TWI627245B - 金屬表面接著性橡膠組成物、橡膠組成物金屬層合體、加硫橡膠製品、及加硫橡膠製品之製造方法 - Google Patents
金屬表面接著性橡膠組成物、橡膠組成物金屬層合體、加硫橡膠製品、及加硫橡膠製品之製造方法 Download PDFInfo
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- TWI627245B TWI627245B TW103114694A TW103114694A TWI627245B TW I627245 B TWI627245 B TW I627245B TW 103114694 A TW103114694 A TW 103114694A TW 103114694 A TW103114694 A TW 103114694A TW I627245 B TWI627245 B TW I627245B
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- rubber
- rubber composition
- mass
- parts
- metal surface
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 210
- 239000005060 rubber Substances 0.000 title claims abstract description 210
- 239000000203 mixture Substances 0.000 title claims abstract description 113
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 239000000853 adhesive Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000004636 vulcanized rubber Substances 0.000 title claims description 28
- 230000001070 adhesive effect Effects 0.000 title claims description 11
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 150000001993 dienes Chemical class 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000002250 absorbent Substances 0.000 claims abstract description 18
- 230000014759 maintenance of location Effects 0.000 claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims description 54
- 239000011593 sulfur Substances 0.000 claims description 36
- 229910052717 sulfur Inorganic materials 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 35
- 238000005987 sulfurization reaction Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000004927 clay Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229920000459 Nitrile rubber Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 8
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920003049 isoprene rubber Polymers 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229920006037 cross link polymer Polymers 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 241000894007 species Species 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 143
- 238000002156 mixing Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 9
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- 239000000126 substance Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
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- 239000004744 fabric Substances 0.000 description 8
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- 239000004677 Nylon Substances 0.000 description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 6
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- 238000004804 winding Methods 0.000 description 6
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
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- 238000001704 evaporation Methods 0.000 description 5
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- 238000003860 storage Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000011701 zinc Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
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- 238000004806 packaging method and process Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
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- 230000002787 reinforcement Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
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- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
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- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
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- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
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- XHLHIFBBLKNHQC-UHFFFAOYSA-N 6-(butylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CCCCNC1=NC(S)=NC(S)=N1 XHLHIFBBLKNHQC-UHFFFAOYSA-N 0.000 description 1
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
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- C—CHEMISTRY; METALLURGY
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- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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Abstract
本發明係提供一種與經金屬鍍敷的補強層之接著性良好的橡膠組成物。金屬表面接著性橡膠組成物,係與金屬表面進行接著的金屬表面接著性橡膠組成物,其相對可硫加硫的二烯系聚合物100質量份,含有1.0質量份以上15質量份以下的水、與0.5質量份以上10質量份以下的作為水分保留劑之吸水性樹脂或者0.5質量份以上20質量份以下的作為水分保留劑之無機保水劑。
Description
本發明係關於金屬表面接著性橡膠組成物、橡膠組成物金屬層合體、加硫橡膠製品、及加硫橡膠製品之製造方法。
作為於產業上之各種用途中所利用的油壓軟管及高壓軟管(以下,統稱為油壓軟管等),已知有為了即使在溫度或壓力之變動範圍大的嚴苛環境中亦不會產生液漏等保有作為軟管的功能,而將補強絲及鋼線材等交織而成的補強層設置於橡膠層與橡膠層之間的構造者。如此之補強層,係為了提高與橡膠層之接著性,例如,表面以黃銅(brass)等之金屬加以鍍敷而使用。
於專利文獻1中,係記載有一種橡膠組成物,其係藉由摻合橡膠成分與多孔質無機填充劑,於加硫時釋出水分,而提高經鍍黃銅的補強層與橡膠層之接著性。
〔專利文獻1〕日本特開2002-13083號公報
然而,於專利文獻1記載的橡膠組成物中,因長期保管中的水分蒸發,而無法保留加硫時所需的水分,結果,有橡膠層與補強層之接著性降低的情況。尤其,為了提昇生產性而以作為連續加硫方式之烘箱加硫方式進行加硫時,加硫時水分的蒸發顯著,而有無法得到橡膠層與補強層之充分接著性的情況。因而,盼望出現一種與經金屬鍍敷的補強層之接著性良好的橡膠組成物。
本發明之目的為提供與經金屬鍍敷的補強層之接著性良好的橡膠組成物、如此之橡膠組成物與補強層之橡膠組成物金屬層合體、將如此之橡膠組成物金屬層合體進行加硫之加硫製品、及加硫製品之製造方法。
本發明之金屬表面接著性橡膠組成物,係與金屬表面進行接著的金屬表面接著性橡膠組成物,其係相對可硫加硫的二烯系聚合物100質量份,含有1.0質量份以上15質量份以下的水與0.5質量份以上10質量份以下的作為水分保留劑之吸水性樹脂。
於本發明之金屬表面接著性橡膠組成物中,較佳為前述吸水性樹脂為由丙烯酸聚合物部分鈉鹽交聯物、改性丙烯酸系交聯聚合物、及聚醚化合物選出之至少1種。
於本發明之金屬表面接著性橡膠組成物中,較佳為前述聚醚化合物為聚環氧乙烷或聚乙二醇。
本發明之金屬表面接著性橡膠組成物,係與金屬表面進行接著的金屬表面接著性橡膠組成物,其係相對可硫加硫的二烯系聚合物100質量份,含有1.0質量份以上15質量份以下的水與0.5質量份以上20質量份以下的作為水分保留劑之無機保水劑。
於本發明之金屬表面接著性橡膠組成物中,較佳為前述無機保水劑為由水膨潤性黏土、二氧化矽、氫氧化鋁、氧化鋁、碳酸鈣、碳酸鎂、及沸石所選出之至少1種。
於本發明之金屬表面接著性橡膠組成物中,較佳為前述金屬表面為經鍍黃銅的金屬表面。
於本發明之金屬表面接著性橡膠組成物中,較佳為前述二烯系聚合物包含由天然橡膠(NR)、異戊二烯橡膠(IR)、苯乙烯-丁二烯橡膠(SBR)、腈-丁二烯橡膠(NBR)、乙烯-丙烯-二烯橡膠(EPDM)、及氯丁二烯橡膠(CR)所選出之至少1種。
於本發明之金屬表面接著性橡膠組成物中,較佳為再含有加硫劑。
本發明之橡膠組成物金屬層合體,係層合有由上述金屬表面接著性橡膠組成物所構成的橡膠層與具有金屬表面的補強層。
於本發明之橡膠組成物金屬層合體中,較佳為前述金屬表面為經鍍黃銅的金屬表面。
於本發明之橡膠組成物金屬層合體中,較佳為前述補強層具有線料編成的編織(葉片(blade))構造或螺旋構造。
本發明之加硫橡膠製品,係上述橡膠組成物金屬層合體的前述橡膠層在含硫加硫劑存在下被加硫,並與前述補強層接著。
於本發明之加硫橡膠製品中,較佳為油壓軟管或高壓軟管。
於本發明之加硫橡膠製品中,較佳為前述油壓軟管或前述高壓軟管藉由通過烘箱加硫裝置內而被加硫。
本發明之加硫橡膠製品的製造方法,係具有將表面經鍍黃銅的補強層與至少一橡膠層層合,製作層合體的層合步驟、使前述層合體通過烘箱加硫裝置內,將前述橡膠層加硫,再與前述經鍍黃銅的補強層接著之加硫接著步驟,且前述橡膠層相對可硫加硫的二烯系聚合物100質量份,含有1.0質量份以上15質量份以下的水與0.5質量份以上10質量份以下的作為水分保留劑之吸水性樹脂的橡
膠組成物中,再含有含硫加硫劑。
本發明之加硫橡膠製品的製造方法,係具有將表面經鍍黃銅的補強層與至少一橡膠層層合,製作層合體之層合步驟、使前述層合體通過烘箱加硫裝置內,將前述橡膠層加硫,再與前述經鍍黃銅的補強層接著之加硫接著步驟,且前述橡膠層相對可硫加硫的二烯系聚合物100質量份,含有1.0質量份以上15質量份以下的水與0.5質量份以上20質量份以下的作為水分保留劑之無機保水劑的橡膠組成物中,再含有含硫加硫劑。
依據本發明,可提供與經金屬鍍敷,尤其,鍍黃銅的補強層之接著性良好的橡膠組成物、如此之橡膠組成物與補強層之橡膠組成物金屬層合體、將如此之橡膠組成物金屬層合體進行加硫之加硫製品、及加硫製品之製造方法。本發明係可適合使用於藉由烘箱加硫方式所連續生產的軟管。
1‧‧‧油壓軟管(加硫橡膠製品)
2‧‧‧內側橡膠層
3‧‧‧補強層
4‧‧‧外側橡膠層
6‧‧‧心軸
6C‧‧‧軟管主體
14‧‧‧加硫裝置
18‧‧‧耐隆布
〔第1圖〕第1圖係顯示本實施形態之油壓軟管的一例子之局部破斷立體圖。
〔第2圖〕第2圖係顯示製造作為加硫橡膠製品之油壓軟管的一例子之步驟圖。
〔第3圖〕第3圖係說明第2圖之加硫步驟的細節之模式圖。
〔第4圖〕第4圖係顯示第2圖之被投入加硫裝置的心軸周圍之層構造的一例子之局部剖面圖。
以下,針對本發明進行詳細地說明。另外,本發明並不受以下之實施形態及實施例記載的內容所限定。此外,於以下記載的實施形態及實施例之構成要素中,係包含該業者所容易想定者、實質上相同者、所謂均等的範圍者。進而,在以下記載之實施形態及實施例所揭示的構成要素,係可適當組合,亦可適當選擇使用。
以下,針對本發明形態之橡膠組成物進行說明。本實施形態之橡膠組成物,係與鍍黃銅線補強層進行接著的橡膠組成物,其係相對可硫加硫的二烯系聚合物100質量份,含有1.0質量份以上15質量份以下的水與0.5質量份以上10質量份以下的作為水分保留劑之吸水性樹脂,或者0.5質量份以上20質量份以下的作為水分保留劑之無機保水劑。以下,針對構成橡膠組成物之各成分進行說明。
可硫加硫的二烯系聚合物,係可列舉例如:天然橡膠(NR)、異戊二烯橡膠(IR)、苯乙烯-丁二烯橡膠(SBR)、腈-丁二烯橡膠(NBR)、乙烯-丙烯-二烯橡膠(EPDM)、及氯丁二烯橡膠(CR)。可硫加硫的二烯聚合物,係可1種單獨使用,亦可併用2種以上。
於本實施形態中,可硫加硫,係意味著將硫作為媒介而形成交聯構造之性質。硫係藉由後述之加硫劑而提供。
就可得到良好的橡膠混合加工性及橡膠外觀的觀點而言,可硫加硫的二烯系聚合物之摻合量,較佳為相對橡膠組成物全體,為20質量%以上70質量%以下。
水,係可為自來水,亦可為蒸餾水、離子交換水、及過濾水等之純水。此外,亦可為吸附於填料(例如,碳黑)的水分。水的摻合量,較佳為相對二烯系聚合物100質量份,為1.0質量份以上,更佳為3.0質量份以上,此外較佳為15質量份以下,更佳為11質量份以下。若水的摻合量為上述範圍內,則藉由與後述之水分保留劑一起摻合於組成物中,即使長期保管時,亦可於加硫時將適度的水分安定地保留在組成物中,即使以水分蒸發大的烘箱加硫方式進行的連續生產之軟管生產中,亦可良好地保有橡膠層與補強層之接著性。若考慮以上觀點,則水的摻合量,較佳為相對二烯系聚合物100質量份,為1.0質量份
以上15質量份以下,更佳為3.0質量份以上11質量份以下。
水分保留劑,係具有將水安定地保留於橡膠組成物(化合物)中的功能者。於本實施形態中,水分保留劑係可使用吸水性樹脂及無機保水劑。此等係可使用1種,亦可併用2種以上。
一般而言,吸水性樹脂,係指每1g樹脂呈現10g以上之吸水量。吸水性樹脂,較佳為親水性高,且具有將水吸入孔隙(孔)中的立體網狀構造之多孔質材料。吸水性樹脂,較佳為例如由丙烯酸聚合物部分鈉鹽交聯物、改性丙烯酸系交聯聚合物、及聚醚化合物所成之群中選出的至少1種。
丙烯酸聚合物部分鈉鹽交聯物係可列舉例如:商品名「Acrylic(註冊商標)CA」(日本觸媒公司製)等。
改性丙烯酸系交聯聚合物係可列舉例如:商品名「Acrylic(註冊商標)CS」(日本觸媒公司製)等。
聚醚化合物係可列舉例如:聚環氧乙烷、及聚乙二醇等。
吸水性樹脂的摻合量,較佳為相對二烯系聚合物100質量份,為0.5質量份以上,更佳為3.0質量份以上,此外較佳為10質量份以下,更佳為6質量份以下。若吸水性樹脂的摻合量為上述範圍內,則藉由與前述之水一起摻合於組成物中,即使長期保管時,亦可於加硫時將適度的水分安定地保留在組成物中,即使於以水分蒸發大的烘箱加硫方式進行的連續生產之軟管生產中,亦可良好地保有橡膠層與補強層之接著性。另外,若吸水性樹脂的摻合量過多,則由於會因其吸水性高而使外觀變差,因此較佳為於上述範圍內使用。若考慮以上觀點,則吸水性樹脂的摻合量,較佳為相對二烯系聚合物100質量份,為0.5質量份以上10質量份以下,更佳為3.0質量份以上6質量份以下。
無機保水劑,例如,較佳為將水吸入孔隙(孔)中之多孔質材料。無機保水劑,可列舉例如:水膨潤性黏土、二氧化矽(白碳(white carbon))、氫氧化鋁、氧化鋁、碳酸鈣、碳酸鎂、及沸石等。二氧化矽,係可列舉例如:結晶性二氧化矽、沉澱二氧化矽、非晶質二氧化矽(例如,高溫處理二氧化矽)、氣相二氧化矽(fumed silica)、燒成二氧化矽、沉降二氧化矽、粉碎二氧化矽、及熔融二氧化矽等。此等當中,較佳為水膨潤性黏土、及二氧化矽,更佳為水膨潤性黏土。無機保水劑,係
可單獨使用,亦可併用2種以上。
水膨潤性黏土,係指吸水後本身的體積會增大的黏土。水膨潤性黏土,係可列舉:蒙脫石、鋁膨潤石、鋰膨潤石、鎂膨潤石、及滑鎂皂石(stevensite)等之膨潤石系黏土礦物、以及蛭石等。其中,較佳為以蒙脫石作為主成分之膨土。
無機保水劑的摻合量,較佳為相對二烯系聚合物100質量份,為0.5質量份以上,更佳為3.0質量份以上,此外較佳為20質量份以下,更佳為12質量份以下。若無機保水劑的摻合量為上述範圍內,則藉由與前述之水一起摻合於組成物中,即使長期保管時,亦可於加硫時將適度的水分安定地保留在組成物中,即使於以水分蒸發大的烘箱加硫方式進行的連續生產之軟管生產中,亦可良好地保有橡膠層與補強層之接著性。若考慮以上觀點,則無機保水劑的摻合量,較佳為相對二烯系聚合物100質量份,為0.5質量份以上20質量份以下,更佳為3.0質量份以上12質量份以下。
橡膠組成物,較佳為在硫的存在下進行加硫,以進一步摻合含硫加硫劑而成者為佳。含硫加硫劑,係可列舉例如:硫、二硫化四甲基秋蘭姆(tetramethylthiuram disulfide;TMTD)、二硫化四乙基秋蘭姆(tetraethylthiuram disulfide;TETD)、二硫化四丁胺
甲硫醯基(tetrabutylthiuram disulfide;TBTD)、四硫化雙五亞甲基秋蘭姆(Dipentamethylenethiuram tetrasulfide;DPTT)、二硫化四苄基秋蘭姆(tetrabenzylthiuram disulfide)、及二硫化二嗎啉(dimorpholine disulfide)、硫化烷基酚等之有機含硫化合物。硫係可列舉例如:粉末硫、沉澱性硫、高分散性硫、表面處理硫、及不溶性硫等。
加硫劑,亦可進一步摻合以下之非硫系加硫劑。非硫系加硫劑,係可列舉例如:有機過氧化系、金屬氧化物系、酚樹脂、及苯醌二肟等之加硫劑。
有機過氧化物系之加硫劑,可列舉例如:二異丙苯過氧化物、苯甲醯過氧化物、t-丁基過氧化物、2,4-二氯苯甲醯過氧化物、2,5-二甲基-2,5-二(t-丁基過氧基)己烷、及2,5-二甲基己烷-2,5-二(過氧苯甲酸酯(peroxybenzoate))等。
其他的加硫劑,係可列舉例如:中國白(Chinese white)、氧化鎂、酚樹脂等之樹脂、p-苯醌二肟、p-二苯甲醯苯醌二肟、聚-p-二亞硝基苯、及亞甲二苯胺等。
本實施形態之橡膠組成物,較佳為進一步含有加硫促進劑。加硫促進劑,係可列舉例如:醛-氨系加硫促進劑、酸-胺系加硫促進劑、硫脲系加硫促進劑、胍系加硫促進劑、噻唑系加硫促進劑、亞磺醯胺系加硫促進劑、秋蘭姆系加硫促進劑、二硫胺基甲酸鹽系加硫促進
劑、及黃嘌呤酸鹽系加硫促進劑。此等係可單獨使用,亦可併用2種以上。
此外,橡膠組成物,在發揮本發明效果的範圍內,可因應需要而含有其他的添加劑。其他的添加劑,係可列舉例如:填充劑、可塑劑、軟化劑、抗老化劑、有機系活性劑、抗氧化劑、抗靜電劑、難燃劑、交聯促進助劑、加硫阻滯劑、及接著助劑。
填充劑,係可列舉例如:碳黑、黏土、滑石、氧化鐵、氧化鋅(ZnO)、氧化鈦、氧化鋇、氧化鎂、碳酸鋅、硫酸鋇、雲母(mica)、及矽藻土等。此等係可單獨使用1種,亦可併用2種以上。碳黑,係可因應用途適當選擇而使用。碳黑,較佳為ISAF及FEF等。尤其,碳黑,已知有生成凝碳膠(結合橡膠),可因應需要而適當使用。黏土,係可列舉:蠟石黏土、高嶺土(Kaolin clay)、及燒成黏土等。
可塑劑,係可列舉例如:鄰苯二甲酸二辛酯(DOP)、鄰苯二甲酸二丁酯(DBP)、己二酸二辛酯(DOA)、琥珀酸異癸酯、二乙二醇二苯甲酸酯、季戊四醇酯、油酸丁酯、乙醯蓖麻油酸甲酯、磷酸三甲苯酯、磷酸三辛酯、偏苯三甲酸酯、己二酸丙二醇聚酯、及己二酸丁二醇聚酯、環烷油等。此等係可單獨使用1種,亦可併用2種以上。
軟化劑,具體而言係可列舉例如:芳香系油、環烷系油、石蠟系油、石油樹脂、植物油、及液狀橡膠等。此等係可單獨使用1種,亦可併用2種以上。
抗老化劑,係可列舉例如:N-(1,3-二甲基丁基)-N’-苯基-p-伸苯基二胺(6PPD)、N,N’-二萘基-p-伸苯基二胺(DNPD)、N-異丙基-N’-苯基-p-伸苯基二胺(IPPD)、苯乙烯化苯酚(SP)、及2,2,4-三甲基-1,2-二氫喹啉聚合物(RD)等。此等係可單獨使用1種,亦可併用2種以上。
有機系活性劑,係可列舉例如:硬脂酸、油酸、月桂酸、硬脂酸鋅等。此等係可單獨使用1種,亦可併用2種以上。
抗氧化劑係可列舉例如:丁基羥基甲苯(BHT)、丁基羥基苯甲醚(BHA)。
抗靜電劑係可列舉例如:四級銨鹽;聚乙二醇、環氧乙烷衍生物等之親水性化合物。
難燃劑,係可列舉例如:氯烷基磷酸鹽、二甲基.甲基膦酸鹽、溴.磷化合物、銨多磷酸鹽、溴新戊烷-聚醚、及溴化聚醚等。此外,非鹵系難燃劑,係可列舉例如:氫氧化鋁、氫氧化鎂、三甲苯.磷酸鹽、及二苯基甲苯酚基.磷酸鹽。
交聯促進劑,係可合併使用一般的橡膠用助劑。橡膠用助劑,係可使用例如:中國白;硬脂酸、油酸、此等之Zn鹽。
加硫阻滯劑,係可列舉例如:鄰苯二甲酸
酐、苯甲酸、柳酸、乙醯水楊酸等之有機酸;N-亞硝基-二苯基胺、N-亞硝基-苯基-β-萘基胺、N-亞硝基-三甲基-二氫喹啉之聚合物等之亞硝基化合物;三氯三聚氰胺(trichloromelamine)等之鹵化物;2-巰基苯并咪唑、及N-(環己基硫)鄰苯二甲醯亞胺(PVI)等。此等係可單獨使用1種,亦可併用2種以上。
接著助劑,係可列舉例如:三嗪硫醇系化合物(例如,2,4,6-三巰基-1,3,5-三嗪、6-丁基胺基-2,4-二巰基-1,3,5-三嗪)、間苯二酚、甲酚、間苯二酚-甲醛膠乳、單羥甲基三聚氰胺、單羥甲基脲、乙烯馬來醯亞胺、環烷酸鈷、硬脂酸鈷、新癸酸鈷、及十二酸鈷等。此等係可單獨使用1種,或者亦可併用2種以上。
上述之各種添加劑,係分別可單獨使用1種,亦可併用2種以上。
本實施形態之橡膠組成物之製造方法,並無特別限定,可使用以往周知的方法。橡膠組成物,係可藉由將二烯系聚合物、水、以及水分保留劑與因應需要之加硫劑及其他的添加劑一併摻合而製造。橡膠組成物,例如,可藉由將上述二烯系聚合物、水、以及水分保留劑與因應需要之加硫劑及其他的添加劑,利用班布里混合機(Banbury mixer)、捏合機進行混練而製造。
本實施形態之橡膠組成物金屬層合體,係上述橡膠組成物與表面經金屬鍍敷的線料補強層之層合體。於第1圖顯示將橡膠組成物金屬層合體作為軟管體現的情況之基本構造。第1圖係顯示本實施形態之油壓軟管的一例子之局部破斷立體圖。如第1圖所示,軟管1,係具有:流體通過內部的內側橡膠層2、設置於內側橡膠層2之外側周圍的補強層3、以及設置於補強層3之外側周圍的外側橡膠層4。內側橡膠層2及/或外側橡膠層4,係以上述實施形態之橡膠組成物所構成的橡膠層。補強層3,係鋼線材編織而成的線料板(wire blade),線料的表面係鍍黃銅。補強層3,係配設成挾持於內側橡膠層2與外側橡膠層4之間。內側橡膠層2、補強層3、及外側橡膠層4,係藉由內側橡膠層2及外側橡膠層4之加硫而接著固定。
如上所述,內側橡膠層2及外側橡膠層4之至少一方,係以上述實施形態之橡膠組成物所構成。就軟管之耐候性的觀點而言,較佳為至少使用上述實施形態之橡膠組成物來形成外側橡膠層4。
上述內側橡膠層2的厚度,例如,較佳為0.2mm以上4.0mm以下,更佳為0.5mm以上2.0mm以下。相同地,上述外側橡膠層4的厚度,例如,較佳為0.2mm以上4.0mm以下,更佳為0.5mm以上2.0mm以
下。
就強度保持的觀點而言,補強層3,係設置於內側橡膠層2與外側橡膠層4之間的層。補強層3,係藉由鋼線材線編織而成的線料板而形成。
補強層3,除線料板以外,形成為將鋼線材線呈螺旋狀捲繞於內側橡膠層2周圍的螺旋線者亦可。形成補強層的材料及編法或織法或者捲繞方式,係可因應用途,例如,因應耐壓力而適當選擇。於油壓軟管等中,較佳為藉由線料板而形成補強層。
線材料,係可列舉例如:鋼琴線(碳鋼)、硬鋼線及不鏽鋼線等。線材料,就加工性及強度等的觀點而言,特佳為鋼琴線(碳鋼)及硬鋼線。
補強層3,係為了提高與橡膠層之接著性,而將表面加以金屬鍍敷。此金屬鍍敷,係對於鋼琴線及硬鋼線施以黃銅(brass)塗佈者。於黃銅塗佈中,係將銅鍍敷於鋼線上,將鋅鍍敷於銅上,施加熱擴散處理而形成黃銅塗佈。
上述橡膠組成物與補強層3的橡膠組成物金屬層合體,係在含硫加硫劑的存在下進行交聯,亦即加硫,藉此形成內側橡膠層2及外側橡膠層4之橡膠的分子間會藉由
硫而交聯。藉由此交聯,而賦予內側橡膠層2及外側橡膠層4彈性與拉伸強度,並且在與補強層3的界面將構成黃銅塗佈的金屬(銅、鋅)與硫結合而將內側橡膠層2及外側橡膠層4與補強層3接著。
含硫加硫劑,較佳為在形成作為橡膠組成物之化合物時,與其他的材料一起摻合。另外,含硫加硫劑的摻合,係只要藉由硫,形成二烯系聚合物的分子鏈彼此會藉由硫而交聯,藉由於內側橡膠層2及外側橡膠層4與補強層3之界面的金屬(銅、鋅)與硫之結合等而接著內側橡膠層2及外側橡膠層4與補強層3,則不限定於化合物調製時之摻合。
加硫方法,係可列舉在含硫加硫劑的存在下,將橡膠組成物在特定溫度以特定時間進行加熱處理的方法。加硫溫度,較佳為130℃以上180℃以下。加硫時間,較佳為30分鐘以上240分鐘以下。藉由此範圍之溫度與時間的組合,而可得到作為加硫橡膠製品所期望的物性,例如,彈性、拉伸強度、外觀、橡膠-金屬界面之接著性及橡膠-金屬界面之附橡膠。
於本實施形態之加硫橡膠製品,係可適合作為油壓軟管等使用。油壓軟管等之製造方法,係可列舉例如:將橡膠組成物金屬層合體封入高壓容器內而在蒸氣罐內進行交聯之蒸氣加硫方式、與將以耐隆布等覆蓋橡膠組成物金屬層合體者在熱風乾燥爐內進行加硫之烘箱加硫方式等。一般而言,蒸氣加硫方式係分批式處理,烘箱加硫
方式係連續式處理。油壓軟管之製造方法,較佳為作為連續式處理之烘箱加硫方式。
以下,針對本發明形態之加硫橡膠製品之製造方法進行說明。在此,以作為加硫橡膠製品之油壓軟管的情況為例子進行說明。
如第1圖所示般,油壓軟管1,係具有於內側橡膠層2的外周面依序層合了補強層3與外側橡膠層4的構造。另外,於第1圖所示之例子中,雖將補強層3設為一層,但亦可設為於層間配置有中間橡膠層的複數之補強層3。另外,如上所述般,外側橡膠層4,較佳為以上述實施形態之橡膠組成物來形成,內側橡膠層2,較佳為使用將耐油性優異的丙烯腈丁二烯橡膠(NBR)作為主成分之橡膠組成物來形成。
以下參照第2圖及第3圖來說明本實施形態之油壓軟管之製造方法。第2圖係顯示油壓軟管之製造裝置的一例子之步驟圖。第3圖,係更詳細說明於第2圖之階段S103中,使用了加硫裝置14之加硫步驟的模式圖。
如第2圖所示般,橡膠軟管,係藉由下述步驟而得
到:於心軸6的外周面形成內側橡膠層2的橡膠材之壓出步驟(階段S101)、補強層3之編織步驟(階段S102)、外面橡膠層4之壓出/加硫步驟(階段S103)、及心軸6之拔出步驟(階段S104)。所製造的橡膠軟管,係經過水壓檢查,進一步經過檢查捲取步驟,而捆包、出貨。
首先,於階段S101中,於自捲出機5抽出之心軸6的外周面,藉由第1壓出機7將被覆了未加硫之內側橡膠層2的軟管6A捲取於捲取捲出機8。
接著,於階段S102中,以覆蓋構成自捲取捲出機8抽出的軟管6A之內側橡膠層2的方式,藉由編織機(braiding machine)9編織,而將形成有補強層3的軟管6B捲取於捲取捲出機10。於此補強層3的繩(cord)中,係使用金屬線。金屬線,為了使與橡膠之接著性為良好,而使用經鍍黃銅的鋼線。另外,補強層3,亦可藉由將金屬線螺旋捲繞於形成在心軸6的周圍之內側橡膠層2的周圍而形成。
接著,於階段S103中,於自捲取捲出機10抽出的軟管6B之補強層3上,藉由第2壓出機11,將被覆未加硫的外側橡膠層4而形成軟管主體6C,將該軟管主體6C捲取於捲取機16。於本實施形態中,雖軟管主體6C,係將加硫裝置14設置於離開第2壓出機11後捲取於捲取機16之間,以捲取機16捲取經加硫的軟管6E,但加硫步驟,亦可設置在以捲取機16捲取軟管主體6C之
後。此外,於加硫裝置14前後,係設置有用以將耐隆布等之保護布朝軟管主體6C裝脫的包裝裝置13及解開裝置15。另外,於第2圖中,藉由包裝裝置13,捲繞有耐隆布的加硫前之軟管6D,係成為加硫後、取下耐隆布前之軟管6E。針對加硫步驟係後述。
接著,於階段S104中,加硫後,藉由心軸拔出裝置17從經解開的軟管6F,拔出心軸6而完成軟管6G。
如第3圖所示,離開第2壓出機11的軟管主體6C,係藉由包裝裝置13而將耐隆布18捲繞在周圍。以耐隆布18包圍的軟管主體6C,被搬入加硫裝置14內。加硫裝置14,係藉由熱風19使加硫進行的熱風循環型之連續加硫裝置。此加硫方式係烘箱加硫方式。
第4圖係說明被投入加硫裝置的心軸6周圍之層構造的一例子之局部剖面圖。如第4圖所示,於心軸6周圍,係形成內側橡膠層2,進而於其周圍形成補強層3,進而於其周圍形成外側橡膠層4。於外側橡膠層4的周圍,係捲繞耐隆布18,以此狀態加熱而進行加硫步驟。
如上所述,加硫溫度,較佳為130℃以上180℃以下,且加硫時間,亦即加硫裝置14內之加硫時間,係30分鐘以上240分鐘以下。於此溫度範圍及加硫時間
中,可得到橡膠層與補強層之接著性為良好的油壓軟管。
於軟管製造步驟中,藉由使用橡膠組成物來形成內側橡膠層2及外側橡膠層4至少一者,而可製造與金屬製之補強層的接著性為良好的油壓軟管。
另外,依據橡膠組成物,由於至加硫之前可將適度的水分安定地保留在組成物中,因此即使於水分蒸發大的烘箱加硫方式中,亦可抑制因水分不足所導致之接著不良及接著性的降低。然而,上述形態之橡膠組成物,當然可適合使用於以以往周知的其他加硫方式所進行的橡膠製品之製造中。其他的加硫方式係可列舉例如:壓力加硫、蒸氣加硫、及溫水加硫等。
此外,於上述實施形態中,雖例示以連續處理方式所致之製造步驟,但藉由在以其他步驟製造橡膠層與補強層之後使其貼合的方法亦可製造加硫橡膠製品。
藉由本實施形態之製造方法所製造的油壓軟管,係可適用於各種用途中。油壓軟管的用途,係可適合作為於例如汽車用空調軟管、動力轉向軟管、建設車輛的油壓系統等所使用的油壓軟管等。
此外,於本實施形態中,雖使用油壓軟管作為橡膠組成物金屬層合體及加硫橡膠製品進行說明,但本發明並不限定於此,亦可相同地使用於例如輸送帶(Conveyor belt)等其他的橡膠層合體。
如上所述,依據橡膠組成物金屬層合體、加硫橡膠製品、及加硫橡膠製品之製造方法,即使於以烘箱加硫方式所進行之連續生產方式中,亦可提供橡膠層與補強層之接著性為良好的加硫橡膠製品。尤其,即使在乾燥狀態長期保管之後使用時,亦可提供形成與補強層之接著性良好的橡膠製品之組成物。此加硫橡膠製品,係可適合作為油壓軟管、高壓軟管等使用。
以下,藉由實施例具體地說明本發明。但,本發明並不限定於此等。
以密閉式混合機(Bumbary mixers)將表1及表2所示之摻合比的原料進行混練,得到實施例1~22之橡膠組成物。另外,表中之數值的單位,係除了特別指明的情況以外,皆表示將二烯系聚合物的合計質量設為100時之質量份。
以密閉式混合機(Bumbary mixers)將表3及表4所示之摻合比的原料進行混練,得到比較例1~14之橡膠組成物。另外,表中之數值的單位,係除了特別指明的情況以外,皆表示將二烯系聚合物的合計質量設為100時之質量份。
表1~表4所記載的個成分之詳細內容係如下述。
.NBR:商品名「Nancar 3345」、南帝化學工業公司製、丙烯腈含量34質量%、木尼黏度(ML1+4,100℃)45
.EPDM:商品名「EPT 4070」、三井化學公司製、乙烯含量56質量%、亞乙基降冰片烯含量8質量%、木尼黏度(ML1+4,125℃)47
.SBR:商品名「Nipol 1502」、日本ZEON公司製、乳化聚合SBR、鍵結苯乙烯含量23.5質量%、木尼黏度(ML1+4,100℃)52
.CR:商品名「DENKA氯丁二烯S-41」、電氣化學工業公司製、非硫改性氯丁二烯橡膠、木尼黏度(ML1+4,100℃)48
.吸水性樹脂1:丙烯酸聚合物鈉中和鹽交聯物、商品名「Acrylic CA-K4」、日本觸媒公司製
.吸水性樹脂2:改性丙烯酸系交聯聚合物、商品名「Acrylic CS-6S」、日本觸媒公司製
.吸水性樹脂3:聚伸烷基氧化物、商品名「Aquacalk TW」、住友精化公司製
.吸水性樹脂4:聚乙二醇、商品名「macrogol 6000P」、三洋化成公司製
.水膨潤性黏土:商品名「Benclay MK-101H」、水澤化學工業公司製
.濕式法二氧化矽:商品名「NIPSIL AQ」、Tosoh
Silica公司製
.氫氧化鋁:商品名「HIGILITE H-42M」、SHEPHERD CHEMICAL公司製
.碳酸鎂:商品名「碳酸鎂TT」、Naikai鹽業公司製
.水:自來水
.硫:細井化學工業公司製
.加硫促進劑1:N-t-丁基苯并噻唑-2-亞磺醯胺、商品名「Nocceler NS-P」、大內新興化學工業公司製
.加硫促進劑2:一硫化四甲基秋蘭姆、商品名「SANCELER TS-G」、三新化學工業公司製
.加硫促進劑3:二苯基胍、商品名「SOXINOL D-G」、住友化學公司製
.抗焦劑(antiscorching agent):N-環己基硫鄰苯二甲醯亞胺、FLEXSYS公司製
.ISAF級碳黑:商品名「SHOBLACK N220」、Showa Cabot公司製
.FEF級碳黑:商品名「HTC#100」、新日化Carbon公司製
.硬黏土:商品名「Suprex Clay」、Kentucky-Tennessee clay company製
.氧化鋅3種:正同化學工業公司製
.氧化鎂:商品名「kyowamag 150」、協和化學工業公司製
.硬脂酸:日本油脂公司製
.抗臭氧劑:商品名「OZONONE 6C」、精工化學公司製
.可塑劑:己二酸二辛酯、商品名「DIACIZER DOA」、Mitsubishi Kasei Vinyl公司製
.加工油:芳香系油、商品名「A-OMIX」、三共油化工業公司製
使用在實施例1~22及比較例1~14所得到的各橡膠組成物作為外側橡膠層,並與以鍍黃銅線板所製作的補強層接著,以下述方式製作軟管狀試驗片。
首先,於外徑34mm之心軸上,將表面經鍍黃銅的線料捲繞成板狀,形成補強層。接著,於補強層之上,貼合從所得到之各橡膠組成物所調製出的厚度2.5mm之未加硫薄片,而得到未加硫軟管狀試驗片。其次,以覆蓋未加硫軟管狀試驗片之外側的方式捲繞耐隆66製之焙固帶(保護布),而進行加硫。
加硫係在以下的4種條件下進行,評估所得到的軟管狀加硫試驗片之接著強度與附橡膠。另外,接著強度及附橡膠,係分別經10次測定後之值的平均值。
.加硫條件1:將使用剛混練後之橡膠組成物所製作出的未加硫軟管狀試驗片在142℃的蒸氣罐內進行加硫90分鐘(蒸氣加硫)。
.加硫條件2:將使用剛混練後之橡膠組成物所製作出的未加硫軟管狀試驗片在142℃的常壓烘箱內進行加硫135分鐘(烘箱加硫)。
.加硫條件3:將未加硫軟管狀試驗片在25℃、55%相對濕度(%RH)之乾燥環境下保管2週之後,在142℃之常壓烘箱內進行135分鐘加硫(烘箱加硫)。
.加硫條件4:將未加硫軟管狀試驗片在25℃、30%相對濕度(%RH)之乾燥環境下保管4週之後,在142℃之常壓烘箱內進行135分鐘加硫(烘箱加硫)。
針對在上述各加硫條件所得到的各軟管狀加硫試驗片,評估接著強度(kN/m)與附橡膠(%)。在此,接著強度(kN/m),係指以剝離速度50mm/分鐘將外側橡膠層從外側橡膠層與補強層的界面剝離時所需要之每單位寬度(m)的力量大小(kN)。在此,附橡膠,係指軟管狀加硫試驗片的外側橡膠層殘留在補強層表面的比例,且以百分率表示殘留橡膠層相對於補強層表面積全體的面積比率者。
將接著強度及附橡膠之測定的結果顯示於表5~表8。於表5~表8中之接著試驗片1~4,係對應於在
上述加硫條件1~4所製作出的試驗片之試驗結果。於接著強度為2.5kN/m以上,且附橡膠為60%以上的情況,可說是外側橡膠層與補強層之接著性良好。
進而,針對各組成物,利用以下的基準評估混練時之橡膠混合加工性。將針對實施例1~22的評估結果顯示於表5及表6,將針對比較例1~14的評估結果顯示於表7及表8。
○:整合度為良好。
△:整合度不良亦不差。
×:整合度差。
進而,針對各軟管狀加硫試驗片,利用以下的基準藉由目視評估外側橡膠層的外觀。將針對實施例1~22的評估結果顯示於表5及表6,將針對比較例1~14的評估結果顯示於表7及表8。
○:無凹坑狀的缺陷(多孔)。
×:有凹坑狀的缺陷(多孔)。
如表5及表6得以明瞭般地,實施例1~22之組成物係其橡膠混合加工性良好,亦即,以密閉式混合機所進行之混練後的橡膠組成物之整合度佳。此外,加硫後之橡膠外觀亦無多孔而為良好。進而,使用實施例1~22之組成物所製作出的軟管狀加硫試驗片,係與補強層的接著強度皆為2.5kN/m以上,且附橡膠為60%以上。進而,使用實施例1~22之組成物所製作出的軟管狀加硫試驗片,即使保管4週之後,接著強度亦皆為2.5kN/m以上,且附橡膠為60%以上。
如表7及表8所得以明瞭般地,針對使用比較例1~14之組成物所製作出的軟管狀加硫試驗片,保管4週後之接著強度亦皆未達2.5kN/m以上,且附橡膠皆未達60%。此外,針對比較例4、5、7、11、12、14,橡膠混合加工性及橡膠外觀皆不良。
Claims (16)
- 一種金屬表面接著性橡膠組成物,其係與金屬表面進行接著的金屬表面接著性橡膠組成物,其特徵係相對可硫加硫的二烯系聚合物100質量份,含有3.0質量份以上15質量份以下的水與0.5質量份以上10質量份以下的作為水分保留劑之吸水性樹脂。
- 如請求項1記載之金屬表面接著性橡膠組成物,其中,前述吸水性樹脂為由丙烯酸聚合物部分鈉鹽交聯物、改性丙烯酸系交聯聚合物、及聚醚化合物選出之至少1種。
- 如請求項2記載之金屬表面接著性橡膠組成物,其中,前述聚醚化合物為聚環氧乙烷或聚乙二醇。
- 一種金屬表面接著性橡膠組成物,其係與金屬表面進行接著的金屬表面接著性橡膠組成物,其特徵為相對可硫加硫的二烯系聚合物100質量份,含有3.0質量份以上15質量份以下的水與0.5質量份以上20質量份以下的作為水分保留劑之無機保水劑。
- 如請求項4記載之金屬表面接著性橡膠組成物,其中,前述無機保水劑為由水膨潤性黏土、二氧化矽、氫氧化鋁、氧化鋁、碳酸鈣、碳酸鎂、及沸石所選出之至少1種。
- 如請求項1~請求項5中任1項記載之金屬表面接著性橡膠組成物,其中,前述金屬表面為經鍍黃銅的金屬表面。
- 如請求項1~請求項5中任1項記載之金屬表面接著性橡膠組成物,其中,前述二烯系聚合物包含由天然橡膠(NR)、異戊二烯橡膠(IR)、苯乙烯-丁二烯橡膠(SBR)、腈-丁二烯橡膠(NBR)、乙烯-丙烯-二烯橡膠(EPDM)、及氯丁二烯橡膠(CR)所選出之至少1種。
- 如請求項1~請求項5中任1項記載之金屬表面接著性橡膠組成物,其中再含有加硫劑。
- 一種橡膠組成物金屬層合體,其特徵係層合有請求項1~請求項5中任1項記載之金屬表面接著性橡膠組成物所構成的橡膠層與具有金屬表面的補強層。
- 如請求項9記載之橡膠組成物金屬層合體,其中,前述金屬表面為經鍍黃銅的金屬表面。
- 如請求項10記載之橡膠組成物金屬層合體,其中,前述補強層具有線料編成的編織構造或螺旋構造。
- 一種加硫橡膠製品,其特徵係請求項9記載之橡膠組成物金屬層合體的前述橡膠層在含硫加硫劑存在下被加硫,並與前述補強層接著。
- 如請求項12記載之加硫橡膠製品,其為油壓軟管或高壓軟管。
- 如請求項13記載之加硫橡膠製品,其中,前述油壓軟管或前述高壓軟管藉由通過烘箱加硫裝置內而被加硫。
- 一種加硫橡膠製品的製造方法,其特徵係具有將表面經鍍黃銅的補強層與至少一橡膠層層合,製作層合體的層合步驟、使前述層合體通過烘箱加硫裝置內,將前述橡膠層加硫,再與前述經鍍黃銅的補強層接著之加硫接著步驟,且前述橡膠層相對可硫加硫的二烯系聚合物100質量份,含有3.0質量份以上15質量份以下的水與0.5質量份以上10質量份以下的作為水分保留劑之吸水性樹脂的橡膠組成物中,再含有含硫加硫劑。
- 一種加硫橡膠製品的製造方法,其特徵係具有將表面經鍍黃銅的補強層與至少一橡膠層層合,製作層合體之層合步驟、使前述層合體通過烘箱加硫裝置內,將前述橡膠層加硫,再與前述經鍍黃銅的補強層接著之加硫接著步驟,且前述橡膠層相對可硫加硫的二烯系聚合物100質量份,含有3.0質量份以上15質量份以下的水與0.5質量份以上20質量份以下的作為水分保留劑之無機保水劑的橡膠組成物中,再含有含硫加硫劑。
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- 2014-04-18 CN CN201480022600.6A patent/CN105143333B/zh active Active
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Also Published As
Publication number | Publication date |
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US10047251B2 (en) | 2018-08-14 |
WO2014175186A1 (ja) | 2014-10-30 |
CN105143333B (zh) | 2017-12-26 |
CN105143333A (zh) | 2015-12-09 |
US20160096981A1 (en) | 2016-04-07 |
TW201504374A (zh) | 2015-02-01 |
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