CN108350394A - 具有良好储存能力的含水配制剂 - Google Patents
具有良好储存能力的含水配制剂 Download PDFInfo
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- CN108350394A CN108350394A CN201680065859.8A CN201680065859A CN108350394A CN 108350394 A CN108350394 A CN 108350394A CN 201680065859 A CN201680065859 A CN 201680065859A CN 108350394 A CN108350394 A CN 108350394A
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- Prior art keywords
- acid
- aqueous formulation
- hydroxyl
- formulation according
- alkoxylated
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- 239000013011 aqueous formulation Substances 0.000 title claims abstract description 29
- 238000003860 storage Methods 0.000 title description 2
- -1 alkali metal salt Chemical class 0.000 claims abstract description 77
- 150000001875 compounds Chemical class 0.000 claims abstract description 75
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004703 alkoxides Chemical group 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007513 acids Chemical class 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 150000002334 glycols Chemical class 0.000 claims abstract description 7
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 7
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 17
- 229920002873 Polyethylenimine Polymers 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 239000004220 glutamic acid Substances 0.000 claims description 7
- 235000013922 glutamic acid Nutrition 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002156 mixing Methods 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 2
- RMGUNXLDOFELHW-UHFFFAOYSA-N 2-aminoacetic acid;oxalic acid Chemical compound NCC(O)=O.OC(=O)C(O)=O RMGUNXLDOFELHW-UHFFFAOYSA-N 0.000 claims 1
- GURWNTAGBOGUEB-UHFFFAOYSA-N acetic acid;n-ethylethanamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CCNCC GURWNTAGBOGUEB-UHFFFAOYSA-N 0.000 claims 1
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 5
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- 239000007864 aqueous solution Substances 0.000 description 13
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- 230000007797 corrosion Effects 0.000 description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 7
- 239000003599 detergent Substances 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 125000002704 decyl 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])* 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- C11D1/345—Phosphates or phosphites
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Abstract
含水配制剂，其包含：(A)至少一种选自以下的有机络合剂：(A1)氨基聚羧酸的碱金属盐，和(A2)部分或完全被碱中和的每个分子携带至少两个‑CH2‑N(CH2COOH)‑单元的聚合物，(B)至少一种以下酸的至少一种盐：硝酸、硫酸、氨基磺酸、甲磺酸、C1‑C2‑羧酸、C2‑C4‑羟基‑单羧酸、未取代或被羟基取代的C2‑C7‑二羧酸和各自未取代或被羟基取代的C4‑C6‑三羧酸，(C)至少一种选自以下的化合物：(C1)磷酸C2‑C10‑单烷基酯，(C2)任选每个羟基被1‑10个烃氧化物基团烷氧基化的C3‑C10‑炔醇，和(C3)任选每个羟基被1‑10个烃氧化物基团烷氧基化的C4‑C10‑炔二醇，所述含水配制剂的pH值为7.5‑10。
Description
本发明涉及含水配制剂，其包含：
(A)至少一种选自以下的有机络合剂：
(A1)氨基聚羧酸的碱金属盐，和
(A2)部分或完全被碱中和的每个分子携带至少两个-CH2-N(CH2COOH)-单元的聚合物，
(B)至少一种以下酸的至少一种盐：硝酸、硫酸、氨基磺酸、甲磺酸、C1-C2-羧酸、C2-C4-羟基-单羧酸、未取代或被羟基取代的C2-C7-二羧酸和各自未取代或被羟基取代的C4-C6-三羧酸，
(C)至少一种选自以下的化合物：
(C1)磷酸C2-C10-单烷基酯，
(C2)任选每个羟基被1-10个烃氧化物基团烷氧基化的C3-C10-炔醇，和
(C3)任选每个羟基被1-10个烃氧化物基团烷氧基化的C4-C10-炔二醇，
所述含水配制剂的pH值为7.5-10。
氨基聚羧酸酯类型诸如甲基甘氨酸二乙酸(MGDA)和谷氨酸二乙酸(GLDA)和它们相应的碱金属盐的螯合剂为用于碱土金属离子诸如Ca2+和Mg2+的有用的多价螯合剂。许多氨基聚羧酸酯显示良好的生物降解性，因此为环保的。出于该原因，推荐它们并且用于各种目的，诸如硬表面清洁剂。现代硬表面清洁剂可作为即用型溶液和浓缩物供应。即用型溶液的优点在于它们可无需进一步加工步骤诸如稀释而使用。然而，许多水与活性成分一起船运。出于该原因，市场需要享受较低运输成本益处的浓缩物。
氨基羧酸酯类型的螯合剂的浓缩的溶液通常为碱性的。它们对一些类型的金属表面(例如，铝)强腐蚀。最常观察到的腐蚀类型尤其是表面和点状腐蚀。尤其是氨基聚羧酸的碱金属盐和部分酸化或未酸化的携带-CH2-N(CH2COOH)-单元的聚合物的碱金属盐可能对铝表面有害。
WO 2005/103334公开了含有表面活性剂、络合剂和碱性来源例如Na2CO3的稀释的溶液以及它们用于清洁由铝制备的表面和由有色金属和合金(诸如铜、黄铜、青铜、锌和铋)制备的表面。
在WO 2008/138817中，公开了含有抗微生物剂和腐蚀抑配制剂的含有抗微生物剂的配制剂。这样的配制剂以强稀释形式使用，用于医疗器具的消毒。在WO 2014/49633中，测试含磷化合物的强稀释溶液作为腐蚀抑配制剂。
本发明的目的是提供没有内在腐蚀危险可在铝容器中运输的络合剂的碱性溶液。本发明的目的还有提供制备没有内在腐蚀危险可在铝容器中运输的络合剂的碱性溶液的方法。
因此，发现在开头限定的含水配制剂，在下文也称为“本发明配制剂”。本发明配制剂的pH值为7.5-10，优选8.5-10，更优选9-10，甚至更优选9.0-9.5。
本发明配制剂为含水配制剂。在本发明的上下文中，术语含水配制剂不仅指唯一的溶剂为水的溶液而且还指含有至少一种非含水溶剂的配制剂。可能的非含水溶剂需要在环境温度下与水混溶，而没有相分离。实例为乙二醇、1,2-丙二醇和C1-C4-链烷醇，诸如乙醇和异丙醇。在本发明配制剂中，水为主要溶剂，例如至少50％体积，指所有溶剂的总和，优选至少90％体积。最优选，在本发明配制剂中含有仅痕量的或不可检测量的非含水溶剂。
本发明配制剂含有
(A)至少一种有机络合剂，下文中也称为组分(A)或化合物(A)或络合剂(A)，其选自
(A1)氨基聚羧酸的碱金属盐，下文中也称为组分(A1)或化合物(A1)或络合剂(A1)，和
(A2)部分或完全被碱中和的每个分子携带至少两个-CH2-N(CH2COOH)-单元的聚合物。这样的聚合物在下文中也称为“聚合物(A2)”。
碱金属或碱均称为碱金属阳离子，诸如锂、钠、钾、铷和铯和至少两种前述的组合。优选的碱金属为钠和钾以及钠和钾的组合，例如2:1摩尔至10:1。甚至更优选钠。在本发明的上下文中忽略痕量(诸如100ppm或更少重量)的碱土金属或过渡金属诸如Fe(+II)和Fe(+III)。
在本发明的上下文内，氨基聚羧酸(A1)理解为指每个分子具有至少一个叔氨基的次氮基三乙酸和其他有机化合物，如以上提及的，其携带一个或两个可部分或完全被中和的CH2-COOH基团。实例为次氮基三乙酸(NTA)、乙二胺四乙酸(EDTA)、二亚乙基三胺五乙酸(DTPA)、羟乙基乙二胺三乙酸(HEDTA)、谷氨酸二乙酸(GLDA)和甲基甘氨酸二乙酸(MGDA)的碱金属盐。
在本发明的另一实施方案中，氨基聚羧酸(A1)选自每个分子携带至少一个仲氨基的有机化合物，如以上提及的，其具有一个或两个可部分或完全被中和的CH(COOH)-CH2–COOH基团。实例为亚氨基二琥珀酸(IDS)的碱金属盐。
化合物(A1)作为盐使用，这意味着，每个分子至少一个羧酸基团，优选至少两个，甚至更优选每个分子平均多于两个羧酸基团被碱中和。在本发明的一个实施方案中，化合物(A1)被碱(例如钠)完全中。在其他实施方案中，化合物(A1)被碱部分中和，例如，被2.2-2.8当量的NaOH中和的MGDA，或被3.1-3.8当量的NaOH中和的GLDA。
在本发明的一个实施方案中，化合物(A1)选自根据通式(I)的化合物
[R1-CH(COO)-N(CH2-COO)2]M3-xHx (I)
其中
M选自相同或不同的碱金属阳离子，并且为CH2CH2COOM
x为0-0.8，优选0.1-0.75，
R1选自CH2-OH和C1-C4-烷基，例如甲基、异丙基、仲丁基和异丁基，优选甲基。
在本发明的一个实施方案中，化合物(A1)为根据以下通式的化合物
[CH3-CH(COO)-N(CH2-COO)2]M3-xHx
其中
x为0-0.8，优选0.1-0.75，
M选自钾和钠和它们的混合物，优选钠。
在本发明的另一实施方案中，化合物(A1)为选自根据通式(II)的化合物的根据(A1)的化合物
[OOC-CH2CH2C-CH(COO)-N(CH2-COO)2]M4-xHx (II)
其中
M选自相同或不同的碱金属阳离子，优选钾和钠和它们的混合物，甚至更优选钠，
x为0-0.8，优选0.1-0.75。
一些化合物(A1)诸如MGDA和GLDA可以两种不同的对映异构体形式存在。在这样的实施方案中，化合物(A1)可选自相应的外消旋混合物和对映异构纯的化合物，优选相应的L-异构体和富集对映体的混合物，其中优选L-对映异构体占优势，例如对映异构过量10-95％的混合物。
在本发明的一个实施方案中，化合物(A)选自聚合物(A2)。每一个CH2-N-(CH2-COOH)-单元在N上携带另外的取代基，例如另一个亚甲基或另一个CH2COOH-基团。
在一个优选的实施方案中，聚合物(A2)选自部分或完全被碱金属中和的聚胺，其中N原子部分或完全被CH2COOH基团取代。
在聚合物(A2)的上下文中，术语“聚胺”指每个重复单元含有至少一个氨基的聚合物和共聚物。所述氨基可选自NH2基团、NH基团并优选叔氨基。在聚合物(B2)中，优选叔氨基，由于碱性聚胺已被转化为羧甲基衍生物，并且N原子完全或优选部分(例如50-95摩尔％，优选70-90摩尔％)被CH2COOH基团取代，部分或完全被碱金属阳离子中和。在本发明的上下文中，其中在相应的聚乙烯基胺或聚亚烷基亚胺中经历取代的多于95摩尔％至100摩尔％的N原子被CH2COOH基团取代的这样的聚合物(A2)将被认为是被CH2COOH基团完全取代。来自例如聚乙烯基胺或聚亚烷基亚胺的NH2基团每个N原子可被一个或两个CH2COOH基团取代，优选每个N原子被两个CH2COOH基团取代。
在本发明的上下文中，在聚合物(A2)中CH2COOH基团的数量除以CH2COOH基团可能的总数，假定每个NH基团一个CH2COOH基团，每个NH2基团两个CH2COOH基团，将也称为“取代程度”。
取代程度可例如通过测定在转化为CH2COOH-取代的聚合物(A2)之前聚合物(A2)及其相应的聚胺的胺数(胺值)来确定，优选根据ASTMD2074-07。
聚胺的实例为聚乙烯基胺、聚亚烷基聚胺，特别是聚亚烷基亚胺，诸如聚丙烯亚胺和聚乙烯亚胺。
在本发明的上下文内，聚亚烷基聚胺优选理解为指每个分子包含至少6个氮原子和至少五个C2-C10-亚烷基单元，优选C2-C3-亚烷基单元的那些聚合物，例如五亚乙基六胺，特别是每个分子具有6-30个亚乙基单元的聚乙烯亚胺。在本发明的上下文内，聚亚烷基聚胺理解为指通过一种或多种环状亚胺的均聚或共聚，或通过(共)聚合物与至少一种环状亚胺接枝得到的那些聚合材料。实例为与乙烯亚胺接枝的聚乙烯基胺和与乙烯亚胺接枝的聚亚氨基胺。
优选的聚合物(B)为聚亚烷基亚胺，诸如聚乙烯亚胺和聚丙烯亚胺，优选聚乙烯亚胺。聚亚烷基亚胺(诸如聚乙烯亚胺和聚丙烯亚胺)可为线性、基本上线性或支化的。
在本发明的一个实施方案中，聚乙烯亚胺选自高度支化的聚乙烯亚胺。高度支化的聚乙烯亚胺的特征在于它们的高支化程度(DB)。支化程度可例如通过13C-NMR光谱来确定，优选在D2O中，并且如下定义：
DB＝D+T/D+T+L
其中D(树枝)相应于叔氨基的分数，L(线性)相应于仲氨基的分数，T(末端)相应于伯氨基的分数。
在本发明的上下文内，高度支化的聚乙烯亚胺为DB为0.25-0.90的聚乙烯亚胺。
在本发明的一个实施方案中，聚乙烯亚胺选自平均分子量Mw为600-75000g/mol，优选800-25000g/mol的高度支化的聚乙烯亚胺(均聚物)。
在本发明的另一实施方案中，聚乙烯亚胺选自乙烯亚胺的共聚物，诸如乙烯亚胺与乙烯亚胺以外的每个分子具有两个NH2基团的至少一种二胺(例如丙烯亚胺)或与每个分子具有三个NH2基团的至少一种化合物(诸如三聚氰胺)的共聚物。
在本发明的一个实施方案中，聚合物(A2)选自支化的聚乙烯亚胺，部分或完全被CH2COOH基团取代，部分或完全被Na+中和。
在本发明的上下文内，聚合物(A2)以共价修饰的形式使用，尤其是使得总计高达至多100摩尔％，优选总计50-98摩尔％的聚合物(A2)的伯和仲氨基的氮原子已与至少一种羧酸(诸如例如Cl-CH2COOH)或至少一当量的甲醛和一当量的氢氰酸或其盐反应，所述百分数基于在聚合物(A2)中伯和仲氨基的总N原子。在本申请的上下文中，所述反应(修饰)可因此为例如烷基化。最优选，高达至多100摩尔％，优选总计50-99摩尔％的聚合物(A2)的伯和仲氨基的氮原子已与甲醛和氢氰酸(或其盐)反应，例如通过Strecker合成。可形成聚合物(A2)基础的聚亚烷基亚胺的叔氮原子通常不携带CH2COOH基团。
聚合物(A2)可例如平均分子量(Mn)为至少500g/mol；优选，聚合物(A2)的平均分子量为500-1,000,000g/mol，特别优选800-50,000g/mol，例如根据ASTM D2074-07，测定在烷基化前后相应的聚胺的胺数(胺值)，并且计算CH2COOH基团的相应的数量。分子量指相应的过钠盐。
在根据本发明的含水溶液中，聚合物(A2)的CH2COOH基团部分或完全被碱金属阳离子中和。非中和的基团COOH可例如为游离酸。优选90-100摩尔％的聚合物(A2)的CH2COOH基团为中和的形式。
优选聚合物(A2)的经中和的CH2COOH基团被相同的碱金属中和为化合物(A)。
聚合物(A2)的CH2COOH基团可部分或完全被任何类型的碱金属阳离子中和，优选被K+，特别优选被Na+中和。
在本发明的一个实施方案中，聚合物(A2)选自部分或完全羧甲基化的聚乙烯亚胺，完全或部分被碱中和。
本发明配制剂另外含有
(B)至少一种以下酸的至少一种盐：硝酸、硫酸、氨基磺酸、甲磺酸、C1-C2-羧酸、C2-C4-羟基单羧酸、未取代或被羟基取代的C2-C7-二羧酸和各自未取代或被羟基取代的C4-C6-三羧酸。
合适的C1-C2-羧酸的实例为甲酸和乙酸。
合适的C2-C4-羟基单羧酸的实例为羟基乙酸、乳酸(例如L-乳酸、D-乳酸和(D,L)-乳酸)和α-羟基丁酸，优选乳酸。
在未取代或被羟基取代的C2-C7-二羧酸之外，优选未取代或被羟基取代的C3-C6-二羧酸。
未取代或被羟基取代的C2-C7-二羧酸的实例为丙二酸、琥珀酸、谷氨酸、己二酸、庚二酸、苹果酸、酒石酸和至少两种前述的混合物，优选乳酸、琥珀酸、谷氨酸、己二酸和至少两种前述的混合物，特别优选己二酸以及琥珀酸、谷氨酸和己二酸的混合物。
各自未取代或被羟基取代的C4-C6-三羧酸的实例为1,2,3-丙烷三羧酸和柠檬酸，优选柠檬酸。
在本发明的优选实施方案中，化合物(B)选自硝酸、硫酸、氨基磺酸、甲磺酸、甲酸、乙酸、柠檬酸、己二酸、至少两种前述的组合以及琥珀酸、谷氨酸和己二酸的混合物的钠盐和钾盐。
化合物(B)为盐，优选碱金属盐。碱金属或碱均称为碱金属阳离子，诸如锂、钠、钾、铷和铯和至少两种前述的组合。优选的碱金属为钠和钾以及钠和钾的组合，例如2:1摩尔至10:1。甚至更优选钠。在本发明的上下文中忽略痕量(诸如100ppm或更少重量)的碱土金属或过渡金属，诸如Fe(+II)和Fe(+III))。
本发明配制剂另外含有
(C)至少一种化合物，下文中也称为化合物(C)或组分(C)，所述化合物(C)选自
(C1)磷酸C2-C10-单烷基酯，简单来说，下文中也称为化合物(C1)，
(C2)任选每个羟基被1-10个烃氧化物基团烷氧基化的C3-C10-炔醇，简单来说，下文中也称为化合物(C2)，和
(C3)任选每个羟基被1-10个烃氧化物基团烷氧基化的C4-C10-炔二醇，简单来说，下文中也称为化合物(C3)。
在本发明的一个实施方案中，本发明配制剂含有精确地一种化合物(C)，因此一种化合物(C1)或一种化合物(C2)或一种化合物(C3)。在本发明的其他实施方案中，本发明配制剂含有两种或更多种化合物(C)，例如两种或更多种化合物(C1)或两种或更多种化合物(C2)或两种或更多种化合物(C3)。在本发明的又一实施方案中，本发明配制剂含有至少一种化合物(C2)和至少一种化合物(C3)，或者它们含有至少一种化合物(C1)和至少一种化合物(C2)，或者它们含有至少一种化合物(C1)和至少一种化合物(C3)。优选，本发明配制剂含有精确地一种化合物(C)，或者它们含有两种或更多种化合物(C1)或两种或更多种化合物(C2)或两种或更多种化合物(C3)。
化合物(C1)选自根据以下通式的化合物
(MO)2P(＝O)-OR2，
其中R2选自C2-C10-烷基。R2可为例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、正戊基、异戊基、仲戊基、异戊基、正己基、异己基、正庚基、异庚基、正辛基、异辛基、正壬基、异壬基、正癸基、异癸基，优选C6-C10-烷基。
M如上定义。
含有化合物(C1)的许多本发明配制剂具有浑浊或不透明或甚至浆料样外观。不管外观，稳定性和低腐蚀性优良。
在本发明的一个实施方案中，化合物(C2)为根据下式的化合物
HC≡C-CH2-O(-CH2-CHR2-O-)nH (C2)
化合物(C3)为根据下式的化合物：
H(-O-CHR2-CH2)n-O-CH2-C≡C-CH2-O(-CH2-CHR2-O-)mH (C3.1)，
H(-O-CHR2-CH2)n-O-CH2-CH2-C≡C-CH2-CH2-O(-CH2-CHR2-O-)mH(C3.4)，
其中在每一种情况下彼此独立，R2相同或不同，并且选自H和甲基和乙基，优选H和甲基。甚至更优选，R2为甲基。
指数n(适当地，m)彼此独立为0-10的数，优选0-5，甚至更优选1-3。在本发明的上下文中，指数n(适当地，m)为平均值。尤其是在当n(适当地，m)大于3的实施方案中，则指数n(适当地，m)可采用分数值，像例如3.5或4.2。
在本发明的优选实施方案中，化合物(C)选自其中n为1-3并且R2(或所有R2，适当地)为甲基的那些化合物(C2)。在这样的实施方案中，化合物(C2)相应于每摩尔被1-3摩尔环氧丙烷烷氧基化的炔丙醇。
在本发明的另一个优选的实施方案中，化合物(C)选自每个羟基被0-10分子，优选0-5分子，更优选0-3分子的环氧乙烷和/或环氧丙烷烷氧基化的1,4-丁炔二醇。在这样的实施方案中，化合物(C3)相应于每摩尔被1-3摩尔环氧丙烷烷氧基化的1,4-丁炔二醇。
在本发明的一个实施方案中，本发明配制剂含有至少一种组分(A)、组分(B)和组分(C)以外的活性成分。活性成分的实例为至少一种选自阴离子表面活性剂和非离子表面活性剂的表面活性剂。
合适的阴离子表面活性剂的实例为C8-C18-烷基硫酸酯、C8-C18-脂肪醇聚醚硫酸酯、乙氧基化的C4-C12-烷基酚(乙氧基化：1-50摩尔环氧乙烷/摩尔)的硫酸半酯、C12-C18磺基脂肪酸烷基酯例如C12-C18磺基脂肪酸甲酯(此外C12-C18-烷基磺酸和C10-C18-烷基芳基磺酸)的碱金属和铵盐。优选前述化合物的碱金属盐，特别优选钠盐。
合适的阴离子表面活性剂的其他实例为皂，例如硬脂酸(stearoic acid)、油酸、棕榈酸、醚羧酸酯和烷基醚磷酸酯的钠或钾盐。
优选的非离子表面活性剂为烷氧基化的醇、环氧乙烷和环氧丙烷的二嵌段和多嵌段共聚物以及脱水山梨糖醇与环氧乙烷或环氧丙烷的反应产物、烷基多糖苷(APG)、羟烷基混合醚和氧化胺。
烷氧基化的醇和烷氧基化的脂肪醇的优选实例为例如通式(III)的化合物
其中各变量如下定义：
R3选自支化或线性C8-C22-烷基，例如n-C8H17、n-C10H21、n-C12H25、n-C14H29、n-C16H33或n-C18H37，
R4选自C1-C10-烷基，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基或异癸基，
R5相同或不同，并且选自氢和线性C1-C10-烷基，优选在每一种情况下相同并且为乙基，特别优选氢或甲基。
变量e和f为0-300，其中e和f的总和为至少1，优选3-50。优选，e为1-100，f为0-30。
在一种实施方案中，通式(III)的化合物可为嵌段共聚物或无规共聚物，优选嵌段共聚物。
烷氧基化的醇的其他优选的实例为例如通式(IV)的化合物
其中各变量如下定义：
R5相同或不同并且选自氢和线性C1-C0-烷基，优选在每一种情况下相同并且为乙基，特别优选氢或甲基，
R6选自支化或线性C6-C20-烷基，特别是n-C8H17、n-C10H21、n-C12H25、n-C13H27、n-C15H31、n-C14H29、n-C16H33、n-C18H37，
a为0-10的数，优选1-6，
b为1-80的数，优选4-20，
d为0-50的数，优选4-25。
a+b+d的总和优选为5-100，甚至更优选9-50。
羟烷基混合醚的优选实例为通式(V)的化合物
其中各变量如下定义：
R3选自支化或线性C8-C22-烷基，例如iso-C11H23、iso-C13H27、n-C8H17、n-C10H21、n-C12H25、n-C14H29、n-C16H33或n-C18H37，
R5相同或不同，并且选自氢和线性C1-C10-烷基，优选在每一种情况下相同并且为乙基，特别优选氢或甲基，
R6选自C6-C20-烷基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基、异癸基、正十二烷基、正十四烷基、正十六烷基和正十八烷基。
变量e和f为0-300，其中e和f的总和为至少1，优选5-50。优选，e为1-100，f为0-30。
通式(IV)和(V)的化合物可为嵌段共聚物或无规共聚物，优选嵌段共聚物。
其他合适的非离子表面活性剂选自由环氧乙烷和环氧丙烷组成的二嵌段和多嵌段共聚物。其他合适的非离子表面活性剂选自乙氧基化或丙氧基化的脱水山梨糖醇酯。氧化胺或烷基多糖苷，尤其是线性C4-C16-烷基多聚葡萄糖和支化的C8-C14-烷基多糖苷，诸如平均通式(VI)的化合物同样合适。
其中：
R7为C1-C4-烷基，特别是乙基、正丙基或异丙基，
R8为-(CH2)2-R7，
G1选自具有4-6个碳原子的单糖，尤其是选自葡萄糖和木糖，
Y为1.1-4，y为平均数，
非离子表面活性剂的其他实例为通式(VII)和(VIII)的化合物
AO选自环氧乙烷、环氧丙烷和环氧丁烷，
EO为环氧乙烷CH2CH2-O，
R6选自C6-C20-烷基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基、异癸基、正十二烷基、正十四烷基、正十六烷基和正十八烷基，
R9选自支化或线性的C8-C18-烷基，
A3O选自环氧丙烷和环氧丁烷，
w为15-70的数，优选30-50，
w1和w3为1-5的数，和
w2为13-35的数。
还可存在选自前述的两种或更多种不同的非离子表面活性剂的混合物。
在本发明的备选实施方案中，本发明配制剂不含组分(A)、组分(B)和组分(C)以外的活性成分。
在本发明的优选实施方案中，本发明配制剂的总固含量为20-45％，优选30-40％。总固含量包括组分(A)、组分(B)、组分(C)，以及适当地，其他活性成分诸如表面活性剂，但是排除结晶的水。总固含量低于20％的本发明配制剂导致输送太多的水，这是不令人满意的。如果化合物(A1)选自外消旋MGDA，则具有较高总固含量的本发明配制剂容易导致活性成分尤其是化合物(A1)沉积。
在本发明的一个实施方案中，本发明配制剂包含
总计10-45％重量络合剂(A)，优选20-45％，更优选30-45％；
总计1-15％重量盐(B)，优选3-10％，更优选4-8％；
总计0.01-1.5％重量化合物(C)，优选0.05-1％，更优选0.1-0.7％；
百分数指整个含水配制剂。
在其中采用表面活性剂(D)的实施方案中，优选的量为0.5-10％，指整个相应的含水配制剂。
本发明配制剂显示优良的稳定性。尤其是，本发明配制剂显示仅低腐蚀倾向，尤其是对铝。它们可储存在铝鼓或铝容器中，并且它们可在其暴露于相应的本发明配制剂的至少一个表面或一部分表面由铝制成的装置中船运和转移。
本发明的另一方面涉及本发明含水配制剂作为或用于制造清洁剂的用途，下文中也称为本发明用途。
本发明的另一方面涉及制造清洁剂(例如硬表面清洁剂)的方法，所述方法包括将至少一种本发明含水配制剂与水混合。所述混合可在任何温度下实现，但是优选环境温度。1:2至高达1:50范围的稀释因子的稀释是可能的。待加入的水可具有任何温度，例如5-30℃。
在本发明的上下文中，术语“清洁剂”包括用于家庭护理和用于工业或公共机构应用的清洁剂。术语“清洁剂”包括用于洗碗(尤其是手动洗碗和自动洗碗)和洁具清洗的组合物以及用于硬表面清洁的组合物，诸如但不限于用于浴室清洁、厨房清洁、地板清洁、管道除垢、窗户、清洁、汽车清洁包括货车清洁，此外，开放工厂植物清洁、原地清洁、金属清洁、消毒剂清洁、农场清洁、高压清洁的组合物，但是不包括洗衣洗涤剂组合物。
其他成分也可加入到清洁剂尤其是硬表面清洁剂中。这样的其他成分包括但不限于染料、香料、抗微生物剂和分散剂。
本发明的另一方面涉及制造方法，下文中也称为本发明制造方法。本发明制造方法为制造本发明配制剂的方法。优选，通过在一个或多个步骤中将以下物质与水混合来进行本发明制造方法
(A)至少一种选自以下的有机络合剂：
(A1)氨基聚羧酸的碱金属盐，和
(A2)部分或完全被碱中和的每个分子携带至少两个-CH2-N(CH2COOH)-单元的聚合物，
(B)至少一种以下酸的至少一种盐：硝酸、硫酸、氨基磺酸、甲磺酸、C1-C2-羧酸、C2-C4-羟基单羧酸、未取代或被羟基取代的C2-C7-二羧酸和各自未取代或被羟基取代的C4-C6-三羧酸，
(C)至少一种选自以下的化合物：
(C1)磷酸C2-C10-单烷基酯，
(C2)每个羟基被1-10个烃氧化物基团烷氧基化的C3-C10-炔醇，和
(C3)每个羟基被1-10个烃氧化物基团烷氧基化的C4-C10-炔二醇。
本发明制造方法可在任何温度下进行。进行本发明制造方法的优选温度为10-70℃，优选15-45℃。
本发明制造方法可在任何压力下进行，但是优选常压。可以任何顺序来混合各组分。但是，优选向络合剂(A)的含水溶液中加入盐(B)的相应的酸。随后加入其他组分，诸如化合物(C)。用于稀释目的的水可在任何阶段加入。本发明制造方法非常适用于制备本发明含水溶液。
通过工作实施例来进一步说明本发明。
一般性评论：
通过混合以下组分来制备含水溶液：
根据表1，烧杯装料40％重量络合剂(A)的含水溶液。随后，加入盐(B)的相应的酸，直至达到相应的pH值。随后，加入10％水和根据表1量的化合物(C)。视情况而定，得到相应的本发明溶液或相应的对比溶液。
如下实现腐蚀测试：
视情况而定，将100ml量的本发明溶液或对比溶液(在每一种情况下，下文中称为“测试溶液”)放入可密封的塑料烧杯中。将得自德国Rocholl GmbH，74858Aglasterhausen的具有以下性质(99.5％Al，尺寸20mm×50mm×1mm，密度2.7g/cm3)的铝盘用乙酸乙酯清洁，干燥，称重，随后立即放置在测试溶液中，其方式使得其被完全浸没，并且主要表面未与烧杯的底部或壁接触。随后将烧杯放置在55℃的加热室中。
7天后，将铝盘从测试溶液移除，用蒸馏水和海绵彻底清洁，干燥并称重。
如下计算每年的重量损失[mm/年]：
重量损失(mm/年)为测得的重量损失(以G计)乘以365天/年再乘以10，除以2.7g/cm3，2.14cm2表面和7天而标准化。
I.制造本发明配制剂和对比配制剂
使用以下物质：
(A1.1)：(D,L)-MGDA-Na3，作为40％重量含水溶液
(A1.2)：(D,L)-GLDA-Na4，作为40％重量含水溶液
(A1.3)：NTA-Na3，作为40％重量含水溶液
(A1.4)：EDTA-Na4，作为40％重量含水溶液
(A1.5)：DTPA-Na5，作为40％重量含水溶液
(B.1)：柠檬酸，大量，
(B.2)：甲基磺酸，作为70％重量含水溶液
(B.3)：硫酸，作为96％含水溶液
(B.4)：硝酸，作为65％重量含水溶液
(B.5)：乙酸
(B.6)：甲酸
(C1.1)：(MO)2P(＝O)-OC6-C10-烷基和MO-P(＝O)-(OC6-C10-烷基)2，C6-C10-烷基为相应的正烷基的组合
(C2.1)：HC≡C-CH2-O(-PO-)1.3H(PO：环氧丙烷)。N＝1.3指平均值。
作为对比腐蚀抑配制剂，使用以下物质：
制备以下本发明配制剂(AF)和对比配制剂C-(AF)，参见表1。
II.腐蚀测试结果
如以上解释的测定平均铝磨蚀。结果在表1中汇总。它们为2次测试的平均值。
表1：本发明配制剂和对比配制剂的组成和腐蚀测试结果
表1(续)：本发明配制剂和对比配制剂的组成和腐蚀测试结果
表1(续)：本发明配制剂和对比配制剂的组成和腐蚀测试结果
Claims (15)
1.含水配制剂，其包含：
(A)至少一种选自以下的有机络合剂：
(A1)氨基聚羧酸的碱金属盐，和
(A2)部分或完全被碱中和的每个分子携带至少两个-CH2-N(CH2COOH)-单元的聚合物，
(B)至少一种以下酸的至少一种盐：硝酸、硫酸、氨基磺酸、甲磺酸、C1-C2-羧酸、C2-C4-羟基-单羧酸、未取代或被羟基取代的C2-C7-二羧酸和各自未取代或被羟基取代的C4-C6-三羧酸，
(C)至少一种选自以下的化合物：
(C1)磷酸C2-C10-单烷基酯，
(C2)任选每个羟基被1-10个烃氧化物基团烷氧基化的C3-C10-炔醇，和
(C3)任选每个羟基被1-10个烃氧化物基团烷氧基化的C4-C10-炔二醇，
所述含水配制剂的pH值为7.5-10。
2.根据权利要求1的含水配制剂，其中所述配制剂的pH值为8.5-10。
3.根据前述权利要求中任一项的含水配制剂，其中所述配制剂的总固含量为20-45％。
4.根据前述权利要求中任一项的含水配制剂，其中氨基聚羧酸的碱金属盐(A1)选自甲基甘氨酸二乙酸、谷氨酸二乙酸、次氮基三乙酸、乙二胺四乙酸和二乙胺三胺五乙酸的碱金属盐。
5.根据前述权利要求中任一项的含水配制剂，其中聚合物(A2)选自部分或完全羧甲基化的聚乙烯亚胺。
6.根据前述权利要求中任一项的含水配制剂，其中烷氧基化的C3-C10-炔醇(C2)选自每摩尔被1-3摩尔环氧乙烷和/或环氧丙烷烷氧基化的炔丙醇。
7.根据前述权利要求中任一项的含水配制剂，其中烷氧基化的C4-C10-炔二醇选自每个羟基被1-10分子的环氧乙烷和/或环氧丙烷烷氧基化的1,4-丁炔二醇。
8.根据前述权利要求中任一项的含水配制剂，其含有
总计10-45％重量络合剂(A)，
总计1-15％重量盐(B)，
总计0.01-1.5％重量化合物(C)，
百分数指整个含水配制剂。
9.根据前述权利要求中任一项的含水配制剂，其中碱金属选自钠和钾以及它们的混合物。
10.根据前述权利要求中任一项的含水配制剂，其中络合剂(A1)选自根据通式(I)的化合物
[R1-CH(COO)-N(CH2-COO)2]M3-xHx (I)
其中
M选自相同或不同的碱金属阳离子，
x为0-0.8，
R1选自CH2-OH和C1-C4-烷基。
11.根据权利要求1-9中任一项的含水配制剂，其中络合剂(A1)选自根据通式(II)的化合物
[OOC-CH2CH2C-CH(COO)-N(CH2-COO)2]M4-xHx (II)
其中
M选自相同或不同的碱金属阳离子，
x为0-0.8。
12.根据前述权利要求中任一项的含水配制剂，其中该配制剂含有至少一种选自阴离子表面活性剂和非离子表面活性剂的表面活性剂。
13.根据前述权利要求中任一项的含水配制剂作为或用于制造清洁配制剂的用途。
14.制造清洁配制剂的方法，所述方法包括将至少一种含水配制剂根据权利要求1-12中任一项的含水配制剂与水混合。
15.制造根据权利要求1-12中任一项的配制剂的方法，通过在一个或多个步骤中将以下物质与水混合：
(A)至少一种选自以下的有机络合剂：
(A1)氨基聚羧酸的碱金属盐，和
(A2)部分或完全被碱中和的每个分子携带至少两个-CH2-N(CH2COOH)-单元的聚合物，
(B)至少一种以下酸的至少一种盐：硝酸、硫酸、氨基磺酸、甲磺酸、C1-C2-羧酸、C2-C4-羟基-单羧酸、未取代或被羟基取代的C2-C7-二羧酸和各自未取代或被羟基取代的C4-C6-三羧酸，
(C)至少一种选自以下的化合物：
(C1)磷酸C2-C10-单烷基酯，
(C2)任选每个羟基被1-10个烃氧化物基团烷氧基化的C3-C10-炔醇，和
(C3)任选每个羟基被1-10个烃氧化物基团烷氧基化的C4-C10-炔二醇。
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| Application Number | Priority Date | Filing Date | Title |
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| EP15194066 | 2015-11-11 | ||
| EP15194066.5 | 2015-11-11 | ||
| PCT/EP2016/076373 WO2017080880A1 (en) | 2015-11-11 | 2016-11-02 | Aqueous formulations with good storage capabilities |
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| CN108350394A true CN108350394A (zh) | 2018-07-31 |
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| CN201680065859.8A Pending CN108350394A (zh) | 2015-11-11 | 2016-11-02 | 具有良好储存能力的含水配制剂 |
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| US (1) | US10961485B2 (zh) |
| EP (1) | EP3374484A1 (zh) |
| JP (2) | JP2018536740A (zh) |
| CN (1) | CN108350394A (zh) |
| BR (1) | BR112018008729A8 (zh) |
| RU (1) | RU2746881C2 (zh) |
| WO (1) | WO2017080880A1 (zh) |
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| WO2023186679A1 (en) * | 2022-03-30 | 2023-10-05 | Basf Se | Process for making aqueous solutions containing a complexing agent in high concentration |
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| US4578208A (en) * | 1983-05-07 | 1986-03-25 | Henkel Kommanditgesellschaft Auf Aktien | Compositions and processes for cleaning and passivating metals |
| US20040242446A1 (en) * | 2003-06-02 | 2004-12-02 | Samsung Electronics Co., Ltd. | Cleaning agent including a corrosion inhibitor used in a process of forming a semiconductor device |
| US20050205835A1 (en) * | 2004-03-19 | 2005-09-22 | Tamboli Dnyanesh C | Alkaline post-chemical mechanical planarization cleaning compositions |
| US20120048295A1 (en) * | 2009-03-11 | 2012-03-01 | Fujifilm Electronic Materials U.S.A., Inc. | Cleaning formulation for removing residues on surfaces |
| CN103562144A (zh) * | 2011-04-14 | 2014-02-05 | 巴斯夫欧洲公司 | 溶解和/或抑制污垢沉积在系统表面的方法 |
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| DE1816348A1 (de) * | 1968-12-21 | 1970-06-25 | Henkel & Cie Gmbh | Wasch-,Bleich- und Reinigungsmittel |
| CA1275794C (en) * | 1986-02-28 | 1990-11-06 | Christine Perry | Adducts of propargyl alcohol and their use as corrosion inhibitors in acidizing systems |
| US6827795B1 (en) * | 1999-05-26 | 2004-12-07 | Procter & Gamble Company | Detergent composition comprising polymeric suds enhancers which have improved mildness and skin feel |
| US7939601B1 (en) * | 1999-05-26 | 2011-05-10 | Rhodia Inc. | Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants |
| WO2002098549A2 (en) * | 2001-06-04 | 2002-12-12 | Rhodia, Inc. | Compositions of alkanolamine salts of alkyl phosphate esters |
| DE10345801A1 (de) * | 2003-09-30 | 2005-04-14 | Basf Ag | Verfahren zum Beizen metallischer Oberflächen unter Verwendung von alkoxylierten Alkinolen |
| KR20050044085A (ko) * | 2003-11-07 | 2005-05-12 | 삼성전자주식회사 | 집적회로 소자의 세정액 및 그 세정액을 이용한 세정방법 |
| EP1580302A1 (en) | 2004-03-23 | 2005-09-28 | JohnsonDiversey Inc. | Composition and process for cleaning and corrosion inhibition of surfaces of aluminum or colored metals and alloys thereof under alkaline conditions |
| US7241724B2 (en) * | 2005-08-18 | 2007-07-10 | Conopco, Inc. | Personal care compositions comprising alkyl phosphate surfactants and selected auxiliary surfactants |
| WO2008138817A2 (de) | 2007-05-11 | 2008-11-20 | Basf Se | Verfahren und zusammensetzung zur desinfektion von empfindlichen oberflächen |
| RU2339586C1 (ru) * | 2007-08-06 | 2008-11-27 | Виталий Аркадьевич Хуторянский | Способ удаления накипи и защиты от отложений солей и коррозии |
| US20140080748A1 (en) * | 2012-09-20 | 2014-03-20 | The Procter & Gamble Company | Easy rinse detergent compositions comprising isoprenoid-based surfactants |
| EP2901920A4 (en) | 2012-09-25 | 2016-04-20 | Terumo Corp | BIOLOGICAL INFORMATION PROCESSING SYSTEM, BIOLOGICAL INFORMATION MEASURING SYSTEM, CONTROL DEVICE, METHOD FOR CONTROLLING THE SAME, AND RECORDING MEDIUM |
| US20140261567A1 (en) | 2013-03-15 | 2014-09-18 | Ecolab Usa Inc. | Inhibiting corrosion of aluminum on alkaline media by phosphinosuccinate oligomers and mixtures thereof |
| BR112015029557A2 (pt) * | 2013-05-27 | 2020-03-10 | Basf Se | solução aquosa, processo para fabricação de uma solução aquosa, e, uso de uma solução aquosa |
| JP6727233B2 (ja) * | 2015-05-13 | 2020-07-22 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | キレート剤の混合物の作製方法 |
-
2016
- 2016-11-02 US US15/770,241 patent/US10961485B2/en active Active
- 2016-11-02 JP JP2018524437A patent/JP2018536740A/ja active Pending
- 2016-11-02 RU RU2018121332A patent/RU2746881C2/ru not_active Application Discontinuation
- 2016-11-02 EP EP16790976.1A patent/EP3374484A1/en not_active Withdrawn
- 2016-11-02 BR BR112018008729A patent/BR112018008729A8/pt active Search and Examination
- 2016-11-02 CN CN201680065859.8A patent/CN108350394A/zh active Pending
- 2016-11-02 WO PCT/EP2016/076373 patent/WO2017080880A1/en active Application Filing
-
2021
- 2021-10-15 JP JP2021169328A patent/JP2022009170A/ja active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4578208A (en) * | 1983-05-07 | 1986-03-25 | Henkel Kommanditgesellschaft Auf Aktien | Compositions and processes for cleaning and passivating metals |
| US20040242446A1 (en) * | 2003-06-02 | 2004-12-02 | Samsung Electronics Co., Ltd. | Cleaning agent including a corrosion inhibitor used in a process of forming a semiconductor device |
| US20050205835A1 (en) * | 2004-03-19 | 2005-09-22 | Tamboli Dnyanesh C | Alkaline post-chemical mechanical planarization cleaning compositions |
| US20120048295A1 (en) * | 2009-03-11 | 2012-03-01 | Fujifilm Electronic Materials U.S.A., Inc. | Cleaning formulation for removing residues on surfaces |
| CN103562144A (zh) * | 2011-04-14 | 2014-02-05 | 巴斯夫欧洲公司 | 溶解和/或抑制污垢沉积在系统表面的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2018121332A3 (zh) | 2019-12-13 |
| US20180312782A1 (en) | 2018-11-01 |
| JP2018536740A (ja) | 2018-12-13 |
| JP2022009170A (ja) | 2022-01-14 |
| BR112018008729A8 (pt) | 2019-02-26 |
| RU2746881C2 (ru) | 2021-04-21 |
| RU2018121332A (ru) | 2019-12-13 |
| US10961485B2 (en) | 2021-03-30 |
| WO2017080880A1 (en) | 2017-05-18 |
| EP3374484A1 (en) | 2018-09-19 |
| BR112018008729A2 (pt) | 2018-10-30 |
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