CN1171131A - 成型金属表面的清洁和调节方法 - Google Patents
成型金属表面的清洁和调节方法 Download PDFInfo
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- CN1171131A CN1171131A CN95197029A CN95197029A CN1171131A CN 1171131 A CN1171131 A CN 1171131A CN 95197029 A CN95197029 A CN 95197029A CN 95197029 A CN95197029 A CN 95197029A CN 1171131 A CN1171131 A CN 1171131A
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- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
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- RZEWIYUUNKCGKA-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanol;octadecanoic acid Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCCC(O)=O RZEWIYUUNKCGKA-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical group CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
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- 229910015275 MoF 6 Inorganic materials 0.000 description 1
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 1
- FOUZISDNESEYLX-UHFFFAOYSA-N N-hydroxyethyl glycine Natural products OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 1
- 229910001229 Pot metal Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
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- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- BJWZZFCHXXUQTD-UHFFFAOYSA-M dodecanoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CCCCCCCCCCCC([O-])=O BJWZZFCHXXUQTD-UHFFFAOYSA-M 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- DMMXZLMYEUEJFT-UHFFFAOYSA-N ethyl 16-methylheptadecanoate Chemical compound CCOC(=O)CCCCCCCCCCCCCCC(C)C DMMXZLMYEUEJFT-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- KWMLJOLKUYYJFJ-VFUOTHLCSA-N glucoheptonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O)C(O)=O KWMLJOLKUYYJFJ-VFUOTHLCSA-N 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
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- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000001303 quality assessment method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical class [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- BXXNEFQMLKWMCP-UHFFFAOYSA-M tetradecanoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CCCCCCCCCCCCCC([O-])=O BXXNEFQMLKWMCP-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/68—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
- C10M107/34—Polyoxyalkylenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/48—Lubricating compositions characterised by the base-material being a macromolecular compound containing phosphorus
-
- C—CHEMISTRY; METALLURGY
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Abstract
一种用于成型金属表面,特别是饮料容器的润滑剂和表面调节剂,可降低所述金属表面的静摩擦系数并可使所述金属表面在低温下干燥。通过与金属表面接触形成添加剂的含水组合物包括选自磷酸酯,醇,包括单-、二-、三-和多元酸的脂肪酸,脂肪酸衍生物如盐、羟基酸、酰胺、醇、酯、醚和其衍生物,及其混合物;和至少一种选自金属态或离子态锆、钛、铈、铝、铁、锡、钒、钽、铌、钼、钨和铪的元素。为了避免在含水润滑剂和表面调节剂形成组合物中形成淤渣,该组合物应尽可能少地含菲环如通过乙氧基化松香制备的常规表面活性剂。为了确保最大限度地减少在含水润滑剂和表面调节剂形成组合物中的这类表面活性剂,应在前面的清洗步骤中避免或最大限度地减少含菲环的表面活性剂。
Description
该申请是共同未决的美国专利申请序列号No.126143(1993年9月23日提交)的部分继续,而后者又是已放弃的申请序列号No.910483(1992年7月8日提交)的部分继续,而后者又是已放弃的共同未决的申请序列号No.785635(1991年10月31日提交)的部分继续,而后者又是已授权美国专利No5080814(申请序列号No.521219、1990年5月8日提交)的继续申请,而后者又是已授权美国专利No.4944889(申请序列号No.395620,1989年8月18日提交)的继续申请,而后者又是已授权美国专利No.4859351(申请序列号No.07/057129,1987年7月1日提交)的部分继续申请。前述专利的全部内容,只要不与本文所述明显矛盾之外,均引入本文作为参考。
本发明涉及用于成形金属表面的清洁剂和表面调节剂,具体涉及可在对涂于铝罐上的涂料或漆的附着力无不利影响下改进铝罐的可移动性,且可降低干燥所述表面所需的烘箱温度的润滑剂和表面调节剂。本发明更具体涉及清洁和这样的表面调节相结合的方法,当表面调节剂含金属元素作为其化学组成的一部分时,该方法可在表面调节过程中最大限度地减少形成的淤渣和其它不希望的相分离。
铝罐通常用作各种产品的容器。铝罐生产出来后,一般将其用酸性清洁剂清洗以除去其中的铝细屑和其它污染物。考虑到环境和随后的酸性清洗残留于罐上的残余物可能会影响封装于罐中的饮料的味道,导致人们对通过碱清洗除去这些细屑和污染物感兴趣。然而,处理铝罐通常会导致不同的罐外金属表面腐蚀与罐内金属表面腐蚀的比例。例如,达到罐内无铝细屑表面所需的最优条件通常导致罐在传送带上的移动问题,原因在于增加了罐外表面的粗糙度。
当试图将罐输送过一次灌充嘴和印刷机时,这些铝罐的移动性问题特别明显。因此在铝罐制造工业中,日益希望在对涂于铝罐上的涂料或漆的附着力无不利影响下改进铝罐内外表面的静摩擦系数。改进铝罐移动性的原因通常是制造业中在不增加建立新设备的额外成本下提高产量的趋势。增加产量的需求希望制造厂家增加它们的生产线和印刷机的速度以在单位时间内生产更多的罐。例如,在不对铝罐进行降低其表面摩擦系数的任何处理下,铝罐通过印刷工段的最大速度通常平均为约1150个罐/分钟,且希望将该速度增加至约1800至2000个罐/分钟或更高。
然而,通过酸或碱清洁剂彻底清洗的铝罐通常具有高的表面粗糙度的特性,因此具有高的静摩擦系数。当试图增加其生产线速度时,该性能阻碍了罐通过灌充嘴和印刷机的流动。结果,除了罐损坏率高外,还出现了印刷机传输失效问题、经常堵塞、停车和产量降低。
另一个对改进铝罐表面性能的考虑,涉及当铝罐通过印刷或贴标签工段时这种改进会干扰要印刷的铝罐的性能或对此性能造成不利影响。例如铝罐清洗后,可在其外表面上印刷标签,并可将漆涂于罐的内表面上。在这种情况下,涂料和漆的附着力是主要要考虑的。
此外,在铝罐制造业中目前的趋势涉及使用厚度更薄的铝金属坯料,降低铝罐金属坯料厚度已造成的问题是,当清洗后,铝罐希望更低的烘箱温度以通过柱强度压力质量控制试验。然而,降低烘箱温度会造成罐到达印刷工段时未充分干燥,由此造成标签油墨污点和更高的罐次品率。
因此,为了提高产量、降低生产线堵塞、尽量减少停车时间、降低罐损坏、改进油墨沉积和降低已清洗的罐的烘箱温度,希望提供一种改进铝罐通过一次灌充嘴和印刷机的移动性的方法。因此,本发明目的在于提供此类改进铝罐移动性的方法并克服上述问题。
在目前广泛使用的工业实践上,至少对于大规模操作,通常对铝罐进行下表A中所述的连续六个清洁和漂洗操作。(某些时候也使用表A中所述的任何步骤前与室温自来水接触的步骤;当使用时,该步骤通常称为各编号步骤的“连接”步骤。)
表A | |
步骤数 | 各步骤期间对表面的作用 |
1 | 含水酸预清洗 |
2 | 含水酸和表面活性剂清洗 |
3 | 自来水漂洗 |
4 | 弱酸后清洗,转化型涂布,或自来水漂洗 |
5 | 自来水漂洗 |
6 | 去离子(“DI”)水漂洗 |
目前可以通过在上述步骤4或6中使用合适的表面活性剂生产能够满意地移动且随后在其上涂布的油墨和/或漆具有合适的附着力的罐。已经开发了用于上述步骤4中的优选处理方法并描述于US 5,030,323和5,064,500中。对于这些处理,将金属元素(不是必须的或甚至通常为元素形式)包括于润滑剂和形成的表面调节层中。
长期实际使用润滑剂和表面调节剂的成形处理(将金属加入形成的表面调节剂层中)的经验显示这些处理对形成的至少一种分离不纯相(通称为“淤渣”或“某些类似术语”)敏感。淤渣通常是粘性的,因此淤渣中的小颗粒容易与正在处理的容器粘附,若发生这种情况,则会造成被称为“金属暴露”的不理想现象,即随后涂布的内部安全卫生漆不能完全使铝罐中封装的饮料产品与金属罐体的接触隔离。因此,若形成足够量的淤渣,必须将其在连续进行罐调节前除去。由于淤渣的粘性,难以满意地除去,因此最大限度减少和(若可能)防止形成淤渣是本发明目的之一。
除权利要求和操作实施例中外或除非另有说明,表示本发明所用组分量或反应条件的所有数据应认为在所有情况下被术语“约”修饰以描述本发明的最宽范围。然而,在所给数值范围内实施通常是优选的。同样,除非另有说明,描述组合物组分的所有百分数或“份数”等都是指与总量相比的组分的重量或质量。
根据本发明,已发现在洗涤后涂于铝罐上的润滑剂和表面调节剂可增强其移动性,同时在优选实施方案中可提高水膜沥干和蒸发性能,由此可使烘箱温度降低约25°至约100°F,而对标签印刷过程无不利影响。润滑剂和表面调节剂降低罐外表面上的静摩擦系数使生产线速度显著增加,同时在满足质量控制要求下显著改进水膜沥干和蒸发速率使因降低能量需求而节能。
更具体地,根据本发明的一个优选实施方案,已发现将薄的有机膜涂于铝罐外表面上可起到有助于降低静摩擦系数的润滑剂的作用,该有机膜可因此提供改进的罐移动性并提高罐可干燥的速度且仍然通过质量控制柱强度压力试验。已发现改进移动性和罐的干燥速度的程度取决于有机膜的厚度或量,并取决于涂于罐上的物质的化学性质。
本发明的铝罐润滑剂和表面调节剂(例如)可选自水溶性烷氧基化表面活性剂如有机磷酸酯类;醇类;脂肪酸类包括单-、二-、三-和多元酸类;脂肪酸衍生物如盐类、羟基酸类、酰胺类、酯、醚和其衍生物;及其混合物。
在本发明一个优选实施方案中,铝罐润滑剂和表面调节剂优选包括饱和脂肪酸如乙氧基化硬脂酸或乙氧基化异硬脂酸的水溶性衍生物,或其碱金属盐如聚氧乙基化的硬脂酸盐和聚氧乙基化的异硬脂酸盐。此外,用于铝罐的润滑剂和表面调节剂可包括具有至少约4个碳原子的水溶性醇并可含有至多约50mol环氧乙烷。当醇包括平均含约20mol环氧乙烷/mol醇的聚氧乙基油醇时已获得极好的结果。
在本发明的另一优选方面中,铝罐碱洗或酸洗后并在输送前的外表面最后干燥前用于在铝罐上形成膜的有机材料包括水溶液有机物质,该有机物质选自磷酸酯,醇,脂肪酸包括单-、二-、三-和多元酸衍生物包括盐、羟基酸、酰胺、醇、酯、醚及其衍生物以及它们的混合物。这种有机物质优选为水溶液的一部分,该水溶液包括适合在清洁的铝罐上形成薄膜的水溶性有机物质以在干燥后提供静摩擦系数不大于1.5的表面,而在无这种膜涂层时在相同类型的表面不能获得这样的静摩擦系数。
在本发明的一个实施方案中,可通过烷氧基化、优选乙氧基化、丙氧基化或其混合使有机物质具有水溶性。然而,非烷氧基化的磷酸酯,特别是磷酸与各种醇的含游离酸或中和的单-和二酯也适用于本发明。具体的例子包括购自Henkel Corp的Tryfac 5573磷酸酯(一种含游离酸的酯);及购自Union Carbide Corporation的Triton H-55、Triton H-66和Triton QS-44。
优选的非乙氧基化醇类包括下列醇类:
合适的一元醇和其与无机酸的酯包括每分子含有3至约20个碳原子的水溶性化合物。具体的例子包括十二烷基硫酸钠如购自Witco Corp的Dupono WAQ、Duponol QC、Duponol WA和Duponol C及专利产品烷基磺酸钠如购自E.I.du Pont de Nemours & Co.的Alkanol 189-S。
合适的多元醇包括含有两个或多个羟基的脂族或芳烷基多元醇。具体的例子包括甘油、山梨糖醇、甘露糖醇、黄原胶、己二醇、葡糖酸、葡糖酸盐、葡庚糖酸盐、季戊四醇和其衍生物,糖类和烷基聚苷如购自Henkel Corp.的APG 300和APG 325。特别优选的多元醇包括三甘油(triglycerol),特别是甘油或其脂肪酸酯如蓖麻油三酸甘油酯。
根据本发明,我们已发现特别当铝罐生产线的运行被中断造成铝罐在高温下暴露持续一段时间时,烷氧基化的,尤其是乙氧基化的蓖麻油三酸甘油酯作为润滑剂和表面调节剂导致铝罐移动性进一步改进。因此,特别优选的物质包括Trylox5900、Trylox5902、Trylox5904、Trylox5906、Trylox5907、Trylox5909、Trylox5918和氢化蓖麻油衍生物如Trylox5921和Trylox5922,都购自Henkel Corp。
优选的脂肪酸包括丁酸、戊酸、己酸、辛酸、癸酸、壬酸、月桂酸、肉豆蔻酸、棕榈酸、油酸、硬脂酸、亚油酸和蓖麻油酸;丙二酸、丁二酸、戊二酸、己二酸、马来酸、酒石酸、葡糖酸和二聚体酸;及这些酸的盐;亚氨基二丙酸盐如购自Exxon Chemical Co.的AmphotericN和Amphoteric400;购自Henkel Corp.的硫代丁二酸盐衍生物如TexaponSH-135 Special和TexaponSB-3;柠檬酸、次氮基三乙酸和1,2,4-苯三酸;购自GAFChemicals Corp的CheeloxHEEDTA、N-(羟乙基)-乙二胺三乙酸酯。
优选的酰胺通常包括具有四至二十个碳原子的酰胺或取代酰胺。具体的例子是购自Rhone-Poulenc的AlkamideL 203月桂酸单乙醇酰胺、AlkamideL7DE月桂酸/肉豆蔻酸链烷醇酰胺、AlkamideDS 280/s硬脂酸二乙醇酰胺、AlkamideCD椰子二乙醇酰胺、AlkamideDIN 100月桂酸/亚油酸二乙醇酰胺、AlkamideDIN 295/s亚油酸二乙醇酰胺、AlkamideDL203月桂酸二乙醇酰胺;购自Mona Industries Inc.的Monamid 150-MW肉豆蔻酸乙醇酰胺、Monamid 150-CW癸酸乙醇酰胺、Monamid 150-IS异硬脂酸乙醇酰胺;及购自Akzo Chemicals Inc.的Ethomid HT/23和Ethomid HT60聚氧乙基化的氢化动物脂胺。
优选的阴离子有机衍生物通常包括脂肪酸的硫酸盐和磺酸盐衍生物,包括天然和合成衍生的醇、酸和天然产物的硫酸盐和磺酸盐衍生物。具体的例子包括:十二烷基苯磺酸盐如购自Dow Chemical Co.的Dowfax2A1、Dowfax2AO、Dowfax3BO和Dowfax3B2;购自Henkel Corp.的LomarLS缩合萘磺酸、钾盐。硫代丁二酸盐衍生物如购自Mona Industries的MonamateCPA改性链烷醇酰胺的硫代丁二酸二钠、MonamateLA-100月桂基硫代丁二酸二钠;购自Union Carbide Chemical and Plastics Co.的TritonGR-5M二辛基硫代丁二酸钠;购自Sherex Chemical Co.,Inc.的VarsulfSBFA30脂肪醇醚硫代丁二酸盐、VarsulfSBL 203脂肪酸链烷醇酰胺硫代T二酸盐、VarsulfS1333蓖麻油酸单乙醇酰胺硫代丁二酸盐。
另一类优选的有机物质包括水溶性的烷氧基化,优选乙氧基化、丙氧基化或混合的乙氧基化和丙氧基化物质,最优选选自脂肪酸(包括单-、二-、三-和多元酸)的胺盐、氨基脂肪酸、脂肪胺N-氧化物和季盐的乙氧基化和非乙氧基化有机物及水溶性聚合物。
脂肪酸的优选胺盐包括脂肪酸铵、季铵、鏻和碱金属盐及其在阳离子或阴离子部分或这两部分都含有高达50mol烯化氧的衍生物。具体的例子包括购自Exxon Chemicaol Co.的Amphoteric N和Amphoteric 400亚氨基二丙酸钠盐;购自Henkel Corp.的Deriphat 154 N-动物脂-β-亚氨基二丙酸二钠和Deriphat 160 N-月桂基-β-亚氨基二丙酸二钠。
优选的氨基酸包括α和β氨基酸和二酸及其盐,包括烷基和烷氧基亚氨基二丙酸和它们的盐及肌氨酸衍生物和它们的盐。具体例子包括购自Akzo Chemical Inc.的ArmeenZ,N-椰子基-β-氨基丁酸;购自ExxonChemical Co.的Amphoteric N,Amphoteic 400;肌氨酸(N-甲基甘氨酸);羟乙基甘氨酸;HamposylTL-40月桂酰基肌氨酸三乙醇胺,HamposylO肌氨酸月桂酰基酯,Hamposyl AL-30月桂酰基肌氨酸铵,HamposylL肌氨酸月桂酰基酯和HamposylC肌氨酸椰子基酯,都购自W.R.Grace& Co.。
优选的胺N-氧化物包括其中至少一个烷基取代基含三个碳原子至高达20个碳原子的的胺氧化物。具体例子包括:购自Akzo的AromoxC/12双-(2-羟乙基)椰子基烷基胺氧化物,AromoxT/12双-(2-羟乙基动物脂烷基胺氧化物,AromoxDMC二甲基椰子基烷基胺氧化物,AromoxDMHT氢化二烷基胺氧化物,AromoxDM-16二甲基十六烷基烷基胺氧化物;和购自Exxon Chemical Co.的TomahA0-14-2和Tomh A0-728。
优选的季铵盐包括含有至少一个含12至20个碳原子的取代基和0至50mol环氧乙烷和/或0至15mol环氧丙烷的脂肪胺的季铵衍生物,其中抗衡离子由卤素、硫酸盐、硝酸盐、羧酸盐、烷基或芳基硫酸盐、烷基或芳基磺酸盐或其衍生物组成。具体例子包括购自Akzo Chemicals Inc.的Arquad12-37W十二烷基三甲基氯化铵,Arquad18-50十八烷基三甲基氯化铵,Arquad 210-50二-庚基二甲基氯化铵,Arquad 218-100二-十八烷基二甲基氯化铵,Arquad 316(W)三-十六烷基甲基氯化铵,Arquad B-100苄基二甲基(C12-18)烷基氯化铵,Ethoquad C/12椰子基甲基[POE(2)]氯化铵,Ethoquad C/25椰子基甲基[POE(15)]氯化铵,Ethoquad C/12硝酸盐,Ethoquad T/13 Acetate乙酸三(2-羟乙基)动物脂烷基铵,Duoquad T-50 N,N,N′,N′,N′-五甲基-N-动物脂-1,3-二铵二氯化物,Propoquad 2HT/11二(氢化动物脂烷基)(2-羟基-2-甲基乙基)甲基氯化铵,Propoquad T/12动物脂烷基-甲基-双-(2-羟基-2-甲基乙基)甲基硫酸铵;购自Mona Industries Inc.的Monaquad P-TS硬脂酰氨基丙基PG-磷酸二氯化二铵;购自Chemax Inc.的Chemquad 12-33月桂基三甲基氯化铵,Chemquad 16-50十六烷基三甲基氯化铵;和四甲基壬酸铵,四甲基月桂酸铵,四甲基肉豆蔻酸铵,四甲基油酸铵,四甲基硬脂酸铵或四甲基硬脂酸异铵。
优选的水溶性聚合物包括环氧乙烷、环氧丙烷、环氧丁烷、丙烯酸和其衍生物、马来酸和其衍生物、乙烯基苯酚和其衍生物及乙烯醇的均聚物和共聚物。具体例子包括购自Union Carbide Corp.的Carbowax 200、Carbowax 600、Carbowax900、Carbowax 1450、Carbowax 3350、Carbowax 8000和Compound 20M;购自BASF Wyandotte Corp.的PluronicL61、PluronicL81、Pluronic31R1、Pluronic25R2、Tetronic304、Tetronic701、Tetronic908、Tetronic90R4和Tetronic150R1;购自Rohm & Haas Company的Acusol 410N聚丙烯酸的钠盐,Acusol445聚丙烯酸,Acusol460ND马来酸/烯烃共聚物的钠盐,和Acusol479N丙烯酸/马来酸共聚物的钠盐;及聚乙烯基苯酚的N-甲基葡糖胺衍生物和聚乙烯基苯酚的N-甲基乙醇胺衍生物。
另一些改进可通过将上述有机物质与选自金属态或离子态锆、钛、铈、铝、铁、钒、钽、铌、钼、钨、铪或锡的无机物质取得以生产混有一种或多种这些金属与一种或多种上述有机物质的薄膜。生产的薄膜具有的静摩擦系数不大于1.5且低于无此薄膜时的摩擦系数,由此改进罐在高速输送时的移动性,而不影响随后容器喷漆、其它喷涂、印刷或其它类似涂饰。当在上述第4步使用时,这类润滑剂和表面调节剂是特别优选的。
这些无机物质的加入工艺(以含锆的物质作为参考)详细描述于1991年7月9日的US5,030,323和1991年11月12日的US5,064,500中,其公开的全部内容完全符合本文的详细叙述,因此这里作为参考引入。用其它金属态物质取代这些专利之一中详细描述的物质为本领域熟练技术人员的公知的知识范围。
为提供改进的水溶性(特别是本文描述的非乙氧基化的有机物质的水溶性)和干燥后在罐表面上形成静摩擦系数小于1.5的合适薄膜,在本发明方法的另一优选实施方案中,使用包括一种或多种表面活性剂,优选烷氧基化的表面活性剂,更优选乙氧基化的表面活性剂,和此非乙氧基化的有机物质的润滑剂和表面调节剂形成组合物以在最后干燥和输送前与清洁的罐表面接触。优选的表面活性剂包括乙氧基和非乙氧基化硫酸或磺酸脂肪醇,如月桂醇和椰子醇。合适的表面活性剂是各种阴离子、非离子、阳离子或两性表面活性剂。烷基聚苷如平均聚合度为1.2至2.0的C8-C18烷基聚苷也是合适的。适合并用的其它类表面活性剂是含有1.5至100mol环氧乙烷的壬基苯酚和辛基苯酚,优选与6至50mol环氧乙烷缩合的壬基苯酚如购自Rhone-Poulenc的IgepalCO-887;烷基/芳基聚醚如TritonDF-16;及磷酸酯如Triton H-66和Triton QS-44,都是购自UnionCarbide Co.的Triton产品,和Ethox 2684和Ethfac 136,都购自Ethox Chemicals Inc.,是代表性的例子;线型和支化醇和其衍生物的聚乙氧基化和/或聚丙氧基化的衍生物,如Trycol6720(Henkel Corp.),Surfonic LF-17(Huntsman Chemical Co.)和Antarox LF-330(Rhone-Poulenc);线性和支化脂肪醇的磺化衍生物,如Neodol 25-3S(Shell Chemical Co.);磺化芳基衍生物,如Dyasulf 9268-A,Dyasulf C-70,Lomar D(Henkel Corp.)和Dowfax 2Al(DowChemical Co.);及环氧乙烷和环氧丙烷共聚物,如Pluronic L-61,Pluronic 81,Pluronic 31R1,Tetronic 701,Tetronic 90R4和Tetronic 150R1,都购自BASF Corp.。
已令人吃惊地发现,含菲环结构的表面活性剂(这里应理解为不仅含于菲本身中而且含于通过将菲环氢化至不足以断裂存在于菲中的三个环的任何一个制得的分子中)是润滑剂和表面调节剂形成组合物的不利构成组分(至少若组合物还含有上述选自金属态或离子态锆、钛、铈、铝、铁、钒、钽、铌、钼、钨、铪或锡的无机物质时)。当这些表面活性剂与这些无机物质的任何一种同时存在时,形成的淤渣显著增加。已发现形成淤渣的趋势一般可在不需实际处理罐条件下在实验室中通过如下方式测试:将污物如铝细粉、可溶性含铝物质、拉伸油和清洁剂表面活性剂人为加入待测试耐淤渣形成的润滑剂和表面调节剂形成组合物中,然后将人为污染的组合物反复通过喷涂步骤并观察其中排入喷涂液的容器中形成的泡沫头上是否出现干燥絮凝物。本测试中存在或不存在干燥絮凝物至少粗略定量相关地表明,是否淤渣在操作如此测试的润滑剂和表面调节剂形成组合物中可能变成一个问题,若存在,则形成的淤渣量可在实际使用中观察到。
目前,具有菲环结构的表面活性剂,特别是衍生自松香的松香酸酯、氢化松香酸酯和烷氧基化松香酸酯表面活性剂最常用于与各润滑剂和表面调节剂形成组合物接触前的容器处理清洗步骤,如表2中所示的步骤2中。由于在实际的高速度和大批量罐处理中不能完全避免用于后续处理步骤的组合物中夹带入一些清洁剂表面活性剂,因此这些清洁剂表面活性剂确实应在使用包括上述选自金属态或离子态锆、钛、铈、铝、铁、钒、钽、铌、钼、钨、铪或锡的无机物质的润滑剂和表面调节剂形成组合物之前很小心和限量地用于各处理步骤中。
更具体地,优选的是(优选性随所给顺序增加且对于各组合物是独立的),(i)含上述选自金属态或离子态锆、钛、铈、铝、铁、钒、钽、铌、钼、钨、铪或锡的无机物质的各种润滑剂和表面调节剂形成组合物,(II)容器与润滑剂和表面调节剂形成组合物接触前为提供润滑剂和表面调节剂层与容器接触的各清洁剂或漂洗组合物应在总碳原子中含有不大于5、4、3、2、1、0.5、0.4、0.3、0.2、0.1、0.05、0.04、0.03、0.02、0.01、0.005、0.004、0.003、0.002、0.001、0.0005、0.0004、0.0003、0.0002、0.0001、0.00005、0.00004、0.00003、0.00002、0.00001%的上述菲环结构部分。对于使用的润滑剂和表面调节剂形成组合物,最大限度地降低含菲环化合物的浓度特别有利,如US5,030,323和5,064,500中公开的。
含菲环的非离子表面活性剂至少在最近几年广泛用于清洗铝容器,原因在于对于除去这些容器上经常出现的某些有机污物特别有效。然而目前已发现烷基苯酚基非离子表面活性剂可满意地取代用于此目的含菲环结构的表面活性剂,且烷基苯酚基表面活性剂与含菲环的表面活性剂一样不能促使在含金属的润滑剂和表面调节剂形成组合物中形成淤渣。在含金属的润滑剂和表面调节剂形成组合物之前的用于清洗步骤的特别优选的表面活性剂混合物包括,更优选基本上由,或进一步更优选由如下组分组成:(A)非离子表面活性剂组分,选自符合如下化学式的表面活性剂:其中a为0或1;R代表烷基部分,它可以是支化或非支化的和饱和或不饱和的但不包括任何芳基,且R中的碳原子之和为10-22,更优选12-20,更进一步优选14-18;n为至少2但不大于4,更优选不大于3,最优选2的整数,且在相同分子中可以是相互不同的CnH2nO基团;b为整数,选取的b的数值应使总组分的亲水-亲油平衡(HLB)值为(优选性随所给顺序增加)不低于8、10、10.5、11.0、11.3、11.5、11.7、11.8、11.9、12.0或12.1,和独立地为(优选性随所给顺序增加)不大于20、18、16、15、14、13.7、13.5、13.3、13.1、12.9、12.8、12.7、12.6、12.5、12.4或12.3;和(B)非离子表面活性剂组分,选自符合化学式R′-Ф-(CnH2nO)cH的表面活性剂,其中R′代表烷基部分,它可以是支化或非支化的和饱和或不饱和的但不包括任何芳基,且具有4-16,更优选6-14,更进一步优选8-10,最优选9个碳原子;Φ代表亚苯基; n为至少2但不大于4,更优选不大于3,最优选2的整数;c为整数,选取的c的数值应使总组分的HLB值为(优选性随所给顺序增加)不低于9、10.0、10.6、11.2、11.7、12.2、12.5、12.7、12.9、13.0、13.1、13.2或13.3,和独立地为(优选性随所给顺序增加)不大于21、19、17、16、15、14.7、14.5、14.3、14.1、13.9、13.8、13.7、13.6或13.5。
混合物中组分(A)与组分(B)的比例独立的优选为不低于(优选性随所给顺序增加):0.1、0.2、0.3、0.4、0.5、0.55、0.59、0.63、0.60、0.62、0.64、0.66、0.67、0.68、0.69、0.70或0.71,和独立地为不大于(优选性随所给顺序增加)10、5、4、3、2、1.5、1.2、1.1、1.0、0.9、0.85、0.83、0.81、0.80、0.79、0.78、0.77、0.76、0.75、0.74、0.73或0.72。
根据本发明用于铝罐的润滑剂和表面调节剂可包括磷酸酯或优选乙氧基化的烷基醇磷酸酯。这些磷酸酯是购自GAF Corporation,Wayne,NJ的GafacPE 510和购自Ethox Chemicals,Inc.,Greeneville,SC的Ethfac 136和161及EthoxTM2684。通常有机磷酸酯可包括乙氧基化或非乙氧基化的磷酸烷基和芳基酯。
用于铝罐的润滑剂和表面调节剂可在罐洗涤循环过程中,在其处理循环之一如清洗或转化涂布过程中,在其水漂洗循环之一过程中,或在其最后的水漂洗循环过程中涂于罐上。此外,润滑剂和表面调节剂可在罐最后水漂洗循环前,即在烘箱干燥前或烘箱干燥后,通过细薄雾涂布由水或另一种非易燃溶剂的溶液涂于罐上。已发现,润滑剂和表面调节剂能够淀积于铝罐表面上使其具有所需的特性。润滑剂和表面调节剂可通过喷涂施用,并通过化学或物理吸附与铝表面反应使其具有所需的薄膜。
通常,在罐清洗过程中,在罐已被清洗后,一般将罐暴露于酸性水漂洗液中。根据本发明,这些罐可在随后用包括阴离子表面活性剂如磷酸酯的润滑剂和表面调节剂进行处理。在这种情况下,处理体系的pH值是重要的,通常应为酸性的,及在约1至约6.5,优选约2.5至约5之间。若罐在用酸性水漂洗后不接着用本发明的润滑剂和表面调节剂处理,则经常将罐暴露于自来水漂洗液,然后暴露于去离子水漂洗液中。对此,制备的去离子水漂洗溶液含有本发明的润滑剂和表面调节剂形成组合物,它包括选自上述聚氧乙基化的醇或聚氧乙基化的脂肪酸,或上述其它合适物质的非离子表面活性剂。如此处理后,可在进一步加工前将罐通过烘箱进行干燥。
涂于罐上的润滑剂和表面调节剂的量应足以将罐外表面上的静摩擦系数降低至约1.5或更低,优选约1或更地。一般而言,此量应使罐外表面上的润滑剂和表面调节剂的量为约3mg/m2至约60mg/m2。
本发明的另一实施方案包括本文描述的技术的应用以提供适合于锡罐的润滑剂和表面调节剂,有助于这些罐除水和干燥。本发明描述的组合物和方法适合于此目的。
为更充分地说明本发明,可参考下列实施例,但这些实施例仅是描述和说明性的,并不限制本发明的范围。
实施例1
本实施例说明改进罐通过工业罐生产装置的导轨和印刷工段的移动性,并证明润滑剂和表面调节剂对外表面印刷的标签粘结性及喷涂于罐内表面的漆无不利影响。
将从工业罐生产厂得到的未清洗的铝罐用购自Parker AmchemDivision,Henkel Corporation,Madison Heights,MI的碱清洁剂,采用该公司的Ridoline 3060/306方法清洗。将这些罐在一次加工14个罐的实验室小型清洗器中清洗。将这些罐在清洗器的最后漂洗步骤中用不同量的润滑剂和表面调节剂处理,然后在烘箱中干燥。该润滑剂和表面调节剂包括约10%的聚氧乙基异硬脂酸酯活性浓缩物,一种乙氧基化的非离子表面活性剂,购自Ethox Chemical,Inc.,Greenville,SC.,商品名为EthoxTM MI-14.。可将处理过的罐送回罐生产厂进行线速度和印刷质量评估。将这些印刷罐分为两组,各由4至6个罐组成。都用下列粘结性试验溶液处理20分钟。
试验溶液A:在去离子水∶自来水=3∶1中的1%Joy溶液(市购液态碗碟洗涤剂(Procter and Gamble Co.),温度180°F。
试验溶液B:在去离子水中的1%Joy洗涤剂溶液,温度212°F。
从粘结性试验溶液中取出印刷罐后,将每个罐用锋利的金属划上十字以暴露通过涂料或漆露出的铝线,然后测试涂料粘结性。此测试包括在划十字区域上牢固地贴上Scotch透明胶带No.610,然后通过快速拉动将胶带逆向拉回。试验结果的等级为:10,完好(当胶带不能从表面剥离任何涂料);8,可接受;0,完全失败。用肉眼检查罐的任何涂料或漆剥离痕迹。
此外,用实验室静摩擦试验仪评估其摩擦系数。此设备用于测量与铝罐表面特性有关的静摩擦。这可通过使用经90度弧度升高的斜面,通过用与斜面自由摆动末端相连的恒速马达、线圈和钢丝进行。用与斜面末端相连的支架在分开约0.5英寸的水平位置处夹持2个罐,其盖面对斜面固定末端。将第三个罐以盖面对斜面固定自由摆动末端放置于2个罐上,所有3个罐的边成直线排列,这样它们是相互对齐的。
随着斜面开始经其弧度运动,自动开起计时器。当斜面达到第三个罐自2个较低位置的罐滑动的角度时,光点开关关闭计时器。此时以秒为单位记录的时间通常称为“滑动时间”。静摩擦系数等于罐开始移动时斜面扫过的角度的正切值。粘合性试验的平均值和静摩擦系数评估结果概于下表1中。
表1
*在外壁上目测到较小的剥离(主要在接触标记处)。
试验No. | 润滑剂和表面调节剂浓缩物(%/vol.) | 粘 结 性 评 估试验溶液 OSW ISW ID | 静摩擦系数 | |||
1 | 对比(未处理) | - | - | - | - | 1.42 |
2 | 0.1 | B | 10 | 10 | 10 | 0.94 |
3 | 0.25 | A | 10 | 10 | 10 | - |
4 | 0.5 | B | 9.5* | 10 | 10 | 0.80 |
5 | 0.75 | A | 10 | 10 | 10 | 0.63 |
6 | 1.0 | B | 10 | 10 | 10 | 0.64 |
7 | 2.0 | A | 10 | 10 | 10 | 0.56 |
8 | 5.0 | B | 10 | 10 | 10 | 0.55 |
9 | 10.0 | A | 9.8* | 10 | 10 | 0.56 |
在表1中,“OSW”代表外侧壁,“ISW”代表内侧壁,“ID”内盖。
简而言之,对于涂于清洁的铝罐上的润滑剂和表面调节剂组合物,即使在非常低的活性组分浓度下也提供改进的罐移动性,并且甚至在20至100倍于降低罐静摩擦系数所需使用的浓度下对测试的标签印刷或内部漆的粘结性也无不利影响。
实施例2
本实施例说明在工业罐生产装置中当将罐以1260个罐/分钟的速率通过印刷工段时使用实施例1的罐润滑剂和表面调节剂。
将生产的铝罐用酸性清洁剂(Ridoline 125CO,购自Parker AmchemDivision,Henkel Corporation,Madison Heights,MI),然后用无铬酸盐的转化型涂料(Alodine 404,也购自Parker Amchem Division,Henkel Corporation,Madison Heights,MI)处理。然后,对生产的铝罐测试“滑动”性,发现罐外表面的静摩擦系数为约1.63。在这些罐通过印刷工段加工过程中,罐可以1150至1200个罐/分钟的速率通过印刷工段,无过量的“断路”,即不适当的荷载罐事件。在这种情况下,罐被不合适地荷载于印刷罐的心轴上。每次“断路”造成必须扔掉的罐损失,因为这些罐在最后加工阶段不能被接受。
将约1ml/l的铝罐润滑剂和表面调节剂加入罐清洗器的去离子水体系中,使铝罐外表面的摩擦系数降低至1.46或降低为其原来值的11%。将罐通过印刷机后,发现内外涂层的粘结性不受润滑剂和表面调节剂的影响。此外,印刷机的速度可增加至其1250至1260个罐/分钟的机械极限,不会出现新问题。
在类似的方式中,通过增加铝罐润滑剂和表面调节剂形成组合物在去离子漂洗水体系中的浓度,可降低罐的静摩擦系数20%,而对罐内外涂层的粘结性无不利影响。同时,可在24小时期间将印刷机的速度连续保持在1250个罐/分钟下。
实施例III
本实施例说明将其它材料用作铝罐润滑剂和表面调节剂的基本组分。
将铝罐在105°F下用pH值约12的碱性清洁剂溶液清洗约35秒。将这些铝罐漂洗,然后用三种不同的包括各种磷酸酯溶液的不同润滑剂和表面调节剂处理。磷酸酯溶液1包括浓度为0.5g/l的磷酸酯(购自GAFCoporation,Wayne,Nj,商品名为Gafac PE 510)。磷酸酯溶液2包括浓度为0.5g/l的乙氧基化烷基醇磷酸酯(购自Ethox Chemical,Inc.,Greenville,SC,商品名为Ethfac 161)。磷酸酯溶液3包括浓度为1.5g/l的乙氧基化烷基醇磷酸酯(购自Ethox Chemical,Inc.,Greenville,SC,商品名为Ethfac 136)。
根据静摩擦系数评估罐的移动性,结果如下:
磷酸酯溶液 | pH | 静摩擦系数 |
1 | 3.6 | 0.47 |
2 | 3.3 | 0.63 |
3 | 2.6 | 0.77 |
无 | - | 1.63 |
上述磷酸酯溶液提供铝罐可接受的移动性,但是铝罐完全被“水膜残迹”覆盖。要求铝罐无水膜残迹,即在其上具有薄的连续水膜,因为要不然它们含有大水滴,且水膜是非均匀和不连续的。为确定这是否损坏罐的印刷,评估它们的粘结性。即将印刷的罐切开并在1%的包括去离子水∶自来水=3∶1的液体碗碟洗涤溶液中(Joy)煮沸10分钟。然后将此罐在去离子水中漂洗并干燥。与实施例1一样,在罐内外壁和圆盖内的涂层上切割出8个十字划痕线。将这些划痕线用胶带贴上,然后撕去胶带。将这些罐给出粘结性值等级,平均结果概列于表2中。
表2
磷酸酯溶液 | 粘结性等级 | ||
OSW | ISW | ID | |
对比 | 10 | 10 | 10 |
1 | 9.8 | 6.8 | 1.0 |
2 | 9.8 | 10 | 10 |
3 | 10 | 10 | 10 |
表2中“OSW”代表“外壁”,“ISW”代表“内壁”,“ID”代表“内盖”。
对于对比溶液,在罐外壁、内壁或内盖上未观察到剥离(损失涂层粘结性)。
对于磷酸溶液1,观察到在罐外壁上几乎无剥离,在内壁上无剥离和在内盖上无剥离。
对于溶液2,观察到在罐外壁上几乎无剥离,在内壁上无剥离和在内盖上无剥离。
对于溶液3,在罐外壁、内壁和内盖上都未观察到剥离。
实施例IV
本实施例说明本发明的润滑剂和表面调节剂对要用其处理的铝罐的水沥干特性。
将铝罐用酸性清洁剂(先用Ridoline 125 CO,接着用Alodine 404处理,或仅用Ridoline 125 CO处理)或用碱性清洁剂溶液(Ridoline3060/306方法)处理,所有产品都购自Parker Amchem Division,HenkelCorporation,Madison Heights,MI。然后用含有约0.3wt%的本发明润滑剂和表面调节剂的去离子水溶液漂洗。使如此处理的罐沥干至多30秒后,测定残留于铝罐上的水量。在不使用润滑剂和表面调节剂下进行相同的实验结果概列于表3中。
表3
沥干时间,秒 | 残留水量,每个罐的克数 | |
用DI水处理 | 用0.3%的调节剂处理 | |
6 | 2.4-3.0 | 未测定 |
12 | 2.1-3.5 | 2.8 |
18 | 2.2-3.5 | 2.3 |
30 | 1.8-3.4 | 2.3 |
已发现存在的润滑剂和表面调节剂造成水从罐中更均匀地沥干,并使罐更长时间地保持无“水膜残迹”。
实施例V
本实施例说明烘箱干燥温度对罐壁强度的影响。本试验是提供测量罐弯曲时的压力测定柱强度的质量控制压缩试验。结果概列于表4中。
表4
烘箱温度(°F) | 柱强度(PSI) |
440 | 86.25 |
400 | 87.75 |
380 | 88.25 |
360 | 89.25 |
从表4可以看出,烘箱干燥温度380°F时柱强度试验中获得的获得的值比440°F烘箱温度获得的值增加2psi。
较高的柱强度试验结果是优选的且通常是希望的,原因在于最终罐的薄壁必须在罐装入碳酸溶液后承受从罐内施加的压力。否则,具有低强度壁的罐将膨胀和变形或会容易破裂或甚至爆炸。已发现,因其中存在本发明的润滑剂和表面调节剂组合物带来的更快水膜沥干可使烘箱温度降低,最终获得较高的柱强度结果。更具体地,为了获得足够干燥的漂洗罐,可使罐在进入烘箱前很快沥干。罐在烘箱中停留的时间通常为2至3分钟(在某种程度上取决于线速度、烘箱长度和烘箱温度)。为在此时间范围内获得足够干燥的罐,烘箱的温度通常为约440°F。然而,在其中漂洗水含有约0.3wt%的本发明润滑剂和表面调节剂的一系列试验中,已发现烘箱温度降低至400°F时可获得满意的干燥罐,同时烘箱温度降低至370°F时,仍能获得干燥罐。
实施例组VI
将购自工业罐生产厂的未清洗的铝罐在实施例类型A中用购自ParkerAmchem Division,Henkel Corporation,Madison Heights,Michigan的碱清洁剂,采用Ridoline3060/306方法清洗,在实施例类型B中用购自同一公司的Ridoline 125 CO酸性清洁剂清洗。随后初步漂洗和在最后干燥前,将清洗过的罐用包括在去离子水中的约1wt%的活性有机物(I)(在下表5中具体给出)的润滑剂和表面调节剂处理。在另一组实施例中,随后初步漂洗和最后干燥前,将清洗过的罐用包括在去离子水中的约1wt%的活性有机物(I)和约2g/l(0.2wt%)的无机物(II)(在下表5中具体给出)的反应性润滑剂和表面调节剂处理。在又一组实施例中,随后初步漂洗和最后干燥前,将清洗过的罐用包括在去离子水中的约1wt%的活性有机物(I)和约0.5wt%的表面活性剂(III)(在下表5中具体给出)的润滑剂和表面调节剂处理。在再一类实施例中,随后初步漂洗和最后干燥前,将清洗过的罐用在去离子水中包括约1wt%的活性有机物(I)、约0.2wt%的无机物质(II)和约0.5wt%的表面活性剂(III)(在下表5中具体给出)的润滑剂和表面调节剂处理。
表5
实施例类型 | 活性有机物商品名 | (I)描述 | 无机物(II) | 表面活性剂(III) | pH | 干燥后的静摩擦系数 |
A | Emery 657 | 辛酸 | Al2(SO4)3 | IGEPAL CO-877 | 2.2 | 小于1.5 |
B | Emery 659 | 癸酸 | H2ZrF6 | TRITON X-101 | 2.2 | ″ |
A | Emery 651 | 月桂酸 | FeF3 | NEODOL25-5-3 | 2.3 | ″ |
B | Emery 655 | 肉豆蔻酸 | SnCl4 | TERGITOL TMN-6 | 2.3 | ″ |
A | Emersol 143 | 棕榈酸91% | Ce(NO3)4 | TRITON DF-16 | 2.6 | ″ |
BA | Emersol 153 NF | 硬脂酸92% | H2TiF6 | TRYCOL6720 | 2.6 | ″ |
Emersol 871 | 异硬脂酸 | H2HfF6 | ANTAROXLF-330 | 2.6 | ″ | |
B | Emersol 6313 NF | 油酸75% | (NH4)2ZrF6 | TRITON H-55 | 1.6 | ″ |
A | Empol 1014 | 二聚酸95% | Fe2(SO3)4 | TRITON H-66 | 2.6 | ″ |
B | Emery 1110 | 壬二酸 | Al(NO3)3 | TRITON QS-44 | 2.6 | ″ |
B | Ethox MI5 | 乙氧基化的异硬脂酸 | TiCl4 | TRYCOL 6720 | 3.0 | ″ |
A | Emulphor VN 430 | 聚氧乙基化的油酸 | CeI3 | SURFONIC LF-17 | 3.0 | ″ |
B | Ethox MO5 | 聚氧乙基化的油酸 | FeF3 | LOMAR D | 3.0 | ″ |
A | Monamide 150 LW | 月桂酸链烷醇酰胺 | FeCl3 | DOWFAX 2A1 | 2.0 | ″ |
B | Monamide 150MW | 肉豆蔻酸链烷醇酰胺 | FeBr3 | DYASULF 9268-A | 3.0 | ″ |
A | Monamide 150 IS | 异硬脂酸链烷醇酰胺 | H2ZrF6 | DYASULF C-70 | 4.0 | ″ |
B | Monamide 718 | 硬脂酸链烷醇酰胺 | H2TiF6 | IGEPALCO-887 | 5.0 | ″ |
A | GafacBH 650 | 脂族磷酸酯,酸形式 | Fe(NO3)3 | POLYTERGENTSLF-18 | 2.0 | ″ |
B | Ethox PP16 | 芳族磷酸酯 | (NH4)2ZrF6 | PLURONIC L-61 | 3.0 | ″ |
A | Gafac BL 750 | 脂族磷酸酯,酸形式 | TaF3 | TETRONIC 701 | 6.0 | ″ |
B | Gafac PE510 | 芳族磷酸酯,酸形式 | NbF3 | PLURONIC 31R1 | 5.0 | ″ |
A | Ethfac 142W | 脂族磷酸酯 | H2ZrF6 | PLURONIC 150R1 | 4.0 | ″ |
B | Gafac RA 600 | 脂族磷酸酯,酸形式 | (NH4)2MoF6 | APG 300 | 6.0 | ″ |
A | Armeen Z | N-椰子基-B-氨基丁酸 | H2TiF6 | TRITON CF-21 | 6.0 | ″ |
表5(续)
实施例类型 | 活性有机物商品名 | 描述 | 无机物(II) | 表面活性剂(III) | pH | 干燥后的静摩擦系数 |
B | Hamposy L | 月桂酰基肌氨酸 | VF4 | TRITON DF-18 | 5.0 | ″ |
A | Hamposy C | 椰子酰基肌氨酸 | FeF4 | TRITON GR-7M | 4.0 | ″ |
B | Hamposy O | 油酰基肌氨酸 | SnCL4 | TRITON H-55 | 3.0 | ″ |
A | Hamposy S | 硬脂酰基肌氨酸 | Al2(SO4)3 | TRITON X-100 | 2.0 | ″ |
B | Acusol 410N | 聚丙烯酸,钠盐 | H2ZrF6 | TRITON X-120 | 4.0 | ″ |
A | Neodol 91-2.5 | C9-C11个碳原子/2.5个乙氧基化物 | H2ZrF6 | IGEPAL CO-430 | 6.0 | ″ |
B | Neodol 25-12 | C12-C15个碳原子/12个乙氧基化物 | FeF3 | IGEPAL CO-510 | 5.0 | ″ |
A | Neodol 45-7 | C14-C15个碳原子/7个乙氧基化物 | Ce(NO3)3 | IGEPAL CO-710 | 4.0 | ″ |
B | Triton GR-5M | 硫代丁二酸二辛酯 | Al(NO3)3 | TRYCOL 5882 | 6.0 | ″ |
A | Avanl S70 | 烷基醚磺酸钠 | VOSO4 | TRYCOL 5887 | 5.0 | ″ |
B | Igepon TC-42 | N-椰子和N-甲基牛磺酸钠 | VF3 | TRYCOL 5964 | 4.0 | ″ |
A | Igepon TK-32 | N-甲基-N-妥尔 | VF3 | IGEPAL CO-887 | 3.0 | ″ |
油酸牛磺酸钠 | ||||||
B | Neodol 25-3A | 磺化线型醇,铵盐 | (NH4)2WO4 | IGEPAL CO-630 | 3.0 | ″ |
A | Aromox C/12 | 双(2-羟乙基)可可胺氧化物 | (NH4)2ZrF6 | NEODOL 25-3 | 3.0 | ″ |
B | Aromox DMC | 二甲基可可胺氧化物 | FeF3 | NEODOL 25-35 | 3.0 | ″ |
A | Ethoquad 0/12 | 油酰[POE(15)]氯化铵 | Fe2(SO4)3 | NEODOL 25-9 | 2.0 | ″ |
B | Ethoquad C/12 | 椰子甲基[POE(2)]氯化铵 | Al2(SO4)3 | NEODOL 91-25 | 3.0 | ″ |
A | Ethoquad 18/5 | 十八烷基[POE(15)]氯化铵 | Sn(S(O4) | TRITON Q5-15 | 3.0 | ″ |
B | Propoquad T/12 | 动物脂烷基-甲基-双-(2-羟基-2-甲基乙基)甲基硫酸氨 | Ce2(SO4)3 | TRITON DF-12 | 2.0 | ″ |
A | Ethfac 136 | 磷酸酯 | H2ZrF6 | IGEPAL 10-887 | 2.3 | ″ |
B | Ethox 2684 | 磷酸酯 | H2ZrF6 | IGEPAL CO-887 | 2.7 | ″ |
A | Trylox 5922 | 乙氧基化的氢化蓖麻油 | H2ZrF6 | IGEPAL CO-887 | 2.3 | ″ |
表5(续)
实施例类型 | 活性有机物商品名 | 描述 | 无机物(II) | 表面活性剂(III) | pH | 干燥后的静摩擦系数 |
B | Trylox 5921 | 乙氧基化的氢化蓖麻油 | H2TiF6 | IGEPAL CO-887 | 2.7 | ″ |
A | Trylox 5925 | ″ | H2ZrF6 | TRITON H-66 | 2.7 | ″ |
实施例和比较例组VII
制备两种不同表面活性剂的混合物。第一种由比例111∶156的SURFONICTM LF-17和TRITONTM N-101组成。第二种由比例201∶64.5∶64.5的EMULSOGENTM TP-2144、TRYOLTMLF-1和ANTAROX LF-330组成。除TRITONTM(它是壬基苯酚乙氧基化物)和EMULSOGENTM(它是乙氧基化的松香,因此含有菲环结构)外,所有这些商品表面活性剂都是烷基苯酚。
将约0.2%的各表面活性剂混合物以在铝罐常规酸清洁剂中的用量分别进入硫酸和氢氟酸水溶液中,这些酸-表面活性剂混合物在上表A中定义的步骤2中用作基础处理液。为了模拟配制在通常持续使用的处理大量铝罐中出现的含润滑剂和铝的物质,在这些清洗组合物中还加入(i)2g/L由30份DTITM 5600M3铜润滑剂、37份DTITM 5600WB冷却剂和33份MobilTM629水压润滑剂组成的润滑剂混合物(在上述牌号中包括字母“DTI”的产品购自Diversified Technology Inc. San Antonio,Texas,USA)和(ii)足够量铝酸钠,相当于1980份/1,000,000化学计量当量的铝。为进一步模拟持续操作,表A中定义的步骤3在自来水中含有5%(体积)的清洁剂溶液作为其处理液,而在某些实验中,表A中定义的步骤4(其中处理液主要为FIXO-DINE 500)用0.25或1.0%的清洁剂浴“污染”,在其它实验中,步骤4的处理液无任何清洁剂浴。(通过大量实验证实,平衡时通过加入较少污染溶液定期溢流的处理液除了它通常有意加入的组分外,还含有约5%(体积)的来自前一处理步骤的处理液。步骤2和3的处理液通常定期溢流,而步骤4的处理液一般不溢流。因此步骤4的处理液比预期夹带5%的步骤3的处理液变得更污染,这相当于0.25%的步骤2的处理液。)
在所有这些实验中,观察到当使用含第二种表面活性剂混合物的酸清洗溶液时,步骤4的浴液出现淤渣,但当使用含第一种表面活性剂混合物的酸清洗溶液时,保持无淤渣。
实施例和比较例组VIII
这些实施例和比较例在装置中的实际工业清洗线上进行,其中要清洗的主要原料是DTITM 5600 M3铜润滑剂、DTITM 5600 WB冷却剂和MobilTM629。在本发明这一组中的优选实施例中用于步骤2的清洁剂(当新配制时)由450份66°Baume浓度的硫酸水溶液、93份TRITONTM DF-16(购自Union Carbide Corp.,据报告其HLB值为11.6,由乙氧基化和末端丙氧基化的在醇残基中具有8至10个碳原子的线型醇分子组成)、7份PLURAFACTM D-25(购自BASF Corp.,据报告其HLB值为10.0,由与上述TRITONTM DF-16相同类型的分子构成,但在醇残基中有10至16个碳原子)和450份水组成。步骤4的处理液新配制时为FIXODINE 500。
将这些处理液在按常规溢流和补充各种处理液下在实际清洗1400个铝罐/小时中连续运转7个月(除了偶尔可因设备故障或定期维护可能希望短时间停车外,据信这些时间每月不多于3天)。步骤2的处理液保持140±2°F,步骤4的处理液保持110±1°F。
在该操作中,步骤2中的游离酸和“反应产品”的间隔浓度按ParkerAmchem Technical Process Bulletin No.971,Revision of April 19,1989中的描述测量,步骤4中的游离酸和“反应产品”的间隔浓度按ParkerAmchem Technical Process Bulletin No.1373,Revision of September22,1994中的描述测量。已知通过反应产品值乘以90(对于步骤2)和乘以18(对于步骤4)得到的溶解的铝的浓度(以在每1,000,000份步骤2和步骤4的处理液中的份数表示)为±10%(体积)。TRITONTM DF-16(以下简称为“DF-16”)和PLURAFACTM D-25(以下简称为“D-25”)表面活性剂的浓度通过假定所有游离酸度来自新配制的步骤2处理液完全电离且表面活性剂以与新配制的步骤2的处理液相同的与硫酸的比例存在,由游离酸值计算。一些更适当的值在下表6中给出。在所有这些情况下,步骤4的处理液在液体悬浮液中或泡沫层上面保持无任何可辨认的淤渣,该悬浮液或泡沫层通常在步骤4处理液罐稳定状态运转过程中存在。
表6
特性 | 经如下运转天数后的特性值 | |||||
9 | 71 | 105 | 169 | 204 | 224 | |
对于步骤2 | ||||||
游离酸点 | 16 | 14 | 14 | 14 | 14 | 14 |
溶解的Al+3的ppm | 1080 | 990 | 900 | 1260 | 990 | 990 |
DF-16,g/L | 1.74 | 1.52 | 1.52 | 1.52 | 1.52 | 1.52 |
D-25,g/L | 0.13 | 0.11 | 0.11 | 0.11 | 0.11 | 0.11 |
对于步骤4 | ||||||
pH | 2.6 | 2.7 | 2.7 | 2.6 | 2.6 | 2.6 |
游离酸点 | n.m. | 1.0 | 1.0 | 1.2 | 1.5 | 1.5 |
溶解的Al+3的ppm | n.m. | 252 | 72 | 284 | 306 | 306 |
6个步骤后无水膜残迹的罐的% | ||||||
在外表面上 | 100 | 100 | 100 | 100 | 100 | 100 |
在内表面上 | 90 | 100 | 100 | 100 | 100 | 100 |
与此相反,在其它类似的其中步骤2的处理液含有包括菲环结构的乙氧基化松香酸基表面活性剂的生产操作中,观察到在步骤4的处理液罐的泡沫层上面累积固体淤渣。淤渣由此偶尔分散入加工线中的各种其它处理液中,且当如此分散的淤渣经常转移入处理过的罐的表面时,造成后面涂布的漆完全覆盖罐表面失败。这种完全覆盖的失败希望将上述罐报废,同时它们经常出现足够多,因此希望进行校正测量以保持加工操作的工业经济可行性。
Claims (20)
1.一种方法,包括步骤:(I)用包括表面活性剂组分的含水酸性清洗溶液清洗铝罐,和(II)在步骤(I)后将铝罐与不同于所述含水酸性清洗溶液的含水润滑剂和表面调节剂形成组合物接触,所述含水润滑剂和表面调节剂包括其中溶解、分散、或溶解并分散的组分(i)选自磷酸酯,醇,包括单-、二-、三-和多元酸的脂肪酸,包括盐、羟基酸、酰胺、酯、醚和其衍生物的脂肪酸衍生物,及其混合物的水溶性有机物和(ii)至少一种选自金属态或离子态锆、钛、铈、铝、铁、锡、钒、钽、铌、钼、钨和铪的元素,其中改进包括使用菲环部分的碳原子不超过总碳原子0.1%的含水酸性清洗溶液和菲环部分的碳原子不超过总碳原子0.01%的含水润滑剂和表面调节剂形成组合物。
2.根据权利要求1的方法,其中含水酸性清洗溶液基本上由如下组分组成:(A)非离子表面活性剂组分,选自符合如下化学式的表面活性剂:其中a为0或1;R代表烷基部分,它可以是支化或非支化的和饱和或不饱和的但不包括任何芳基,且R中的碳原子之和为10-22;n为2至4的整数,且在相同分子中可以是相互不同的CnH2nO基团;b为整数,选取的b的数值应使总组分的亲水-亲油平衡(HLB)值为,优选性随所给顺序增加,约8至约20;和(B)非离子表面活性剂组分,选自符合化学式R′-Ф-(CnH2nO)cH的表面活性剂,其中R′代表烷基部分,它可以是支化或非支化的和饱和或不饱和的但不包括任何芳基,且具有4-16个碳原子;Ф代表亚苯基;n的含义与上述式(I)中的相同;c为整数,选取的c的数值应使总组分的HLB值为约9至约21。
3.根据权利要求2的方法,其中R中的碳原子数之和为12至20;n为2或3;选取的b的数值应使组分(A)的HLB值为约10至约18;R′具有4-16个碳原子;选取的c的数值应使组分(B)的HLB值为约10.6至约19;和组分(A)与组分(B)的比例为约0.1至约10。
4.根据权利要求3的方法,其中选取的b的数值应使组分(A)的HLB值为约10.5至约16;选取的c的数值应使组分(B)的HLB值为约11.2至约15;和组分(A)与组分(B)的比例为约0.2至约5。
5.根据权利要求4的方法,其中选取的b的数值应使组分(A)的HLB值为约11.0至约15;选取的c的数值应使组分(B)的HLB值为约11.7至约14.7;和组分(A)与组分(B)的比例为约0.3至约4。
6.根据权利要求5的方法,其中选取的b的数值应使组分(A)的HLB值为约11.3至约15;选取的c的数值应使组分(B)的HLB值为约12.2至约14.5;和组分(A)与组分(B)的比例为约0.4至约3。
7.根据权利要求6的方法,选取的b的数值应使组分(A)的HLB值为约11.5至约14;R′具有8-10个碳原子;选取的c的数值应使组分(B)的HLB值为约12.5至约14.3;和组分(A)与组分(B)的比例为约0.5至约2。
8.根据权利要求7的方法,其中R中的碳原子数之和为14至18;选取的b的数值应使组分(A)的HLB值为约11.7至约13.7;选取的c的数值应使组分(B)的HLB值为约12.7至约14.1;和组分(A)与组分(B)的比例为约0.5至约1.5。
9.根据权利要求8的方法,其中选取的b的数值应使组分(A)的HLB值为约11.8至约13.5;选取的c的数值应使组分(B)的HLB值为约12.9至约13.9;和组分(A)与组分(B)的比例为约0.55至约1.2。
10.根据权利要求9的方法,其中选取的b的数值应使组分(A)的HLB值为约11.9至约13.3;选取的c的数值应使组分(B)的HLB值为约13.0至约13.8;和组分(A)与组分(B)的比例为约0.60至约1.0。
11.根据权利要求10的方法,其中选取的b的数值应使组分(A)的HLB值为约12.0至约13.1;选取的c的数值应使组分(B)的HLB值为约13.1至约13.7;和组分(A)与组分(B)的比例为约0.62至约0.9。
12.根据权利要求11的方法,其中选取的b的数值应使组分(A)的HLB值为约12.1至约12.9;选取的c的数值应使组分(B)的HLB值为约13.2至约13.7;和组分(A)与组分(B)的比例为约0.64至约0.85。
13.根据权利要求12的方法,其中选取的b的数值应使组分(A)的HLB值为约12.1至约12.8;选取的c的数值应使组分(B)的HLB值为约13.3至约13.6;和组分(A)与组分(B)的比例为约0.66至约0.83。
14.根据权利要求13的方法,其中选取的b的数值应使组分(A)的HLB值为约12.1至约12.7,组分(A)与组分(B)的比例为约0.67至约0.80。
15.根据权利要求14的方法,其中选取的b的数值应使组分(A)的HLB值为约12.1至约12.6,组分(A)与组分(B)的比例为约0.68至约0.79。
16.根据权利要求15的方法,其中选取的b的数值应使组分(A)的HLB值为约12.1至约12.5,组分(A)与组分(B)的比例为约0.69至约0.78。
17.根据权利要求16的方法,其中R′具有9个碳原子;选取的b的数值应使组分(A)的HLB值为约12.1至约12.4;和组分(A)与组分(B)的比例为约0.70至约0.77。
18.根据权利要求17的方法,其中选取的b的数值应使组分(A)的HLB值为约12.1至约12.3,组分(A)与组分(B)的比例为约0.71至约0.76。
19.根据权利要求18的方法,其中组分(A)与组分(B)的比例为约0.71至约0.76。
20.根据权利要求19的方法,其中组分(A)与组分(B)的比例为约0.71至约0.73。
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US08/362,687 | 1994-12-22 | ||
US08/362,687 US5584943A (en) | 1987-06-01 | 1994-12-22 | Cleaning and surface conditioning of formed metal surfaces |
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US (1) | US5584943A (zh) |
EP (1) | EP0799293A4 (zh) |
CN (1) | CN1088469C (zh) |
AU (1) | AU695501B2 (zh) |
BR (1) | BR9510244A (zh) |
CA (1) | CA2208429A1 (zh) |
MX (1) | MX9703638A (zh) |
PL (1) | PL320914A1 (zh) |
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CN1068903C (zh) * | 1995-12-01 | 2001-07-25 | 亨凯尔公司 | 转化型涂布的金属表面用润滑剂和表面调整剂 |
WO1997023588A1 (en) * | 1995-12-22 | 1997-07-03 | Henkel Corporation | Acid cleaning/deoxidizing aluminum and titanium without substantial etching |
JPH10182916A (ja) * | 1996-10-21 | 1998-07-07 | Nippon Paint Co Ltd | N複素環を含むアクリル樹脂含有金属表面処理組成物、処理方法及び処理金属材料 |
JP4303365B2 (ja) * | 1998-07-30 | 2009-07-29 | 日本ペイント株式会社 | アルミニウム系金属の洗浄水溶液およびその洗浄方法 |
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AUPQ633300A0 (en) | 2000-03-20 | 2000-04-15 | Commonwealth Scientific And Industrial Research Organisation | Process and solution for providing a conversion coating on a metallic surface ii |
AUPQ633200A0 (en) | 2000-03-20 | 2000-04-15 | Commonwealth Scientific And Industrial Research Organisation | Process and solution for providing a conversion coating on a metallic surface I |
US6544349B1 (en) * | 2000-11-16 | 2003-04-08 | The Fanning Corporation | Method for in situ cleaning of machine components |
US7226696B2 (en) * | 2002-02-27 | 2007-06-05 | Rayovac Corporation | Alkaline cell with performance enhancing additives |
US6872489B2 (en) * | 2002-02-27 | 2005-03-29 | Rovcal, Inc. | Alkaline cell with gassing inhibitors |
US20040147422A1 (en) * | 2003-01-23 | 2004-07-29 | Hatch Andrew M. | Cleaner composition for formed metal articles |
CN101434890B (zh) * | 2007-11-16 | 2011-03-02 | 比亚迪股份有限公司 | 一种水溶性清洗剂组合物 |
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1994
- 1994-12-22 US US08/362,687 patent/US5584943A/en not_active Expired - Fee Related
-
1995
- 1995-12-20 EP EP95943725A patent/EP0799293A4/en not_active Withdrawn
- 1995-12-20 PL PL95320914A patent/PL320914A1/xx unknown
- 1995-12-20 MX MX9703638A patent/MX9703638A/es unknown
- 1995-12-20 BR BR9510244A patent/BR9510244A/pt not_active Application Discontinuation
- 1995-12-20 CA CA002208429A patent/CA2208429A1/en not_active Abandoned
- 1995-12-20 AU AU45129/96A patent/AU695501B2/en not_active Ceased
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Cited By (1)
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CN102330106A (zh) * | 2011-09-01 | 2012-01-25 | 华阳新兴科技(天津)集团有限公司 | 一种环保型清洗切水剂及其制备方法及所用的置换剂 |
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CA2208429A1 (en) | 1996-06-27 |
MX9703638A (es) | 1997-08-30 |
PL320914A1 (en) | 1997-11-10 |
WO1996019553A1 (en) | 1996-06-27 |
AU695501B2 (en) | 1998-08-13 |
EP0799293A1 (en) | 1997-10-08 |
AU4512996A (en) | 1996-07-10 |
US5584943A (en) | 1996-12-17 |
TW341603B (en) | 1998-10-01 |
CN1088469C (zh) | 2002-07-31 |
BR9510244A (pt) | 1997-11-04 |
EP0799293A4 (en) | 1999-04-28 |
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