱塑性彈性體係聚胺基甲酸酯與聚丁二烯之共聚物。
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