CN105555931B - 改性聚天冬氨酸在洗碗洗涤剂中的用途 - Google Patents
改性聚天冬氨酸在洗碗洗涤剂中的用途 Download PDFInfo
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- CN105555931B CN105555931B CN201480050785.1A CN201480050785A CN105555931B CN 105555931 B CN105555931 B CN 105555931B CN 201480050785 A CN201480050785 A CN 201480050785A CN 105555931 B CN105555931 B CN 105555931B
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- acid
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- dishwashing detergent
- modified polyaspartic
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- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 74
- 239000003599 detergent Substances 0.000 title claims abstract description 53
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- 239000000203 mixture Substances 0.000 claims abstract description 53
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- 235000003704 aspartic acid Nutrition 0.000 claims description 26
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 26
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- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 claims description 16
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
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- GGRGTHFWHGANTA-UHFFFAOYSA-N pentane-1,3,3,5-tetracarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)(C(O)=O)CCC(O)=O GGRGTHFWHGANTA-UHFFFAOYSA-N 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 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 group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
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- 239000001384 succinic acid Substances 0.000 description 1
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- 239000003826 tablet Substances 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- POZPMIFKBAEGSS-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;trihydrate Chemical compound O.O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O POZPMIFKBAEGSS-UHFFFAOYSA-K 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 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
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
本发明涉及改性聚天冬氨酸在洗碗洗涤剂中的用途，更特别是用作分散剂、成膜抑制剂和污斑抑制剂。本发明还涉及包含改性聚天冬氨酸的洗碗洗涤剂组合物。
Description
本发明涉及改性聚天冬氨酸在洗碗洗涤剂中的用途，特别是作为分散剂、成膜抑制剂和污斑抑制剂。
多年以来，可通过自由基聚合获得的含羧基单体的聚合物是含磷酸盐和无磷酸盐机器洗碗洗涤剂的重要成分。由于它们的污垢分散和成膜抑制效果，它们显著有助于机器洗碗洗涤剂的清洁和干净漂洗性能。例如，它们确保不在器皿上残留硬度形成性钙和镁离子的盐沉积物。通常将丙烯酸的均聚物和共聚物用于该目的。
可通过自由基聚合获得的含羧基单体的这些聚合物的缺点在于，它们在例如公共污水厂盛行的需氧条件下不可生物降解。
由于日益增长的环境意识，因此对基于丙烯酸的聚羧酸盐的可生物降解聚合物替代品的需求日益增大。然而，市售可生物降解的聚合物如聚天冬氨酸或羧甲基化旋复花粉就商业意义而言仅困难地得到认可。原因是多方面的：在特定应用中的效果不足，由于制备方法复杂和/或原料昂贵而具有过高的成本，聚合物的合成不具有或具有很小的灵活性。例如，与聚丙烯酸的制备方法相反，所实施的聚天冬氨酸制备方法不能就结构、分子量和中和度而言做出大的改变。聚天冬氨酸以中和形式作为钠盐获得。分子量在2000-3000g/mol之间或者在5000-6000g/mol之间波动，这取决于制备方法。如果可能的话，也仅能以极其有限的程度通过靶向工艺变化而使聚合物结构或分子量适于具体应用要求。
WO2011/001170描述了用于机器洗碗的清洁组合物，其包含聚天冬氨酸、液体非离子表面活性剂和至少一种固体非离子表面活性剂，其中并未描述聚天冬氨酸的制备。WO2009/095645描述了洗涤剂和清洁剂组合物，其额外包含改性聚天冬氨酸，其中使用聚天冬氨酸作为成膜防止剂的骨架。所述改性聚天冬氨酸通过使聚天冬氨酸或聚琥珀酰亚胺与PO/EO嵌段共聚物、聚乙烯亚胺或三磷酸腺苷反应而获得。可能的话，就其分子量而言，该聚天冬氨酸骨架仅可困难地调节。
因此，本发明的目的是提供作为洗碗洗涤剂添加剂，特别是作为用于机器洗碗的无磷酸盐洗碗洗涤剂配制剂的添加剂的聚合物，其可用于在水递送体系中抑制成膜，其中可变地调节其聚合物结构及其分子量且可生物降解。此处，所述聚合物的分子量可理想地在1000-10000g/mol之间调节。
该目的通过根据权利要求书以及下文描述和实施例的本发明实现。
本发明涉及改性聚天冬氨酸作为洗碗洗涤剂的添加剂的用途，包含改性聚天冬氨酸的洗碗洗涤剂组合物。就本发明而言，所用的改性聚天冬氨可通过缩聚如下物质：
(i)50-99mol％天冬氨酸；和
(ii)1-50mol％至少一种含羧基的化合物；
且随后通过添加碱水解所述共缩合物而制备；其中(ii)不为天冬氨酸。除本文所述且本发明所用的该改性聚天冬氨酸之外，本发明的洗碗洗涤剂组合物还包含配位剂、助洗剂和/或共助洗剂、非离子表面活性剂、漂白剂和/或漂白活化剂、酶以及任选的其他添加剂。
由于本文所述的聚天冬氨酸制备方法随后为添加碱的水解步骤，本领域技术人员很容易知晓所述聚天冬氨酸首先以盐形式获得。聚天冬氨酸的酸形式可通过酸化所述盐的另一步骤而直接获得，该酸化可以以本领域技术人员已知的方式进行。适于该目的的酸尤其为无机酸，例如硫酸或盐酸。如果仅希望获得聚天冬氨酸的盐(例如作为中间体)，则可省略随后的酸化步骤。因此，就本发明而言，当讨论聚天冬氨酸时，还涵盖其相应的盐，这可通过或通过所述的随后酸化步骤获得且是本领域技术人员所知晓的。
改性聚天冬氨酸盐的任选酸化可例如通过将确定量的浓或稀无机酸如硫酸或盐酸添加至所述改性聚天冬氨酸的钠盐水溶液中而进行。酸化也可通过用酸性离子交换剂如Amberlite IR 120(氢形式)处理而进行，其中使改性聚天冬氨酸的Na盐水溶液流经填充有该离子交换剂的柱。
本发明所用的改性聚天冬氨酸显示出作为洗碗洗涤剂，尤其是用于机器洗碗的洗碗洗涤剂的添加剂的极好适用性，且具有极好的分散、成膜抑制剂和污斑抑制性能。此外，它们可生物降解且可以以可变分子量制备。
因此，本发明涉及改性聚天冬氨酸作为洗碗组合物，特别是用于机器洗碗的洗碗组合物中的添加剂—例如但不限于分散剂、成膜抑制剂或污斑抑制剂—的用途，其中所述改性聚天冬氨酸可通过缩聚如下物质：
(i)50-99mol％，优选60-95mol％，特别优选80-95mol％天冬氨酸；和
(ii)1-50mol％，优选5-40mol％，特别优选5-20mol％至少一种含羧基的化合物；
且随后通过添加碱，例如氢氧化钠溶液水解所述共缩合物而制备，其中(ii)不为天冬氨酸。
本发明还涉及洗碗洗涤剂组合，特别是用于机器洗碗的洗碗洗涤剂组合物，其包含可如本文所示和所述制备的改性聚天冬氨酸。因此，就本发明而言，关于改性聚天冬氨酸制备的描述通常涉及该改性聚天冬氨酸作为洗碗洗涤剂中的添加剂的本发明用途，及其作为本发明洗碗洗涤剂组合物成分的用途。
就本发明所用聚天冬氨酸的制备而言，所用的天冬氨酸(i)可为L-或D-和DL-天冬氨酸。优选使用L-天冬氨酸。
就本发明所用聚天冬氨酸的制备而言，所用的含羧基化合物(ii)可尤其为羧酸(单羧酸或多羧酸)、羟基羧酸和/或氨基酸(除天冬氨酸之外)。该羧酸或羟基羧酸优选为多元的。因此，就此而言，可将多元羧酸用于制备本发明所用的聚天冬氨酸，例如草酸、己二酸、富马酸、马来酸、衣康酸、乌头酸、琥珀酸、丙二酸、辛二酸、壬二酸、二甘醇酸、戊二酸、C1-C26烷基琥珀酸(例如辛基琥珀酸)、C2-C26链烯基琥珀酸(例如辛烯基琥珀酸)、1,2,3-丙烷三甲酸、1,1,3,3-丙烷四甲酸、1,1,2,2-乙烷四甲酸、1,2,3,4-丁烷四甲酸、1,2,2,3-丙烷四甲酸或1,3,3,5-戊烷四甲酸。此外，就此而言，还可使用多元羟基羧酸，例如柠檬酸、异柠檬酸、粘酸、酒石酸、羟基丙二酸或苹果酸。就此而言，可用的氨基酸尤其为氨基羧酸(例如谷氨酸、半胱氨酸)、碱性二氨基羧酸(例如赖氨酸、精氨酸、组氨酸、氨基己内酰胺)、中性氨基酸(例如甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、蛋氨酸、半胱氨酸、正亮氨酸、己内酰胺、天冬酰胺、异天冬酰胺、谷氨酰胺、异谷氨酰胺)、氨基磺酸(例如牛磺酸)、羟基氨基酸(例如羟基脯氨酸、丝氨酸、苏氨酸)、亚氨基羧酸(例如脯氨酸、亚氨基二乙酸)，或芳族或杂环族氨基酸(例如邻氨基苯甲酸、色氨酸、酪氨酸、组氨酸)，但不为天冬氨酸。就本发明所用改性聚天冬氨酸的制备而言，优选的含羧基化合物(ii)为1,2,3,4-丁烷四甲酸、柠檬酸、甘氨酸、谷氨酸、衣康酸、琥珀酸、牛磺酸、马来酸和戊二酸，特别优选1,2,3,4-丁烷四甲酸、柠檬酸、甘氨酸和谷氨酸。
可用于在制备本发明所用改性聚天冬氨酸中水解所述共缩合物的碱为：碱金属和碱土金属碱，如氢氧化钠溶液、氢氧化钾溶液、氢氧化钙或氢氧化钡；碳酸盐，如碳酸钠和碳酸钾；氨和伯、仲或叔胺；具有伯、仲或叔氨基的其他碱。就本发明而言，优选氢氧化钠溶液或氢氧化铵。
本发明所用改性聚天冬氨酸的制备通常如上下文所示和所述经由天冬氨酸与至少一种含羧基的化合物(非天冬氨酸)缩聚且随后通过添加碱水解所述共缩合物而进行。该改性聚天冬氨酸的制备还描述于例如DE4221875.6中。本发明所用改性聚天冬氨酸的制备例如如下文所述。该制备描述必须不理解为限制本发明所用的改性聚天冬氨酸。本发明所用的聚天冬氨酸不仅包括通过如下制备描述制得的那些，而且包括可通过后续方法制得的那些。本发明所用的改性聚天冬氨酸可例如通过以本文所述的摩尔比缩聚组分(i)和(ii)，即天冬氨酸和至少一种含羧基的化合物而制备。缩聚可在100-270℃，优选120-250℃，特别优选180-220℃的温度下进行。缩合(加热)优选在真空下或者在惰性气体气氛(例如N2或氩气)下进行。然而，缩合也可在升高的压力下或在气流如二氧化碳、空气、氧气或水蒸汽中进行。缩合的反应时间通常为1分钟至50小时，优选为5-8小时，这取决于所选的反应条件。缩聚可例如在固相中通过首先制备天冬氨酸和至少一种含羧基化合物(ii)的水溶液或悬浮液且将溶液蒸发至干而进行。在此期间，缩合可能就已经开始。适于缩合的反应装置实例为加热带、捏和机、混合机、桨叶式干燥机、挤出机、回转炉，和其中可实施固体缩合且移除反应水的其他可加热设备。具有低分子量的缩聚物可还在耐压密闭容器中制备，其中不移除或者仅部分移除所形成的反应水。缩聚也可通过红外辐射或微波辐射进行。酸催化的缩聚也是可能的，例如使用磷或硫的无机酸或者使用卤化氢。该类酸催化的缩聚还描述于DE4221875.6中。
通过在天冬氨酸缩聚期间添加少量甲烷磺酸，可控制随后水解聚琥珀酰亚胺中间体而获得的聚天冬氨酸的分子量。因此，就本发明而言，也可通过使用甲烷磺酸作为缩聚中除天冬氨酸(i)和含羧基化合物(ii)之外的添加剂且随后如本文所述使用碱水解所得共缩合物而制备本发明所用的改性聚天冬氨酸。此处，在缩合步骤中，一方面天冬氨酸(i)和含羧基化合物(ii)与另一方面甲烷磺酸的摩尔比应理想地为200:1-5:1，优选为100:1-10:1，特别优选为50:1-12:1。因此，在本发明的该实施方案中，为了制备本发明所用的改性聚天冬氨酸，如本文所述，将50-99mol％，优选60-95mol％，特别优选80-95mol％天冬氨酸和1-50mol％，优选5-40mol％，特别优选5-20mol％含羧基的化合物与甲烷磺酸以200:1-5:1，优选100:1-10:1，特别优选50:1-12:1的比例缩聚。甲烷磺酸如聚天冬氨酸一样，是可生物降解的。少量甲烷磺酸可残留在聚合物产物中，而不导致生态学缺点且不影响在许多应用中的性能。复杂的后处理或纯化是不必要的。避免了因后处理所导致的产率损失。
在天冬氨酸与所设想的含羧基化合物(ii)的热缩聚(使用或不使用甲烷磺酸)期间，缩聚物通常以水不溶性改性聚天冬酰亚胺(polyaspartimide)形式制备，在少数情况下以水溶性形式制备(例如在缩聚L-天冬氨酸和柠檬酸的情况下)。天冬氨酸的共缩合物可例如通过粉碎缩合产物，在10-100℃温度下用水将其萃取而与未反应的原料纯化。在此期间，未反应的原料溶出，且任选所用的甲烷磺酸洗出。未反应的天冬氨酸可通过用1N盐酸萃取而容易地溶出。
所述改性聚天冬氨酸优选由所述缩聚物通过将该共缩聚物淤浆化于水中或者溶解它们(如果所述共缩聚物已为水溶性的，例如获自L-天冬氨酸和柠檬酸的共缩聚物)，并在0-90℃的温度下通过添加碱水解并中和它们而获得。水解和中和优选在8-10的pH下进行。合适的碱例如为碱金属和碱土金属碱，如氢氧化钠溶液、氢氧化钾溶液、氢氧化钙或氢氧化钡。合适的碱还例如为碳酸盐，如碳酸钠和碳酸钾。合适的碱还为氨和伯、仲或叔胺，以及具有伯、仲或叔氨基的其他碱。如果将胺用于聚天冬酰亚胺的反应，则所述胺可由于其高反应性而类似于盐或者类似于酰胺地键合成聚天冬氨酸。在用碱处理的情况下，获得部分或完全中和的共缩聚物，其根据先前缩聚中的进料而包含50-99mol％天冬氨酸(i)和1-50mol％至少一种含羧基的化合物(ii)(其中以本文所述的比例含有或不含有甲烷磺酸)，其呈对应于所述碱的盐形式。
本发明所用的改性聚天冬氨酸和/或其盐可以以水溶液或固体形式，例如以粉末或颗粒形式使用。正如本领域技术人员所已知的那样，粉末或颗粒形式可例如通过喷雾干燥、喷雾造粒、流化床喷雾造粒、辊式干燥或冷冻干燥聚天冬氨酸或其盐的水溶液而获得。
本发明还涉及洗碗洗涤剂组合物，特别是适于机器洗碗的洗碗洗涤剂组合物，其除本文所述且本发明所用的改性聚天冬氨酸之外，还包含配位剂、助洗剂和/或共助洗剂、非离子表面活性剂、漂白剂和/或漂白活化剂、酶和任选的其他添加剂如溶剂。本文所述且本发明所用的改性聚天冬氨酸可以以其各种提供形式通过本领域技术人员已知的方法直接掺入配制剂(混合物)中。就此而言，尤其提及固体配制剂如粉末、片剂、凝胶状配制剂和液体配制剂。
本文所述且本发明所用的改性聚天冬氨酸可特别有利地用于机器洗碗洗涤剂中。此处，它们的特征尤其在于其对无机和有机膜的成膜抑制效果。特别地，它们抑制由碳酸钙和碳酸镁以及磷酸钙和磷酸镁以及膦酸钙和膦酸镁形成膜。此外，它们防止由洗液的污垢成分产生沉积物，如脂肪、蛋白质和淀粉膜。
本发明的洗碗洗涤剂组合物可以以液体、凝胶状或固体形式，作为一个或多个相，作为片剂或者以其他剂量单元形式(包装或未包装的)提供。
本文所述且本发明所用的改性聚天冬氨酸可用于多组分产品体系(单独使用洗涤剂、洗涤助剂和再生盐)中，或者用于其中洗涤剂、洗涤助剂和再生盐的功能组合在一种产品(例如3合1产品、6合1产品、9合1产品或全合一产品)中的那些洗碗洗涤剂中。
本发明的洗碗洗涤剂组合物包含：
(a)1-20重量％，优选1-15重量％，特别优选2-12重量％至少一种本文所述且本发明所用的改性聚天冬氨酸；
(b)0-50重量％配位剂；
(c)0.1-80重量％助洗剂和/或共助洗剂；
(d)0.1-20重量％非离子表面活性剂；
(e)0-30重量％漂白剂、漂白活化剂和漂白催化剂；
(f)0-8重量％酶；和
(g)0-50重量％添加剂。
本发明的洗碗洗涤剂组合物特别适于作为用于机器洗碗的洗碗洗涤剂组合物。因此，在一个实施方案中，本发明的洗碗洗涤剂组合物为机器洗碗洗涤剂组合物。
可使用的配位剂(b)的实例为：次氮基三乙酸、乙二胺四乙酸、二亚乙基三胺五乙酸、羟基乙基乙二胺三乙酸、甲基甘氨酸二乙酸、谷氨酸二乙酸、亚氨基二琥珀酸、羟基亚氨基二琥珀酸、乙二胺二琥珀酸、天冬氨酸二乙酸，以及在每种情况下，其盐。优选的配位剂(b)为甲基甘氨酸二乙酸和谷氨酸二乙酸及其盐。特别优选的配位剂(b)为甲基甘氨酸二乙酸及其盐。根据本发明，优选3-50重量％的配位剂(b)。
可使用的助洗剂和/或共助洗剂(c)尤其为水溶性或水不溶性物质，其主要任务是结合钙和镁离子。这些可为低分子量羧酸及其盐如碱金属柠檬酸盐，尤其为无水柠檬酸三钠或柠檬酸三钠二水合物，碱金属琥珀酸盐，碱金属丙二酸盐，脂肪酸磺酸盐，氧基二琥珀酸盐(oxydisuccinat)，烷基或链烯基二琥珀酸盐，葡糖酸，氧杂二乙酸盐(oxadiacetate)，羧甲基氧基琥珀酸盐，酒石酸盐单琥珀酸盐，酒石酸盐二琥珀酸盐，酒石酸盐单乙酸盐，酒石酸盐二乙酸盐和α-羟基丙酸。
可存在于本发明清洁剂中且具有共助洗剂性质的其他物质类别为膦酸盐。这些尤其为羟基烷烃膦酸盐或氨基烷烃膦酸盐。在羟基烷烃膦酸盐中，1-羟基乙烷-1,1-二膦酸盐(HEDP)作为共助洗剂特别重要。其优选以钠盐、给出中性反应的二钠盐和碱性反应的四钠盐(pH 9)形式使用。合适的氨基烷烃膦酸盐优选为乙二胺四亚甲基膦酸盐(EDTMP)、二亚乙基三胺五亚甲基膦酸盐(DTPMP)及其更高级同系物。它们优选以中性反应钠盐，例如EDTMP的六钠盐或DTPMP的七钠盐和八钠盐形式使用。此处，选自膦酸盐类别的所用助洗剂优选为HEDP。此外，氨基烷烃膦酸盐具有显著的重金属结合能力。因此，尤其当所述组合物还包含漂白剂时，可优选使用氨基烷烃膦酸盐，尤其是DTPMP，或者使用所述膦酸盐的混合物。
硅酸盐可尤其用作助洗剂。可存在具有通式NaMSixO2x+1yH2O的结晶层状硅酸盐，其中M为钠或氢，x为1.9-22，优选1.9-4的数，其中特别优选x的值为2、3或4，且y为0-33，优选0-20的数。此外，可使用SiO2:Na2O之比为1-3.5，优选1.6-3，尤其为2-2.8的无定形硅酸钠。
此外，就本发明的洗碗洗涤剂组合物而言，可用的助洗剂和/或共助洗剂(c)为碳酸盐和碳酸氢盐，其中优选碱金属盐，尤其是钠盐。
作为共助洗剂，还可使用丙烯酸或甲基丙烯酸的均聚物和共聚物，其优选具有2000-50000g/mol的重均摩尔质量。合适的共聚单体尤其为单烯属不饱和二羧酸如马来酸、富马酸和衣康酸，及其酐如马来酸酐。包含磺酸基团的共聚单体如2-丙烯酰胺基-2-甲基丙烷磺酸、烯丙基磺酸和乙烯基磺酸也是合适的。疏水性共聚单体也是合适的，例如异丁烯、二异丁烯、苯乙烯、具有10个或更多个碳原子的α-烯烃。具有羟基官能或氧化烯基团的亲水性单体也可用作共聚单体。例如，可提及：烯丙醇和异戊二烯醇及其烷氧基化物和甲氧基聚乙二醇(甲基)丙烯酸酯。
就本发明的洗碗洗涤剂组合物而言，助洗剂和/或共助洗剂的优选量为5-80重量％，特别优选为10-75重量％、15-70重量％或15-65重量％。
就本发明的洗碗洗涤剂组合物而言，可用的非离子表面活性剂(d)例如为弱起泡或低起泡非离子表面活性剂。这些可以以0.1-20重量％，优选0.1-15重量％，特别优选0.25-10重量％或0.5-10重量％的比例存在。合适的非离子表面活性剂尤其包括通式(I)的表面活性剂：
R1-O-(CH2CH2O)a-(CHR2CH2O)b-R3 (I)
其中R1为具有8-22个碳原子的直链或支化烷基，
R2和R3彼此独立地为氢或具有1-20个碳原子的直链或支化烷基或H，其中
R2优选为甲基，和
a和b彼此独立地为0-300。优选地，a＝1-100且b＝0-30。
就本发明而言，还合适的为式(II)的表面活性剂：
R4-O-[CH2CH(CH3)O]c[CH2CH2O]d[CH2CH(CH3)O]eCH2CH(OH)R5(II)
其中R4为具有4-22个碳原子的直链或支化脂族烃基或其混合物，
R5为具有2-26个碳原子的直链或支化烃基或其混合物，
c和e为0-40的值，和
d为至少15的值。
就本发明而言，还合适的为式(III)的表面活性剂：
R6O-(CH2CHR7O)f(CH2CH2O)g(CH2CHR8O)h-CO-R9 (III)
其中R6为具有8-16个碳原子的支化或未支化烷基，
R7，R8彼此独立地为H，或具有1-5个碳原子的支化或未支化烷基，
R9为具有5-17个碳原子的未支化烷基，
f，h彼此独立地为1-5的数，和
g为13-35的数。
式(I)、(II)和(III)的表面活性剂可为无规共聚物或嵌段共聚物，它们优选呈嵌段共聚物的形式。
此外，就本发明而言，可使用由氧化乙烯和氧化丙烯组成的二或多嵌段共聚物，其可例如以名称(BASF SE)或(BASF Corporation)商购获得。此外，可使用由脱水山梨醇酯与氧化乙烯和/或氧化丙烯的反应产物。同样合适的是氧化胺或烷基糖苷。合适的非离子表面活性剂的综述由EP-A 851 023和DE-A 198 19 187公开。
还可存在两种或更多种不同非离子表面活性剂的混合物。此外，本发明的洗碗洗涤剂组合物可包含阴离子或两性离子表面活性剂，优选呈与非离子表面活性剂的混合物形式。合适的阴离子和两性离子表面活性剂同样在EP-A 851 023和DE-A 198 19 187中提及。
就本发明的洗碗洗涤剂组合物而言，可使用的漂白剂和漂白活化剂(e)为本领域技术人员已知的代表物。漂白剂分为氧漂白剂和含氯漂白剂。所用的氧漂白剂为碱金属过硼酸盐及其水合物以及碱金属过碳酸盐。此处，优选的漂白剂为呈一水合物或四水合物形式的过硼酸钠，过碳酸钠或过碳酸钠的水合物。同样可使用的氧漂白剂为过硫酸盐和过氧化氢。典型的氧漂白剂还为有机过酸如过苯甲酸、过氧化α-萘甲酸、过氧化月桂酸、过氧化硬脂酸、邻苯二甲酰亚胺基过氧己酸、1,12-二过氧十二烷二酸、1,9-二过氧壬二酸、二过氧间苯二甲酸或2-癸基二过氧丁烷-1,4-二酸。此外，如下氧漂白剂也可用于所述洗碗洗涤剂组合物中：专利申请US5,422,028、US5,294,362和US5,292,447中所述的阳离子过氧酸和专利申请US5,039,447中所述的磺酰基过氧酸。氧漂白剂可以以通常为0.1-30重量％，优选1-20重量％，特别优选3-15重量％的量使用，基于全部洗碗洗涤剂组合物。
就本发明的洗碗洗涤剂组合物而言，同样可使用含氯漂白剂以及含氯漂白剂与过氧漂白剂的组合。已知的含氯漂白剂例如为1,3-二氯-5,5-二甲基乙内酰脲、N-氯磺酰胺、氯胺T、二氯胺T、氯胺B、N,N'-二氯苯甲酰脲、二氯对甲苯磺酰胺或三氯乙胺。优选的含氯漂白剂为次氯酸钠、次氯酸钙、次氯酸钾、次氯酸镁、二氯异氰脲酸钾或二氯异氰脲酸钠。就此而言，含氯漂白剂通常可以以0.1-30重量％，优选0.1-20重量％，优选0.2-10重量％，特别优选0.3-8重量％的量使用，基于全部洗碗洗涤剂组合物。
此外，可添加少量漂白稳定剂如膦酸盐、硼酸盐、偏硼酸盐、偏硅酸盐或镁盐。
就本发明而言，漂白活化剂为在过氧化氢解(perhydrolyse-bedingungen)条件下形成优选具有1-10个碳原子，尤其是2-4个碳原子的脂族过氧羧酸和/或取代的过苯甲酸的化合物。就此而言，合适的化合物尤其为包含一个或多个N-或O-酰基和/或任选取代的苯甲酰基的那些，例如选自酐、酯、酰亚胺、酰基化的咪唑或肟的物质。实例为四乙酰基乙二胺(TAED)、四乙酰基亚甲基二胺(TAMD)、四乙酰基甘脲(TAGU)、四乙酰基己二胺(TAHD)、N-酰基亚胺如N-壬酰基琥珀酰亚胺(NOSI)、酰基化的苯酚磺酸盐如正壬酰基-或异壬酰基氧基苯磺酸盐(正或异NOBS)、五乙酰基葡萄糖(PAG)、1,5-二乙酰基-2,2-二氧六氢-1,3,5-三嗪(DADHT)或靛红酸酐(ISA)。适于作为漂白活化剂的同样还有腈季铵盐，例如N-甲基吗啉基乙腈盐(MMA盐)或三甲基铵乙腈盐(TMAQ盐)。优选合适的为选自多酰基化的亚烷基二胺的漂白活化剂，特别优选TAED、N-酰基亚胺，特别优选NOSI，酰基化的苯酚磺酸盐，更优选正或异NOBS、MMA和TMAQ。就本发明而言，漂白活化剂可以以0.1-30重量％，优选0.1-10重量％，优选1-9重量％，特别优选1.5-8重量％的量使用，基于全部洗碗洗涤剂组合物。
除常规漂白活化剂之外或者代替它们，还可在洗涤助剂颗粒中掺入所谓的漂白催化剂。这些物质为漂白增强过渡金属盐或过渡金属配合物如锰-、铁-、钴-、钌-或钼-salen配合物或羰基配合物。还可使用锰、铁、钴、钌、钼、钛、钒和铜与含氮三脚架配体的配合物以及钴-、铁-、铜-和钌-胺配合物作为漂白催化剂。
作为组分(f)，本发明的洗碗洗涤剂组合物可包含0-8重量％酶。如果所述洗碗洗涤剂组合物包含酶，则其通常以0.1-8重量％的量包含这些。可将酶添加至所述洗碗洗涤剂中以提高清洁性能或确保在更温和的条件下(例如在更低的温度下)达到相同品质的清洁性能。酶可以游离形式，或者化学或物理固定于载体上的形式，或者包封形式使用。就此而言，最常用的酶包括脂肪酶、淀粉酶、纤维素酶和蛋白酶。此外，也可使用酯酶、果胶酶、乳糖酶和过氧化物酶。根据本发明，优选使用淀粉酶和蛋白酶。
就本发明的洗碗洗涤剂组合物而言，作为添加剂(g)，可使用例如阴离子或两性离子表面活性剂、碱性载体、聚合物分散剂、腐蚀抑制剂、消泡剂、染料、香料、填料、片剂崩解剂、有机溶剂、成片助剂、崩解剂、增稠剂、增溶剂或水。除已对助洗剂物质所述的碳酸铵或碱金属碳酸盐、碳酸氢铵或碱金属碳酸氢盐和倍半碳酸铵或碱金属倍半碳酸盐之外，可用的碱性载体还例如为氢氧化铵或碱金属氢氧化物、硅酸铵或碱金属硅酸盐和偏硅酸铵或碱金属偏硅酸盐，以及上述物质的混合物。
作为腐蚀抑制剂，可尤其使用选自三唑类、苯并三唑类、二苯并三唑类、氨基三唑类、烷基氨基三唑类和过渡金属盐或配合物的银保护剂。
为了防止玻璃腐蚀(其体现为玻璃器皿上的发雾、虹彩、条纹和线)，优选使用玻璃腐蚀抑制剂。优选的玻璃腐蚀抑制剂例如为镁、锌和铋盐以及配合物。
根据本发明，可任选将石蜡油和硅油用作消泡剂和用于保护塑料和金属表面。消泡剂优选以0.001-5重量％的比例使用。此外，可在本发明的清洁配制剂中添加染料如专利蓝、防腐剂如Kathon CG、香料和其他芳香物质。
就本发明的洗碗洗涤剂组合物而言，合适的填料例如为硫酸钠。
就本发明而言，其他可能的添加剂为两性和阳离子聚合物。
在一个实施方案中，本发明的洗碗洗涤剂组合物不含磷酸盐。就此而言，术语“不含磷酸盐”还包括基本上不含磷酸盐，即技术上无效量的磷酸盐的那些洗碗洗涤剂组合物。这尤其包括具有小于1.0重量％，优选小于0.5重量％磷酸盐的组合物，基于全部组合物。
下文实施例用于阐述本发明且必须不理解为对其进行限制。
实施例1 制备改性的聚天冬氨酸
在每种情况下给出摩尔比。
本发明聚合物
聚合物1：L-天冬氨酸/BTC 1.0:0.1的缩聚物
聚合物1b：在5mol％(基于L-Asp)甲烷磺酸存在下，L-天冬氨酸/BTC1.0:0.1的缩聚物
聚合物2：L-天冬氨酸/BTC 1.0:0.2的缩聚物
聚合物3：L-天冬氨酸/柠檬酸1.0:0.5的缩聚物
聚合物4：L-天冬氨酸/甘氨酸1.0:0.1的缩聚物
聚合物5：L-天冬氨酸/谷氨酸1.0:0.1的缩聚物
聚合物5b：在5mol％(基于L-Asp)甲烷磺酸存在下，L-天冬氨酸/谷氨酸1.0:0.1的缩聚物
BTC＝1,2,3,4-丁烷四甲酸
对比聚合物
聚合物C1：聚天冬氨酸，Na盐，Mw 3000g/mol
聚合物C2：聚天冬氨酸，Na盐，Mw 5400g/mol
本发明聚合物
聚合物1：
在具有搅拌器的2L容量的反应器中装入133.10g L-天冬氨酸、70g水和23.42g 1,2,3,4-丁烷四甲酸。将反应混合物在搅拌下在210℃温度下搅拌4小时，同时蒸出水。将所得改性聚天冬酰亚胺熔体冷却，然后粉碎。为了制备改性聚天冬氨酸的钠盐水溶液，将100g粉碎的反应物分散至100g水中，将混合物加热至70℃，并在该温度下添加足量的50％浓度氢氧化钠水溶液以使pH为7-8。在此期间，分散在水中的粉末逐步溶解，从而获得改性聚天冬氨酸钠盐的澄清水溶液。改性聚天冬氨酸的重均分子量(Mw)为2600g/mol。
聚合物1b：
该聚合物的合成和后处理精确地如聚合物1所述那样进行，但额外向反应器中装入4.81g甲烷磺酸。改性聚天冬氨酸的重均分子量(Mw)为3300g/mol。
聚合物2：
类似于聚合物1的制备，将133.10g L-天冬氨酸和46.83g 1,2,3,4-丁烷四甲酸装入反应器中，在240℃下缩聚2.5小时。将所得改性聚天冬酰亚胺熔体如实施例1所述冷却，粉碎并水解，从而获得改性聚天冬氨酸钠盐的水溶液。改性聚天冬氨酸的重均分子量(Mw)为1870g/mol。
聚合物3：
类似于聚合物1的制备，将133.10g L-天冬氨酸和96.07g柠檬酸装入反应器中，在180℃下缩聚5小时。将所得改性聚天冬酰亚胺熔体冷却，然后粉碎。为了制备改性聚天冬氨酸钠盐的水溶液，将100g冷却和粉碎的反应物溶于100g水中，并在冰冷却下，添加足量的50％浓度氢氧化钠水溶液以使pH为7-8。改性聚天冬氨酸的重均分子量(Mw)为1320g/mol。
聚合物4：
类似于聚合物1的制备，将133.10g L-天冬氨酸、30.00g水和7.51g甘氨酸装入反应器中，在220℃下缩聚7小时。将所得改性聚天冬酰亚胺熔体如实施例1所述冷却，粉碎并水解，从而获得改性聚天冬氨酸钠盐的水溶液。改性聚天冬氨酸的重均分子量(Mw)为6060g/mol。
聚合物5：
类似于聚合物1的制备，将133.10g L-天冬氨酸、30.00g水和14.71g L-谷氨酸装入反应器中，在220℃下缩聚7.5小时。将所得改性聚天冬酰亚胺熔体如实施例1所述冷却，粉碎并水解，从而获得改性聚天冬氨酸钠盐的水溶液。改性聚天冬氨酸的重均分子量(Mw)为3810g/mol。
聚合物5b：
该聚合物的合成和后处理精确地如聚合物5所述那样进行，但额外向反应器中装入4.81g甲烷磺酸。改性聚天冬氨酸的重均分子量(Mw)为6100g/mol。
对比聚合物
聚合物C1(聚天冬氨酸M)：
在圆底烧瓶中，将10g马来酰胺(通过马来酸酐与氨的反应制备)在240℃下缩聚2小时。在此期间，反应物如泡沫那样溶胀，且在冷却后可容易地粉碎。将粉碎的聚天冬酰亚胺如实施例1所述那样水解，从而获得聚天冬氨酸钠盐水溶液。重均分子量(Mw)为3000g/mol。
聚合物C2(聚天冬氨酸T)：
在旋转蒸发器中，将133.10g L-天冬氨酸在220-240℃温度下缩聚2小时。将所得聚天冬酰亚胺如实施例1所述那样水解，从而获得聚天冬氨酸钠盐水溶液。重均分子量(Mw)为5400g/mol。
实施例2 测定分子量(Mw)
实施例的重均分子量(Mw)借助GPC(凝胶渗透色谱法)在如下条件下测定：
将样品溶液经Sartorius Minisart RC 25(0.2μm)过滤。标定使用获自PolymerStandard Service的窄分布Na-PAA标样进行，其分子量为从M＝1250至M＝193 800。此外，使用分子量M＝96的丙烯酸Na和M＝620的PEG标样，这等于Na-PAA M＝150。超出该洗脱范围的值采用外推法。评价极限为约M＝298g/mol。
实施例3洗碗机测试
在下列无磷酸盐测试配制剂PF1中测试聚合物。测试配制剂PF1的组成在表1(数据以重量％计)中给出。
表1：测试配制剂PF1
| 成分 | PF 1 |
| 蛋白酶 | 2.5 |
| 淀粉酶 | 1.0 |
| 非离子表面活性剂 | 5 |
| 聚合物 | 10 |
| 过碳酸钠 | 10.2 |
| 四乙酰基乙二胺 | 4 |
| 二硅酸钠 | 2 |
| 碳酸钠 | 19.5 |
| 柠檬酸钠三水合物 | 35 |
| 甲基甘氨酸二乙酸，Na盐 | 10 |
| 羟基乙烷-(1,1-二膦酸) | 0.8 |
数据以重量％计，基于所有组分的总量
此处，遵循如下实验条件：
洗碗机：Miele G 1222SCL
程序：65℃(含预漂洗)
器皿：3把刀(Karina镍铬刀，Solex Germany GmbH，Eisingen/德国)
3个Amsterdam 0.2L饮用玻璃
3个“OCEAN BLUE”早餐盘(蜜胺)
3个陶瓷盘：19CM带边平盘
设置：刀置于餐盘中，玻璃置于上部篮中，盘置于下部篮中
洗碗洗涤剂：18g
污垢添加：预洗后将50g呈熔融形式的基础污物(Ballastschmutze)与配制剂一起计量加入，参见下文组成
清洗温度：65℃
水硬度：21°德国硬度(Ca/Mg)：HCO3(3:1)：1.35
漂洗周期：15；在每种情况下每个周期之间暂停1小时(开门10分钟，关门50分钟)
评估：15个洗涤周期后视觉评估
在15个周期后，于暗室中在光下于孔板后使用10(非常好)至1(非常差)的评分标准对所述器皿进行评估。对污斑(非常多的密集污斑＝1，无污斑＝10)和膜(1＝非常显著的膜，10＝无膜)给予1-10的评分。
基础污物的组成：
淀粉：0.5％马铃薯淀粉，2.5％肉汁
脂肪：10.2％人造奶油
蛋白质：5.1％蛋黄，5.1％牛奶
其他：2.5％番茄酱，2.5％芥末，0.1％苯甲酸，71.5％水
结果：
具有本发明改性聚天冬氨酸的配制剂的特征尤其在于其对玻璃和刀具上的无机和有机沉积物的极高成膜抑制效果。此外，它们提高了洗碗洗涤剂的清洁能力且有利于水从器皿上流走，这意味着获得了特别透明的玻璃和闪亮的金属餐具。
下表2列出了刀具和饮用玻璃上的成膜(F)和污斑(S)评分。
表2：测试配制剂1(PF 1)的测试结果
| 聚合物 | 刀(F+S) | 玻璃(F+S) |
| 无聚合物 | 7.0 | 7.0 |
| 聚合物1 | 15.3 | 11.7 |
| 聚合物1b | 15.7 | 12.0 |
| 聚合物2 | 14.6 | 11.7 |
| 聚合物3 | 12.7 | 10.0 |
| 聚合物4 | 14.0 | 10.3 |
| 聚合物5 | 13.7 | 10.3 |
| 聚合物5b | 14.3 | 11.1 |
| 聚合物C1 | 8.3 | 7.7 |
| 聚合物C2 | 11.4 | 9.0 |
Claims (17)
1.改性聚天冬氨酸作为洗碗洗涤剂中的添加剂的用途，其中所述改性聚天冬氨酸通过缩聚如下物质：
(i)50-99mol％的比例为200:1-5:1的天冬氨酸和甲烷磺酸；和
(ii)1-50mol％至少一种含羧基的化合物；
且随后通过添加碱水解共缩合物而制备；其中(ii)不为天冬氨酸。
2.根据权利要求1的用途，其中(ii)为5-50mol％至少一种含羧基的化合物。
3.根据权利要求1的用途，其中(ii)为5-20mol％至少一种含羧基的化合物。
4.根据权利要求2的用途，其中(ii)为5-20mol％至少一种含羧基的化合物。
5.根据权利要求1-4中任一项的用途，其中(ii)为单羧酸、多羧酸、羟基羧酸和/或氨基酸。
6.根据权利要求1-4中任一项的用途，其中(ii)选自1,2,3,4-丁烷四甲酸、柠檬酸、甘氨酸和谷氨酸。
7.根据权利要求1-4中任一项的用途，其中所述碱选自碱金属和碱土金属碱；碳酸盐；氨；伯、仲或叔胺；和具有伯、仲或叔氨基的碱。
8.根据权利要求1-4中任一项的用途，用于机器洗碗机的洗碗洗涤剂中。
9.根据权利要求1-4中任一项的用途，其中所述改性聚天冬氨酸通过缩聚如下物质：
(i)50-99mol％的比例为100:1-10:1的天冬氨酸和甲烷磺酸；和
(ii)1-50mol％至少一种含羧基的化合物；
且随后通过添加碱水解共缩合物而制备，其中(ii)不为天冬氨酸。
10.根据权利要求9的用途，其中(i)的量为60-95mol％。
11.根据权利要求9的用途，其中(i)的量为80-95mol％。
12.根据权利要求9的用途，其中天冬氨酸和甲烷磺酸的比例为50:1-12:1。
13.根据权利要求9的用途，其中(ii)的量为5-40mol％。
14.根据权利要求9的用途，其中(ii)的量为5-20mol％。
15.一种洗碗洗涤剂组合物，其包含：
(a)1-20重量％至少一种根据权利要求1-14中任一项的改性聚天冬氨酸；
(b)0-50重量％配位剂；
(c)0.1-80重量％助洗剂和/或共助洗剂；
(d)0.1-20重量％非离子表面活性剂；
(e)0-30重量％漂白剂和漂白活化剂；
(f)0-8重量％酶；和
(g)0-50重量％添加剂。
16.根据权利要求15的洗碗洗涤剂组合物，其中所述组合物适于机器洗碗机。
17.根据权利要求15或16的洗碗洗涤剂组合物，包含：
(a)2-12重量％至少一种根据权利要求1-14中任一项的改性聚天冬氨酸；
(b)3-50重量％甲基甘氨酸二乙酸及其盐；
(c)15-65重量％助洗剂和/或共助洗剂；
(d)0.5-10重量％非离子表面活性剂；
(e)0-30重量％漂白剂和漂白活化剂；
(f)0-8重量％酶；和
(g)0-50重量％添加剂。
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| EP13184570 | 2013-09-16 | ||
| EP13184570.3 | 2013-09-16 | ||
| PCT/EP2014/068924 WO2015036325A1 (de) | 2013-09-16 | 2014-09-05 | Verwendung modifizierter polyasparaginsäuren in spülmitteln |
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| CN105555931A CN105555931A (zh) | 2016-05-04 |
| CN105555931B true CN105555931B (zh) | 2018-11-16 |
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| US (1) | US9796951B2 (zh) |
| EP (1) | EP3047003B1 (zh) |
| JP (1) | JP2016536430A (zh) |
| KR (1) | KR20160055917A (zh) |
| CN (1) | CN105555931B (zh) |
| BR (1) | BR112016005594B1 (zh) |
| CA (1) | CA2923744A1 (zh) |
| ES (1) | ES2851207T3 (zh) |
| MX (1) | MX2016003438A (zh) |
| PL (1) | PL3047003T3 (zh) |
| RU (1) | RU2665581C2 (zh) |
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| BR112018004446B1 (pt) * | 2015-09-08 | 2022-05-03 | Basf Se | Método para produzir ácido poliaspártico |
| EP3205393A1 (en) | 2016-02-12 | 2017-08-16 | Basf Se | Process for preparation of microcapsules |
| PL3788125T3 (pl) * | 2018-05-02 | 2024-07-22 | Basf Se | Preparaty detergentowe do zmywania naczyń zawierające poli(kwas asparaginowy) i polimery szczepione na bazie oligo- i polisacharydów jako dodatki hamujące powstawanie nalotu |
| FR3095132B1 (fr) | 2019-04-19 | 2021-05-07 | Exel Ind | Applicateur de produit de revêtement, installation d’application comprenant un tel applicateur et procédé d’application au moyen d’un tel applicateur |
| WO2021228642A1 (en) | 2020-05-12 | 2021-11-18 | Basf Se | Use of carboxymethylated polymer of lysines as dispersing agent and compositions comprising the same |
| WO2022178075A1 (en) | 2021-02-19 | 2022-08-25 | Nutrition & Biosciences USA 4, Inc. | Oxidized polysaccharide derivatives |
| EP4334363A1 (en) | 2021-05-04 | 2024-03-13 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising insoluble alpha-glucan |
| WO2023287684A1 (en) | 2021-07-13 | 2023-01-19 | Nutrition & Biosciences USA 4, Inc. | Cationic glucan ester derivatives |
| CN118382421A (zh) | 2021-12-16 | 2024-07-23 | 营养与生物科学美国4公司 | 包含在水性极性有机溶剂中的阳离子α-葡聚糖醚的组合物 |
| WO2024015769A1 (en) | 2022-07-11 | 2024-01-18 | Nutrition & Biosciences USA 4, Inc. | Amphiphilic glucan ester derivatives |
| WO2024081773A1 (en) | 2022-10-14 | 2024-04-18 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising water, cationic alpha-1,6-glucan ether and organic solvent |
| WO2024129951A1 (en) | 2022-12-16 | 2024-06-20 | Nutrition & Biosciences USA 4, Inc. | Esterification of alpha-glucan comprising alpha-1,6 glycosidic linkages |
| WO2024130646A1 (en) | 2022-12-22 | 2024-06-27 | Basf Se | Carboxymethylated lysine-based polymer and compositions comprising the same |
| EP4428217A1 (en) | 2023-03-07 | 2024-09-11 | Basf Se | Graft copolymers for corrosion inhibition in an automatic dishwashing process |
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| Publication number | Publication date |
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| MX2016003438A (es) | 2016-07-21 |
| WO2015036325A1 (de) | 2015-03-19 |
| ES2851207T3 (es) | 2021-09-03 |
| JP2016536430A (ja) | 2016-11-24 |
| RU2016114687A (ru) | 2017-10-23 |
| US20160222322A1 (en) | 2016-08-04 |
| CA2923744A1 (en) | 2015-03-19 |
| BR112016005594B1 (pt) | 2021-12-07 |
| KR20160055917A (ko) | 2016-05-18 |
| RU2016114687A3 (zh) | 2018-03-22 |
| US9796951B2 (en) | 2017-10-24 |
| BR112016005594A2 (pt) | 2017-08-01 |
| EP3047003B1 (de) | 2020-11-11 |
| RU2665581C2 (ru) | 2018-08-31 |
| CN105555931A (zh) | 2016-05-04 |
| EP3047003A1 (de) | 2016-07-27 |
| PL3047003T3 (pl) | 2021-05-04 |
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