CN113966383A - 清洁组合物及其用途 - Google Patents
清洁组合物及其用途 Download PDFInfo
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- CN113966383A CN113966383A CN202080043323.2A CN202080043323A CN113966383A CN 113966383 A CN113966383 A CN 113966383A CN 202080043323 A CN202080043323 A CN 202080043323A CN 113966383 A CN113966383 A CN 113966383A
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- Prior art keywords
- acid
- composition
- composition according
- alkali metal
- salt
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- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 238000004140 cleaning Methods 0.000 title claims abstract description 39
- -1 alkali metal salts Chemical class 0.000 claims abstract description 49
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical class NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical class C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 18
- 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 claims abstract description 17
- 235000004279 alanine Nutrition 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 16
- 239000004471 Glycine Substances 0.000 claims abstract description 11
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 229960003767 alanine Drugs 0.000 claims description 17
- 239000007844 bleaching agent Substances 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
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- 239000007788 liquid Substances 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
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- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims description 2
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- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 claims 1
- 238000004851 dishwashing Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 150000003751 zinc Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 8
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- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
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- 239000002184 metal Substances 0.000 description 7
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
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- 239000011521 glass Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
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- 230000005526 G1 to G0 transition Effects 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
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- 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
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical class [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N sodium azide Substances [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000007885 tablet disintegrant Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical group [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- 229910003319 β-Na2Si2O5 Inorganic materials 0.000 description 1
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- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
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Abstract
本发明涉及清洁组合物,其以10:1至1:10的(A):(B)重量比含有(A)至少一种螯合剂,其选自甲基甘氨酸二乙酸(MGDA)的碱金属盐和谷氨酸二乙酸(GLDA)的碱金属盐和柠檬酸的碱金属盐,(B)甘氨酸或丙氨酸的碱金属盐。
Description
本发明涉及清洁组合物,其以10:1至1:10的(A):(B)重量比含有
(A)至少一种螯合剂,其选自甲基甘氨酸二乙酸(MGDA)的碱金属盐和柠檬酸的碱金属盐,
(B)甘氨酸或丙氨酸或前述至少一种的碱金属或铵盐。
现代清洁组合物需要满足许多要求。它们需要在各种条件,例如各种温度下工作。它们需要产生优异的结果,在硬表面清洁剂,特别是自动洗碗制剂的情况下,它们需要在成斑和成膜方面提供优异的结果。如果要清洁玻璃,需要抑制或至少极大减少玻璃腐蚀。清洁组合物需要环保,并且它们必须甚至在只有所谓“硬水”,例如具有较高的Mg2+和Ca2+盐含量的水的条件下工作。
在WO 94/29421中,公开了环保的螯合剂。在EP 0 783 034A2中,公开了这样的螯合剂应该以尽可能纯的形式使用,并且高量杂质导致储存稳定性降低。
在WO 2013/165234中,建议用甘氨酸替代柠檬酸以增强自动洗碗制剂中的脂肪酶的稳定性。在试验中,甘氨酸充当酶稳定剂。
但是,在后一种情况下,清洁性能仍有改进的空间。
还已经发现,在许多情况下,脂肪残留物积聚在自动洗碗机的油脂过滤器或筛网中。这样的残留物通常含有表面活性剂和从餐具上清除的油脂,或来自污垢的降解产物。残留物的沉积是不利的,因为这些过滤器或筛网在被表面活性剂和油脂填满时需要清洁。此外,这样的脂肪残留物在机器一段时间不用时可能变臭,它们甚至可能变成卫生危害。尽管已经公开了对这一问题的解决方案,参见例如WO 2015/000744和WO 2017/005793,但进一步的解决方案是受欢迎的。
因此本发明的目的是提供具有优异清洁性质,如成斑和成膜的环保清洁组合物。本发明的目的还在于提供这样的洗涤剂组合物的用途,和提供制造方法。
相应地,已经发现了一开始规定的洗涤剂组合物,在下文中也称为本发明的组合物或根据本发明的组合物。
本发明的组合物以10:1至1:10的(A):(B)重量比含有
(A)至少一种螯合剂,下文一般称为螯合剂(A)或简称为(A),其中螯合剂(A)选自甲基甘氨酸二乙酸(MGDA)的碱金属盐和谷氨酸二乙酸(GLDA)的碱金属盐和柠檬酸的碱金属盐,
(B)甘氨酸或丙氨酸或前述至少一种的碱金属或铵盐,下文也简称为(B)–或分别称为甘氨酸(B)或丙氨酸(B)。
下面更详细描述螯合剂(A)和甘氨酸(B)和丙氨酸(B)。
碱金属盐可选自锂钾盐和钠盐及其组合。碱金属阳离子的优选实例是钠和钾和钠钾组合,再更优选在根据通式(I a)和(I b)的化合物中所有M相同并且它们都是Na。这同样准用于柠檬酸的碱金属盐。
优选螯合剂(A)选自GLDA的四钠盐和MGDA的三钠盐和GLDA的三钠盐和柠檬酸的三钠盐和MGDA的二钠盐和柠檬酸的二钠盐及其组合。
例如,整体式为
[CH3-CH(COO)-N(CH2-COO)2]M3-xHx (I a)
其中M选自铵和碱金属阳离子,相同或不同,例如钠、钾的阳离子和前述这些的组合。再更优选在根据通式(I a)的化合物中所有M相同并且它们都是Na,且式(I a)中的x在0至1.0,优选0.015至0.5的范围内。
在式(I b)中
[OOC-CH2CH2-CH(COO)-N(CH2-COO)2]M4-xHx (I b)
M如上文定义,且式(I b)中的x在0至2.0,优选0.015至1.0的范围内。
M已在上文定义。
MGDA及其各自的碱金属盐选自外消旋混合物、D-异构体和L-异构体,和选自非外消旋混合物的D-和L-异构体的混合物。优选地,MGDA及其各自的碱金属盐选自外消旋混合物和含有55至85摩尔%L-异构体且其余是D-异构体的混合物。特别优选的是含有60至80摩尔%L-异构体且其余是D-异构体的混合物。其它特别优选的实施方案是外消旋混合物。
GLDA及其各自的碱金属盐选自外消旋混合物、D-异构体和L-异构体,和选自非外消旋混合物的D-和L-异构体的混合物。优选地,GLDA及其各自的碱金属盐选自外消旋混合物和含有55至99摩尔%L-异构体且其余是D-异构体的混合物。特别优选的是含有60至98.5摩尔%L-异构体且其余是D-异构体的混合物。其它特别优选的实施方案是外消旋混合物。
无论如何,螯合剂(A)可能带有非碱金属的阳离子。次要量,如分别为总MGDA、GLDA或柠檬酸的0.01至5摩尔%,因此可能带有碱土金属阳离子,如Mg2+或Ca2+,或Fe2+或Fe3+阳离子。
在本发明的一个实施方案中,螯合剂(A)可含有可能来自各自螯合剂(A)的合成的一种或多种杂质。在MGDA和GLDA的情况下,这样的杂质可选自丙酸、乳酸、丙氨酸、次氮基三乙酸(NTA)等和它们各自的碱金属盐。在IDS的情况下,这样的杂质可选自马来酸、马来酸/富马酸的单酰胺,和外消旋天冬酰胺。这样的杂质通常以次要量存在。“次要量”在本文中是指相对于螯合剂(A)计总共0.1至5重量%,优选最多2.5重量%。在本发明中,当测定根据本发明的组合物的组成时,这样的次要量忽略不计。
本发明的组合物还含有
(B)选自甘氨酸和丙氨酸或前述至少一种的碱金属或铵盐的氨基酸。
丙氨酸(B)和甘氨酸(B)的优选铵盐选自C1-C4烷基铵盐,如二甲基铵、三甲基铵、乙基铵、二乙基铵、三乙基铵,和ω-羟基-C2-C4亚烷基铵盐,如2-羟乙基铵、N,N-二羟乙基铵和N,N,N-三羟乙基铵。
丙氨酸(B)可作为D,L-丙氨酸或作为对映异构体之一,例如作为L-丙氨酸或D-丙氨酸,或以对映体富集形式,例如作为3:1或10:1摩尔比的L-丙氨酸:D-丙氨酸提供。
在本发明的一个实施方案中,(A)和(B)都是钠盐。
本发明的组合物中的(A):(B)的重量比在10:1至1:10,优选5:1至1:4的范围内。当测定(A):(B)的重量比时,在每种情况下该计算基于游离酸(两性离子)。
在本发明的一个实施方案中,(A)和(B)的总和构成所述组合物的10至50重量%,参考总固含量,优选的是15至35重量%。通过在真空中在80℃下蒸发测定固含量。
在环境温度下,本发明的组合物可以是液体、固体或是糊料或浆料的形式。在一个优选实施方案中,本发明的组合物在环境温度下是液体。
在本发明的一个实施方案中,本发明的组合物是中性或碱性的。例如,本发明的清洁组合物可含有非(A)和(B)的组分。优选的是,本发明的组合物含有至少一种附加组分,例如至少一种表面活性剂、至少一种漂白剂、至少一种(甲基)丙烯酸均聚物或丙烯酸与选自甲基丙烯酸、马来酸、衣康酸和AMPS的至少一种共聚单体的共聚物,或至少一种酶,例如蛋白酶或脂肪酶或淀粉酶。
优选的非离子表面活性剂是烷氧基化醇、环氧乙烷和环氧丙烷的二嵌段和多嵌段共聚物、和山梨糖醇酐与环氧乙烷或环氧丙烷的反应产物、烷基聚糖苷(APG)、羟烷基混合醚和胺氧化物。
烷氧基化醇和烷氧基化脂肪醇的优选实例是例如通式(III)的化合物
其中变量如下定义:
R2相同或不同并选自氢和直链C1-C10烷基,优选在每种情况下相同并且是乙基,特别优选是氢或甲基,
R3选自支链或直链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、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,
变量e和f在0至300的范围内,其中e和f之和为至少1,优选在3至50的范围内。优选地,e在1至100的范围内且f在0至30的范围内。
在一个实施方案中,通式(III)的化合物可以是嵌段共聚物或无规共聚物,优选的是嵌段共聚物。
烷氧基化醇的其它优选实例是例如通式(IV)的化合物
其中变量如下定义:
R2相同或不同并选自氢和直链C1-C4烷基,优选在每种情况下相同并且是乙基,特别优选是氢或甲基,
R5选自支链或直链C6-C20烷基,特别是n-C8H17、n-C10H21、n-C12H25、n-C13H27、n-C15H31、n-C14H29、n-C16H33、n-C18H37,
a是在0至10,优选1至6的范围内的数,
b是在1至80,优选4至20的范围内的数,
d是在0至50,优选4至25的范围内的数。
总和a+b+d优选在5至100的范围内,再更优选在9至50的范围内。
羟烷基混合醚的优选实例是通式(V)的化合物
其中变量如下定义:
R2相同或不同并选自氢和直链C1-C10烷基,优选在每种情况下相同并且是乙基,特别优选是氢或甲基,
R3选自支链或直链C8-C22烷基,例如iso-C11H23、iso-C13H27、n-C8H17、n-C10H21、n-C12H25、n-C14H29、n-C16H33或n-C18H37,
R5选自C6-C20烷基,例如正己基、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m和n在0至300的范围内,其中n和m之和为至少1,优选在5至50的范围内。优选地,m在1至100的范围内且n在0至30的范围内。
通式(IV)和(V)的化合物可以是嵌段共聚物或无规共聚物,优选的是嵌段共聚物。
进一步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。进一步合适的非离子表面活性剂选自乙氧基化或丙氧基化山梨糖醇酐酯。胺氧化物或烷基聚糖苷,尤其是直链C4-C16烷基聚葡萄糖苷和支链C8-C14烷基聚糖苷,如平均通式(VI)的化合物同样合适。
其中:
R6是C1-C4烷基,特别是乙基、正丙基或异丙基,
R7是-(CH2)2-R6,
G1选自具有4至6个碳原子的单糖,尤其选自葡萄糖和木糖,
y在1.1至4的范围内,y是平均数。
非离子表面活性剂的进一步实例是通式(VII)和(VIII)的化合物
AO选自环氧乙烷、环氧丙烷和环氧丁烷,
EO是环氧乙烷、CH2CH2-O,
R8选自支链或直链C8-C18烷基,且R5如上文定义,
A3O选自环氧丙烷和环氧丁烷,
w是在15至70,优选30至50的范围内的数,
w1和w3是在1至5的范围内的数,且
w2是在13至35的范围内的数。
合适的其它非离子表面活性剂的综述可见于EP-A 0 851 023和DE-A 198 19187。
也可存在选自上述这些的两种或更多种不同的非离子表面活性剂的混合物。
可存在的其它表面活性剂选自两性(两性离子)表面活性剂和阴离子表面活性剂及其混合物。
两性表面活性剂的实例是在使用条件下在同一分子中带有正电荷和负电荷的那些。两性表面活性剂的优选实例是所谓的甜菜碱-表面活性剂。甜菜碱-表面活性剂的许多实例带有每分子一个季化氮原子和一个羧酸基团。两性表面活性剂的一个特别优选的实例是椰油酰胺基丙基甜菜碱(月桂酰胺基丙基甜菜碱)。
胺氧化物表面活性剂的实例是通式(IX)的化合物
R9R10R11N→O (IX)
其中R9、R10和R11互相独立地选自脂族、脂环族或C2-C4亚烷基C10-C20烷基酰氨基部分。优选地,R9选自C8-C20烷基或C2-C4亚烷基C10-C20烷基酰氨基且R10和R11都是甲基。
一个特别优选的实例是月桂基二甲基氧化胺,有时也称为月桂胺氧化物。另一特别优选的实例是椰油酰基丙基二甲基氧化胺,有时也称为椰油酰胺基丙基胺氧化物。
合适的阴离子表面活性剂的实例是C8-C18烷基硫酸的碱金属和铵盐、C8-C18脂肪醇聚醚硫酸的碱金属和铵盐、乙氧基化C4-C12烷基酚(乙氧基化:1至50摩尔环氧乙烷/mol)的硫酸半酯的碱金属和铵盐、C12-C18磺基脂肪酸烷基酯,例如C12-C18磺基脂肪酸甲基酯的碱金属和铵盐,还有C12-C18烷基磺酸和C10-C18烷基芳基磺酸的碱金属和铵盐。优选的是上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进一步实例是皂,例如钠或钾的硬脂酸盐、油酸盐、棕榈酸盐、醚羧酸盐和烷基醚磷酸盐。
在本发明的一个实施方案中,本发明的组合物可含有0.1至60重量%的选自阴离子表面活性剂、两性表面活性剂和胺氧化物表面活性剂的至少一种表面活性剂。
在一个优选实施方案中,本发明的组合物含有至少一种阴离子表面活性剂。
本发明的组合物可含有至少一种漂白剂,也称为漂白试剂。漂白剂可选自氯漂白剂和过氧化物漂白剂,且过氧化物漂白剂可选自无机过氧化物漂白剂和有机过氧化物漂白剂。优选的是选自碱金属过碳酸盐、碱金属过硼酸盐和碱金属过硫酸盐的无机过氧化物漂白剂。作为液体的本发明的组合物优选不含有漂白剂和酶。
有机过氧化物漂白剂的实例是有机过羧酸,尤其是有机过羧酸。
在本发明的组合物中,碱金属过碳酸盐,尤其是过碳酸钠,优选以包衣形式使用。这样的包衣可以是有机或无机性质的。实例是甘油、硫酸钠、硅酸盐、碳酸钠和前述至少两种的组合,例如碳酸钠和硫酸钠的组合。
合适的含氯漂白剂是例如1,3-二氯-5,5-二甲基乙内酰脲、N-氯磺酰胺、氯胺T、氯胺B、次氯酸钠、次氯酸钙、次氯酸镁、次氯酸钾、二氯异氰脲酸钾和二氯异氰脲酸钠。
本发明的组合物可包含例如3至10重量%的含氯漂白剂。
本发明的组合物可包含一种或多种漂白催化剂。漂白催化剂可选自增强漂白的过渡金属盐或过渡金属络合物,例如锰-、铁-、钴-、钌-或钼-salen络合物或羰基络合物。锰、铁、钴、钌、钼、钛、钒和铜与含氮的三脚配体的络合物以及钴-、铁-、铜-和钌-胺络合物也可用作漂白催化剂。
本发明的组合物可包含一种或多种漂白活化剂,例如N-甲基吗啉鎓-乙腈盐(“MMA盐”)、三甲基铵乙腈盐,N-酰基酰亚胺,例如N-壬酰基琥珀酰亚胺、1,5-二乙酰基-2,2-二氧代六氢-1,3,5-三嗪(“DADHT”)或腈季铵盐(三甲基铵乙腈盐)。
合适的漂白活化剂的进一步实例是四乙酰乙二胺(TAED)和四乙酰己二胺。
本发明的组合物可包含一种或多种缓蚀剂。在本情况下,这被理解为包括抑制金属腐蚀的那些化合物。合适的缓蚀剂的实例是三唑,特别是苯并三唑、双苯并三唑、氨基三唑、烷基氨基三唑,以及酚衍生物,例如氢醌、邻苯二酚、羟基氢醌、没食子酸、间苯三酚或连苯三酚。
在本发明的一个实施方案中,本发明的清洁剂包含总共0.1至1.5重量%的缓蚀剂。
本发明的组合物可包含一种或多种增洁剂,选自有机和无机增洁剂。合适的无机增洁剂的实例是硫酸钠或碳酸钠或硅酸盐,特别是二硅酸钠和偏硅酸钠、沸石、页硅酸盐,特别是式α-Na2Si2O5、β-Na2Si2O5和δ-Na2Si2O5的那些,以及脂肪酸磺酸盐、α-羟基丙酸、碱金属丙二酸盐、脂肪酸磺酸盐、烷基和烯基二琥珀酸盐、酒石酸二乙酸盐、酒石酸单乙酸盐、氧化淀粉和聚合增洁剂,例如聚羧酸盐和聚天冬氨酸。
有机增洁剂的实例尤其是(C)(甲基)丙烯酸均聚物或丙烯酸与选自甲基丙烯酸、马来酸、衣康酸和AMPS的至少一种共聚单体的共聚物,下文也统称为(共)聚合物(C),和单独分别称为聚合物(C)和共聚物(C),在每种情况下作为游离酸或用碱金属,尤其是用钠部分或完全中和。
在本发明的一个实施方案中,有机增洁剂选自聚羧酸盐,例如(甲基)丙烯酸均聚物或(甲基)丙烯酸共聚物的碱金属盐。
合适的共聚单体的实例是单烯属不饱和二羧酸,如马来酸、富马酸、马来酸酐、衣康酸和柠康酸。合适的聚合物特别是聚丙烯酸,其优选具有2000至40 000g/mol,优选2000至10 000g/mol,特别是3000至8000g/mol的平均分子量Mw。共聚的聚羧酸盐也合适,特别是丙烯酸与甲基丙烯酸的那些和丙烯酸或甲基丙烯酸与马来酸和/或富马酸的那些,并且在相同的分子量范围内。
也有可能使用选自单烯属不饱和C3-C10-单-或C4-C10-二羧酸或其酐,如马来酸、马来酸酐、丙烯酸、甲基丙烯酸、富马酸、衣康酸和柠康酸的至少一种单体与至少一种如下所列的亲水或疏水单体的共聚物。
合适的疏水单体是例如异丁烯、二异丁烯、丁烯、戊烯、己烯和苯乙烯、具有10个或更多个碳原子的烯烃或其混合物,例如1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、1-二十烯、1-二十二烯、1-二十四烯和1-二十六烯、C22-α-烯烃、C20-C24-α-烯烃的混合物和具有每分子平均12至100个碳原子的聚异丁烯。
合适的亲水单体是具有磺酸酯或膦酸酯基团的单体,以及具有羟基官能或环氧烷基团的非离子单体。例如,可以提到:烯丙醇、异戊二烯醇、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、甲氧基聚丁二醇(甲基)丙烯酸酯、甲氧基聚(环氧丙烷-co-环氧乙烷)(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚丙二醇(甲基)丙烯酸酯、乙氧基聚丁二醇(甲基)丙烯酸酯和乙氧基聚(环氧丙烷-co-环氧乙烷)(甲基)丙烯酸酯。聚烷撑二醇在此可包含每分子3至50,特别是5至40,尤其是10至30个环氧烷单元。
在此特别优选的含磺酸基团的单体是1-丙烯酰氨基-1-丙磺酸、2-丙烯酰氨基-2-丙磺酸、2-丙烯酰氨基-2-甲基丙磺酸(AMPS)、2-甲基丙烯酰氨基-2-甲基丙磺酸、3-甲基丙烯酰氨基-2-羟基丙磺酸、烯丙基磺酸、甲基烯丙基磺酸、烯丙氧基苯磺酸、甲基烯丙氧基苯磺酸、2-羟基-3-(2-丙烯氧基)丙磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、乙烯基磺酸、丙烯酸3-磺丙酯、甲基丙烯酸2-磺乙酯、甲基丙烯酸3-磺丙酯、磺甲基丙烯酰胺、磺甲基甲基丙烯酰胺和所述酸的盐,如其钠、钾或铵盐。
特别优选的含膦酸酯基团的单体是乙烯基膦酸及其盐。
有机增洁剂的另一实例是羧甲基菊粉。
此外,也可使用两性聚合物作为增洁剂。
本发明的组合物可包含例如总共10至70重量%,优选最多50重量%的增洁剂。在本发明中,螯合剂(A)不算作增洁剂。
在本发明的一个实施方案中,本发明的组合物可包含一种或多种助增洁剂。
本发明的组合物可包含选自例如硅酮油和石蜡油的一种或多种消泡剂。
在本发明的一个实施方案中,本发明的组合物包含总共0.05至0.5重量%的消泡剂。
本发明的组合物可包含一种或多种酶。酶的实例是脂肪酶、水解酶、淀粉酶、蛋白酶、纤维素酶、酯酶、果胶酶、乳糖酶和过氧化物酶。
在本发明的一个实施方案中,本发明的组合物可包含例如最多5重量%的酶,优选的是0.1至3重量%。所述酶可以例如用至少一种C1-C3-羧酸或C4-C10-二羧酸的钠盐稳定化。优选的是甲酸盐、乙酸盐、己二酸盐和琥珀酸盐。
在本发明的一个实施方案中,本发明的组合物,尤其在用作自动洗碗洗涤剂时,可包含至少一种锌盐。锌盐可选自水溶性和水不溶性锌盐。就此而言,在本发明中,水不溶性用于表示在25℃的蒸馏水中的溶解度为0.1g/l或更低的那些锌盐。在水中的溶解度更高的锌盐因此在本发明中被称为水溶性锌盐。
在本发明的一个实施方案中,锌盐选自苯甲酸锌、葡萄糖酸锌、乳酸锌、甲酸锌、ZnCl2、ZnSO4、乙酸锌、柠檬酸锌、Zn(NO3)2、Zn(CH3SO3)2和没食子酸锌,优选ZnCl2、ZnSO4、乙酸锌、柠檬酸锌、Zn(NO3)2、Zn(CH3SO3)2和没食子酸锌。
在本发明的另一实施方案中,锌盐选自ZnO、ZnO·aq、Zn(OH)2和ZnCO3。优选的是ZnO·aq。
在本发明的一个实施方案中,锌盐选自平均粒径(重均)为10nm至100μm的氧化锌。
锌盐中的阳离子可以络合形式存在,例如与氨配体或水配体络合,特别以水合形式存在。为简化描述,在本发明中,如果配体是水配体,通常省略配体。
根据如何调节本发明的混合物的pH值,锌盐可变。因此,例如有可能使用乙酸锌或ZnCl2制备本发明的制剂,但这在水性环境中在pH 8或9下转化成ZnO、Zn(OH)2或ZnO·aq,其可以非络合或络合形式存在。
锌盐可存在于在室温下为固体的那些本发明的自动洗碗制剂中,其优选以具有例如10nm至100μm,优选100nm至5μm的例如通过X-射线散射测定的平均直径(数均)的粒子形式存在。
锌盐可以溶解或固体或胶体形式存在于在室温下为液体的那些用于家居护理应用的洗涤剂组合物中。
在本发明的一个实施方案中,本发明的自动洗碗制剂包含总共0.05至0.4重量%的锌盐,在每种情况下基于所涉组合物的固含量计。
在此,锌盐的分数作为锌或锌离子给出。有可能由此计算抗衡离子分数。
在本发明的一个实施方案中,本发明的自动洗碗制剂含有聚烯亚胺,例如聚丙烯亚胺或聚乙烯亚胺。聚烯亚胺可例如被CH2COOH基团或被聚环氧烷链取代,或未取代。在本发明的一个实施方案中,聚烯亚胺的60至80摩尔%的伯胺和仲胺官能被CH2COOH基团或被环氧乙烷或环氧丙烷取代。特别优选的是未取代的聚乙烯亚胺,其具有500至20,000g/mol的平均分子量Mw,有利地通过在1.5重量%甲酸水溶液作为洗脱剂和交联聚甲基丙烯酸羟乙酯作为固定相中的凝胶渗透色谱法(GPC)测定。在另一些实施方案中,聚乙氧基化聚乙烯亚胺是优选的,其具有2,500至50,000g/mol的平均分子量Mw,有利地通过在1.5重量%甲酸水溶液作为洗脱剂和交联聚甲基丙烯酸羟乙酯作为固定相中的凝胶渗透色谱法(GPC)测定。在另一些实施方案中,聚乙氧基化聚丙烯亚胺是优选的,其具有2,500至50,000g/mol的平均分子量Mw,有利地通过在1.5重量%甲酸水溶液作为洗脱剂和交联聚甲基丙烯酸羟乙酯作为固定相中的凝胶渗透色谱法(GPC)测定。
未取代或如上取代的聚乙烯亚胺和聚丙烯亚胺可少量应用,例如相对于本发明的自动洗碗制剂的总固含量计0.01至2重量%。
在本发明的一个实施方案中,本发明的组合物不含除锌化合物外的重金属。在本发明中,这被理解为是指本发明的组合物不含不充当漂白催化剂的那些重金属化合物,特别是铁和铋的化合物。在本发明中,关于重金属化合物的“不含”被理解为是指不充当漂白催化剂的重金属化合物的含量总共为0至100ppm,通过浸出法测定并基于固含量计。优选地,除锌外,根据本发明的洗涤剂组合物具有基于所涉制剂的固含量计低于0.05ppm的重金属含量。因此不包括锌的分数。
在本发明中,“重金属”被定义为是除锌外的任何具有至少6g/cm3的比密度的金属。特别地,重金属是如铋、铁、铜、铅、锡、镍、镉和铬之类的金属。
优选地,本发明的自动洗碗制剂不含可测得的分数的铋化合物,即例如少于1ppm。
在本发明的一个实施方案中,本发明的组合物包含一种或多种附加成分,如香精、染料、有机溶剂、缓冲剂、片剂崩解剂和/或酸,如甲基磺酸。
本发明的组合物优异地适用于各种清洁剂,例如在硬表面清洁,例如但不限于自动洗碗中,和在洗衣中。它们优异地适用于环保的清洁组合物并提供优异的清洁性质,如甚至在使用硬水时的成斑和成膜。
本发明的另一个方面是一种清洁衣物或硬表面,例如餐具的方法,优选在自动洗碗机中,下文也称为本发明的清洁方法。本发明的清洁方法的特征在于其使用本发明的组合物进行。
术语“硬表面清洁剂”包括用于洗碗,尤其是手动洗碗和自动洗碗和餐具洗涤的组合物,和用于其它硬表面清洁的组合物,例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、车辆清洁,包括卡车清洁,还有开放车间清洁、就地清洗、金属清洁、消毒清洁、农场清洁、高压清洁的组合物,但不是洗衣剂组合物。
下面所用的餐具包括瓷、聚合物、金属、粘土和玻璃器皿。清洁餐具的方法包括除去所有种类的污垢,如脂肪、蛋白质、淀粉、染料等。
更具体地,术语“餐具”包括用于食品的准备、上菜、食用和处置的制品,包括锅、平底锅、托盘、水罐、碗、盘、碟、杯、玻璃杯、叉、刀、勺、刮勺和在机构或家庭厨房或餐厅常见的其它玻璃、金属、陶瓷、塑料复合制品。一般而言,这样的餐具可被称为食品或饮料接触制品,因为它们具有为接触食品和/或饮料提供的表面。当用于这些餐具洗涤应用时,清洁组合物和/或漂洗助剂应该提供有效的剥离(sheeting)作用和低起泡性质。除具有上述理想性质外,对清洁组合物和/或漂洗助剂而言也有用的是可生物降解、环保和通常无毒。这种类型的清洁组合物和/或漂洗助剂可被描述为“食品级”。
本发明的清洁方法在10至90℃的温度下进行。在本发明的清洁方法作为自动洗碗法进行的实施方案中,其优选在45至65℃,更优选50至60℃的温度下进行。所述温度是指在本发明的方法中使用的水的温度。
本发明的方法使用水进行。在本发明的清洁方法作为自动洗碗法进行的实施方案中,水量受所用机器的类型和程序的选择影响。
所用的水可具有在0至25°dH的范围内的德国硬度,被称为永久硬度。
在本发明的清洁方法作为自动洗碗法进行的实施方案中,本发明的清洁方法优选用两种组合物的组合进行,其中一种是本发明的组合物,另一组合物包含至少一种非离子表面活性剂和至少一种选自碱金属硫酸盐和碱金属碳酸(氢)盐的无机盐。
通过实施例进一步例示本发明。
静态CaCO3瓶/结垢试验方法
静态瓶试验在50℃下进行。试验瓶装有50毫升碳酸氢钙溶液,其通过合并钙卤水与碳酸氢盐水溶液而原位形成并对应于ca 25°dH或ca.450ppm Ca。然后分别加入预计算量的本发明的制剂或对比制剂(表1),调节pH至9.9-10.1,然后目视检查。在将试验瓶置于50℃的预热水浴之后,目视检查试验瓶的沉淀物/浑浊并在观察到浑浊/沉淀时记录时间。
表1:静态CaCO3水垢抑制
当(C.2)被(C.3)替代时获得类似结果。
缩写:
(A.1):MGDA-Na3
(A.2):GLDA-Na4
(A.3):柠檬酸三钠
(B.1):甘氨酸的钠盐
(B.2):L-丙氨酸的钠盐
(C.1):聚丙烯酸,25mol-%用氢氧化钠中和,Mw:4,000g/mol,通过GPC测定并参考游离酸
(C.2):共聚物85重量%丙烯酸、15重量%2-丙烯酰氨基-2-甲基丙-1-磺酸(AMPS),用NaOH完全中和,Mw 8,000g/mol,
(C.3):共聚物衣康酸/丙烯酸/AMPS,按重量计6:3:1,Mw 6,500g/mol HEDP:1,1-1-羟乙基二膦酸
在7.4的pH值下(磷酸盐缓冲液)进行所述测量,固定相:交联聚丙烯酸酯,流动相:水,pH值7.4,含0.01M NaN3的磷酸盐缓冲液。
根据表2的组合物用于制造根据本发明的洗涤剂组合物和对比洗涤剂组合物。
表2:组合物
所有数据以g计
“混合羟基醚/聚合物”:来自WO 2019/197315的接枝共聚物A.10和n-C10H21-CH(OH)-CH2-O-(EO)40-n-C10H21的按重量计4:1混合物
首先,由根据表2的进料制备基础混合物。除(T2)外,进料以及各自的络合剂(A)在干燥状态下混合,最后以熔融形式加入(T2)。
关于洗碗方法的一般说明:
成斑、成膜、脂肪残留物和气味试验:
在Miele自动洗碗机,型号G1222 SCL中进行所有洗碗实验。选择程序40℃(“R-time 2”,用于洗涤)和55°用于漂洗。没有加入单独漂洗剂,没有使用再生盐。在试验开始前,将洗碗机的筛网称重。用水、21°dH(德国硬度)、Ca/Mg:HCO3(3:1):1.35进行洗碗实验。在各实验中,将3个刀(不锈钢)、3个蓝色三聚氰胺树脂盘、11个饮水玻璃杯和14个瓷盘放入洗碗机。在各周期之前,加入5克Biskin(一种固体植物油)和5克人造黄油和50克附加Ballast Soil(RA mix)。在根据本发明的实验的各周期中,加入18克根据表3的洗涤剂组合物。
运行5个周期,在周期之间没有干燥时间。在第5个周期后,由三名试验人员记录气味并从机器中取出筛网以供检查和评价-然后再放入机器,关闭并在25℃下储存另外48小时。然后测定筛网(油脂)重量并计算与它们在第一个周期前的重量的差值。最后,逐一和平均目视评估瓷器、玻璃、刀具和塑料上的成膜和污垢。根据下表等级进行目视评估:
7点:优异;无任何痕迹、无成膜
5-6点:良好,1至4个点,几乎不可见成膜
2-4点:勉强,多于4个点至25%的表面被斑点覆盖,中等成膜
1点:25至50%的表面被斑点覆盖
0点:几乎完全被斑点覆盖,显著成膜
在表3中,仅显示平均值(值具有舍入数和0.5作为可能的精密标度)。
气味分成4个等级:4=中性,无气味,至1=明显臭味(腐臭、腥臭);值是3位评估员的平均值。
结果概括在表4中。
在第5个周期后在25℃下储存48小时后测定气味。
表3:自动洗碗试验
Claims (13)
1.清洁组合物,其以10:1至1:10的(A):(B)重量比含有
(A)至少一种螯合剂,其选自甲基甘氨酸二乙酸(MGDA)的碱金属盐和谷氨酸二乙酸(GLDA)的碱金属盐和柠檬酸的碱金属盐,
(B)甘氨酸或丙氨酸或前述至少一种的碱金属或铵盐。
2.根据权利要求1的组合物,其中螯合剂(A)选自GLDA的四钠盐和MGDA的三钠盐和GLDA的三钠盐和柠檬酸的三钠盐和MGDA的二钠盐和柠檬酸的二钠盐及其组合。
3.根据权利要求1或2的组合物,其中(A)和(B)都是钠盐。
4.根据前述权利要求中任一项的组合物,其中MGDA作为对映体的混合物提供,所述混合物主要含有相应的L-对映体,对映体过量(ee)为10至75%。
5.根据前述权利要求中任一项的组合物,其中丙氨酸(B)是L-丙氨酸。
6.根据前述权利要求中任一项的组合物,其中所述组合物另外含有表面活性剂。
7.根据前述权利要求中任一项的组合物,其中所述组合物另外含有漂白剂。
8.根据前述权利要求中任一项的组合物,其中所述组合物另外含有
(C)(甲基)丙烯酸均聚物或丙烯酸与选自甲基丙烯酸、马来酸、衣康酸和AMPS的至少一种共聚单体的共聚物。
9.根据前述权利要求中任一项的组合物,其中所述组合物在环境温度下是液体。
10.根据前述权利要求中任一项的组合物,其中所述组合物另外含有蛋白酶。
11.根据前述权利要求中任一项的组合物,其中(A)和(B)的总和构成所述组合物的10至50重量%,参考总固含量。
12.在自动洗碗机中清洁餐具的方法,其中所述方法使用根据权利要求1-11中任一项的组合物进行。
13.根据权利要求12的方法,其中所述方法用两种组合物的组合进行,其中一种是根据权利要求1-11中任一项的组合物,另一组合物包含至少一种非离子表面活性剂和至少一种选自碱金属硫酸盐和碱金属碳酸(氢)盐的无机盐。
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2019
- 2019-11-15 PL PL19209442.3T patent/PL3822335T3/pl unknown
- 2019-11-15 EP EP19209442.3A patent/EP3822335B1/en active Active
- 2019-11-15 ES ES19209442T patent/ES2933550T3/es active Active
-
2020
- 2020-11-05 JP JP2022527091A patent/JP2023502216A/ja active Pending
- 2020-11-05 BR BR112021021174A patent/BR112021021174A2/pt not_active Application Discontinuation
- 2020-11-05 US US17/776,793 patent/US20220403295A1/en active Pending
- 2020-11-05 EP EP20799731.3A patent/EP4058544A1/en not_active Withdrawn
- 2020-11-05 CN CN202080043323.2A patent/CN113966383A/zh active Pending
- 2020-11-05 WO PCT/EP2020/081075 patent/WO2021094182A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
ES2933550T3 (es) | 2023-02-10 |
EP3822335B1 (en) | 2022-10-12 |
BR112021021174A2 (pt) | 2022-05-24 |
WO2021094182A1 (en) | 2021-05-20 |
PL3822335T3 (pl) | 2023-03-13 |
JP2023502216A (ja) | 2023-01-23 |
EP3822335A1 (en) | 2021-05-19 |
US20220403295A1 (en) | 2022-12-22 |
EP4058544A1 (en) | 2022-09-21 |
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