发明领域field of invention
本发明涉及一种工业二合一清洁组合物，其在单个清洁组合物中提供了去垢性和漂洗助剂两种效力。具体的，组合物和制造和使用其的方法二者提供了用户友好的，固体去垢剂组合物，而无需使用单独的漂洗助剂组合物。该组合物和方法特别好地适用于使用碱金属碳酸盐组合物的工业清洁中，其有益地提供清洁和漂洗性，来允许使用饮用水漂洗，而不加入单独的漂洗试剂。The present invention relates to an industrial 2-in-1 cleaning composition that provides both detergency and rinse aid benefits in a single cleaning composition. In particular, both the compositions and methods of making and using the same provide user-friendly, solid detergent compositions without the use of a separate rinse aid composition. The compositions and methods are particularly well suited for use in industrial cleaning using alkali metal carbonate compositions which advantageously provide cleaning and rinsing properties to allow rinsing with potable water without the addition of separate rinsing agents.
发明背景Background of the invention
碱性去垢剂在消费者和工业洗碗机二者中广泛用于清洁制品。碱性去垢剂的广泛使用归因于它们除去和乳化脂肪，油，疏水性污垢的能力。但是，碱性去垢剂具有需要漂洗助剂来防止在与碱性去垢剂接触的玻璃和其他基底表面上形成膜的缺点。成膜部分是由于使用碱性去垢剂和某些水类型(包括硬水)和水温度的组合引起的。用于产生硬水膜的一种解决方案已经使用了漂洗助剂来除去这样的膜。但是，对漂洗助剂的需要增加了与碱性去垢剂相关的成本，用于配制清洁组合物以及与用于漂洗步骤的加热的水相关的另外的成本。Alkaline detergents are widely used in cleaning articles in both consumer and industrial dishwashers. The widespread use of alkaline detergents is attributed to their ability to remove and emulsify fatty, oily, hydrophobic soils. However, alkaline detergents have the disadvantage of requiring a rinse aid to prevent film formation on glass and other substrate surfaces that come into contact with the alkaline detergent. Filming is caused in part by the use of alkaline detergents in combination with certain water types (including hard water) and water temperatures. One solution for creating hard water films has been to use rinse aids to remove such films. However, the need for rinse aids adds to the costs associated with alkaline detergents, additional costs associated with formulating the cleaning composition and heated water for the rinse step.
此外，漂洗助剂被用于清洗周期之后的漂洗周期来增强干燥时间，以及降低任何清洁不完整(包括膜的除去)。使用漂洗助剂的另外的益处和方法描述在美国专利No.RE38262中，其在此以其全部引入作为参考。将漂洗助剂加入到器皿清洗漂洗周期中需要使用GRAS(通常公认是安全的)成分以及壁空间，用于安装去垢剂分配器和漂洗助剂分配器二者。In addition, rinse aids are used in the rinse cycle following the wash cycle to enhance drying time, as well as reduce any cleaning imperfections (including film removal). Additional benefits and methods of using rinse aids are described in US Patent No. RE38262, which is hereby incorporated by reference in its entirety. Adding rinse aid to the warewash rinse cycle requires the use of GRAS (generally recognized as safe) ingredients and wall space for both the detergent dispenser and the rinse aid dispenser.
需要可选择的，有效的清洁组合物，其提供了期望的清洁结果，同时降低了清洁和漂洗所需组分的数目。There is a need for alternative, effective cleaning compositions that provide desired cleaning results while reducing the number of components required for cleaning and rinsing.
因此，请求保护的发明的一个目标是开发一种碱性去垢剂组合物，其提供了良好的清洁性能和饮用水漂洗中良好的漂洗性，而不在漂洗周期中使用加入的漂洗助剂。It is therefore an object of the claimed invention to develop an alkaline detergent composition which provides good cleaning performance and good rinsability in potable water rinses without the use of added rinse aids in the rinse cycle.
本发明的另一目标是提供一种碳酸盐基碱性去垢剂，其使用了表面活性剂和任选的聚合物的组合，来提供良好的清洁性能和漂洗性，而不在该清洁组合物中使用漂洗助剂。Another object of the present invention is to provide a carbonate based alkaline detergent which uses a combination of surfactants and optionally polymers to provide good cleaning and rinsing properties without the presence of a detergent in the cleaning combination. use rinse aid in your laundry.
本发明的另一目标是提供一种碳酸盐基碱性去垢剂，其使用了表面活性剂和任选的聚合物的组合，其提供了与常规的两部分去垢剂和漂洗助剂至少基本上类似的清洁和漂洗效力。Another object of the present invention is to provide a carbonate based alkaline detergent using a combination of surfactants and optionally polymers which provides At least substantially similar cleaning and rinsing efficacy.
本发明的其他目标，优点和特征将从下面的说明书，结合附图而变得显而易见。Other objects, advantages and features of the present invention will become apparent from the following description, taken in conjunction with the accompanying drawings.
发明内容Contents of the invention
本发明的一个优点是工业去垢剂组合物，其在单个清洁组合物中提供去垢性和漂洗性二者，因此消除了对于另外的漂洗助剂组合物的需要。本发明的组合物因此了一种用户友好的，固体二合一清洁和漂洗作用，有益地消除了工业器皿清洗组合物和使用方法中不同的漂洗助剂。本发明的碱性去垢剂组合物有益地提供了良好的清洁性能和饮用水漂洗的漂洗性二者，而在漂洗周期中不使用加入的漂洗助剂。An advantage of the present invention is an industrial detergent composition that provides both detergency and rinse performance in a single cleaning composition, thus eliminating the need for an additional rinse aid composition. The compositions of the present invention thus provide a user-friendly, solid 2-in-1 cleaning and rinsing action, beneficially eliminating the need for different rinse aids in industrial warewashing compositions and methods of use. The alkaline detergent compositions of the present invention advantageously provide both good cleaning performance and potable rinse rinsability without the use of added rinse aids during the rinse cycle.
在一种实施方案中，本发明提供一种组合物，其包含碳酸盐碱度源和相组合的非离子表面活性剂，这里该组合物取代了分别使用洗碗机去垢剂和漂洗添加剂二者，这归因于该组合物优异的清洁和漂洗性。该去垢剂组合物还可以包括聚合物例如聚羧酸聚合物，增效剂，水调节剂，中和剂，杀菌剂等。In one embodiment, the present invention provides a composition comprising a source of carbonate alkalinity and a nonionic surfactant in combination, where the composition replaces the separate use of a dishwasher detergent and a rinse additive Both, this is due to the excellent cleaning and rinsing properties of the composition. The detergent composition may also include polymers such as polycarboxylate polymers, builders, water conditioners, neutralizers, bactericides, and the like.
在另一实施方案中，本发明提供一种在工业洗碗机中，使用包含碱金属碳酸盐和非离子表面活性剂的碳酸盐基碱性去垢剂来清洁制品的方法。本发明还涉及一种在工业洗碗机中，使用下面的步骤来清洁制品的方法：供给碱性二合一组合物，将该组合物添加入洗碗机的分配器中，用该组合物和水形成清洗溶液，将洗碗机中制品上的污垢与清洗溶液接触，除去该污垢，和使用相同的碱性二合一清洁组合物漂洗该制品，不使用另外的漂洗助剂。In another embodiment, the present invention provides a method of cleaning an article in an industrial dishwasher using a carbonate-based alkaline detergent comprising an alkali metal carbonate and a nonionic surfactant. The invention also relates to a method for cleaning articles in an industrial dishwasher using the following steps: feeding an alkaline two-in-one composition, adding the composition to the dispenser of the dishwasher, using the composition Forming a cleaning solution with water, contacting the soil on an article in a dishwasher with the cleaning solution, removing the soil, and rinsing the article using the same alkaline 2-in-1 cleaning composition without additional rinse aid.
虽然公开了多个实施方案，但是本发明仍然的其他实施方案将从下面的详细说明而对本领域技术人员变得显而易见，其显示和描述了本发明的示例性实施方案。因此，附图和详细说明被认为是示例性的，而非限制性的。While multiple embodiments are disclosed, still other embodiments of the invention will become apparent to those skilled in the art from the following detailed description, which shows and describes exemplary embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative rather than restrictive.
附图说明Description of drawings
图1显示了作为在使用浓度的平均气泡寿命的函数，在160°F的温度下，实验配方(Exp.1)与磷酸盐基碱性去垢剂以及非离子基漂洗助剂相比的平均动态表面张力的图。所示的值是三个独立测量值的平均。根据本发明的一种实施方案，该实验配方显示了表面张力的快速降低和明显下降，其类似于表现良好的市售漂洗助剂，例如漂洗助剂对照2。Figure 1 shows the average bubble life at 160°F for the experimental formulation (Exp. Diagram of dynamic surface tension. The values shown are the average of three independent measurements. According to one embodiment of the invention, the experimental formulation showed a rapid and significant drop in surface tension, similar to well-performing commercial rinse aids, such as Rinse Aid Control 2.
图2显示了作为在使用浓度的平均气泡寿命的函数，在160°F的温度下，实验配方(Exp.2)与磷酸盐基碱性去垢剂以及非离子基漂洗助剂相比的平均动态表面张力的图。所示的值是三个独立测量值的平均。根据本发明的一种实施方案，该实验配方显示了表面张力的快速降低和明显下降，其类似于表现良好的市售漂洗助剂，例如漂洗助剂对照2。Figure 2 shows the average bubble life at 160°F for the experimental formulation (Exp. Diagram of dynamic surface tension. The values shown are the average of three independent measurements. According to one embodiment of the invention, the experimental formulation showed a rapid and significant drop in surface tension, similar to well-performing commercial rinse aids, such as Rinse Aid Control 2.
本发明的不同的实施方案将参考附图来详细描述，其中在几个图中，相同的附图标记代表了相同的零件。提及不同的实施方案并非限制本发明的范围。本文所示的图不限于本发明的不同的实施方案，并且提出以示例性说明本发明。Various embodiments of the invention will be described in detail with reference to the drawings, wherein like reference numerals represent like parts throughout the several views. Reference to different embodiments does not limit the scope of the invention. The figures shown here are not limited to the different embodiments of the invention, but are presented to illustrate the invention.
具体实施方式detailed description
本发明涉及一种二合一工业碱性清洁组合物，其提供了合适的清洁和漂洗性，同时使用了碳酸盐基碱性去垢剂和表面活性剂的组合。在一种示例性实施方案中，该非离子表面活性剂用饮用水产生了有效的含水漂洗。本发明的该实施方案不限于具体的碱性去垢剂，其可以变化，并且是本领域技术人员基于本文提供的公开内容所理解的。进一步要理解的是本文所用的全部术语目的仅仅是描述具体的实施方案，并非打算以任何方式或者范围进行限定。例如，作为本说明书和附加的权利要求中所用的，单数形式不定冠词“一个”、“一种”(“a”，“an”)和定冠词“该”可以包括复数指代物，除非该内容另有明确指示。此外，全部的单位、前缀和符号可以以它的SI接受形式来表示。The present invention relates to a 2-in-1 industrial alkaline cleaning composition which provides suitable cleaning and rinsing while utilizing a combination of carbonate-based alkaline detergents and surfactants. In an exemplary embodiment, the nonionic surfactant produces an effective aqueous rinse with potable water. This embodiment of the invention is not limited to a particular alkaline detergent, which can vary and is understood by those skilled in the art based on the disclosure provided herein. It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any way or scope. For example, as used in this specification and the appended claims, the singular forms of the indefinite articles "a", "an" ("a", "an") and the definite article "the" may include plural referents unless This content expressly indicates otherwise. Additionally, all units, prefixes and symbols may be expressed in their SI accepted form.
说明书中所述的数字范围包含了定义该范围的数字，并且包括处于所定义范围内的每个整数。在整个本发明中，本发明不同的方面是以范围形式提出的。应当理解范围形式的表述仅仅是为了方便和简明，并且不应当解释为对于本发明范围的生硬限制。因此，范围的表述应当被认为明确公开了全部可能的子范围以及该范围内的单个数值。例如，范围例如1-6的表述应当被认为明确公开了子范围例如1-3，1-4，1-5，2-4，2-6，3-6等，以及该范围内的单个数字例如1，2，3，4，5和6。不管该范围的宽度如何，这都是适用的。Numerical ranges stated in the specification are inclusive of the numbers defining the range and include every integer within the defined range. Throughout this disclosure, various aspects of this invention are presented in a range format. It should be understood that the expression in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the expression of a range should be considered as expressly disclosing all possible subranges as well as individual values within that range. For example, the recitation of a range such as 1-6 should be read as expressly disclosing subranges such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc., as well as individual numbers within that range. For example 1, 2, 3, 4, 5 and 6. This applies regardless of the width of the range.
这样首先定义某些术语时，可以更容易的理解本发明。除非另有规定，否则本文所用的全部科技术语具有与本发明实施方案所属领域技术人员通常的理解相同的含义。许多类似于、改变或等价于本文所述那些的方法和材料可以用于本发明实施方案的实践中，而无需过度实验，优选的材料和方法是本文所述的。在描述和要求保护本发明的实施方案中，下面的术语将根据下述定义来使用。This makes it easier to understand the invention when certain terms are first defined. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of the invention belong. Many methods and materials similar, modified, or equivalent to those described herein can be used in the practice of embodiments of the invention without undue experimentation, the preferred materials and methods being described herein. In describing and claiming embodiments of the present invention, the following terminology will be used in accordance with the following definitions.
作为本文使用的，术语“大约”指的是数量中的变化，其可以例如通过在真实世界中用于制造浓缩物或者使用溶液的典型的测量和液体处理程序；通过这些程序中无意的误差；通过用于制造该组合物或进行该方法的成分的制造，来源或者纯度的差异等而发生。术语“大约”还包括这样的量，其因为由具体初始混合物所形成的组合物的不同的平衡条件而不同。无论是否用术语“大约”修正，权利要求都包括等价量。As used herein, the term "approximately" refers to variations in quantities which can be measured, for example, by typical measurement and liquid handling procedures used in the real world to manufacture concentrates or use solutions; through unintentional errors in such procedures; Occurs through differences in the manufacture, source or purity, etc., of the ingredients used to make the composition or perform the method. The term "about" also includes amounts that vary due to the different equilibrium conditions of the composition formed from the particular initial mixture. Whether or not modified by the term "about," the claims include equivalents.
术语“活性物”或者“活性物百分比”或者“活性物重量百分比”或者“活性物浓度”在此可交替使用，并且指的是清洁中所涉及的那些成分的浓度，表达为减去惰性成分例如水或盐的百分比。The terms "active" or "active percent" or "active weight percent" or "active concentration" are used interchangeably herein and refer to the concentration of those ingredients involved in cleaning, expressed as minus the inert ingredients For example the percentage of water or salt.
作为本文使用的，术语“烷基”指的是直链或者支链单价烃基，任选含有独立地选自S，O，Si或者N的一种或多种杂原子取代基。烷基通常包括具有1-20个原子的那些。烷基可以是未取代的或者用那些取代基取代的，所述那些取代基不干扰组合物规定的功能。取代基包括例如烷氧基，羟基，巯基，氨基，烷基取代的氨基，或者卤素。作为本文使用的，“烷基”的例子包括但不限于甲基，乙基，正丙基，正丁基，正戊基，异丁基，异丙基和C8-C20烷基链等。另外，“烷基”可以包括“亚烷基”，“亚烯基”或者“亚炔基(alkylynes)”。As used herein, the term "alkyl" refers to a linear or branched monovalent hydrocarbon group, optionally containing one or more heteroatom substituents independently selected from S, O, Si or N. Alkyl groups generally include those having 1-20 atoms. Alkyl groups may be unsubstituted or substituted with those substituents that do not interfere with the stated function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halo. As used herein, examples of "alkyl" include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, isopropyl and C8-C20 alkyl chains and the like. Additionally, "alkyl" may include "alkylene", "alkenylene" or "alkylynes".
作为本文使用的，术语“亚烷基”指的是直链或者支链二价烃基，任选含有独立地选自S，O，Si或者N的一种或多种杂原子取代基。亚烷基通常包括具有1-20个原子的那些。亚烷基可以是未取代的或者用那些取代基取代的，所述那些取代基不干扰组合物规定的功能。取代基包括例如烷氧基，羟基，巯基，氨基，烷基取代的氨基，或者卤素。作为此处使用的，“亚烷基”的例子包括但不限于亚甲基，亚乙基，丙-1,3-二基，丙-1,2-二基等。As used herein, the term "alkylene" refers to a straight or branched chain divalent hydrocarbon group, optionally containing one or more heteroatom substituents independently selected from S, O, Si or N. Alkylene groups generally include those having 1-20 atoms. The alkylene group may be unsubstituted or substituted with those substituents which do not interfere with the stated function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halo. As used herein, examples of "alkylene" include, but are not limited to, methylene, ethylene, prop-1,3-diyl, prop-1,2-diyl, and the like.
作为本文使用的，术语“亚烯基”指的是直链或者支链二价烃基，其具有一个或多个碳-碳双键和任选含有独立地选自S，O，Si或者N的一种或多种杂原子取代基。亚烯基通常包括具有1-20个原子的那些。亚烯基可以是未取代的或者用那些取代基取代的，所述那些取代基不干扰组合物规定的功能。取代基包括例如烷氧基，羟基，巯基，氨基，烷基取代的氨基，或者卤素。作为本文使用的，“亚炔基”指的是直链或者支链二价烃基，具有一个或多个碳-碳叁键和任选含有独立地选自S，O，Si或者N的一种或多种杂原子取代基。亚炔基通常包括具有1-20个原子的那些。亚炔基可以是未取代的或者用那些取代基取代的，所述那些取代基不干扰组合物规定的功能。取代基包括例如烷氧基，羟基，巯基，氨基，烷基取代的氨基，或者卤素。As used herein, the term "alkenylene" refers to a linear or branched divalent hydrocarbon radical having one or more carbon-carbon double bonds and optionally containing One or more heteroatom substituents. Alkenylene groups generally include those having 1-20 atoms. The alkenylene group may be unsubstituted or substituted with those substituents which do not interfere with the stated function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halo. As used herein, "alkynylene" refers to a straight-chain or branched divalent hydrocarbon radical having one or more carbon-carbon triple bonds and optionally containing one type independently selected from S, O, Si or N. or multiple heteroatom substituents. Alkynylene groups generally include those having 1-20 atoms. Alkynylene groups can be unsubstituted or substituted with those substituents that do not interfere with the stated function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halo.
作为本文使用的，术语“烷氧基”指的是--O--烷基，其中烷基如上定义。作为本文使用的，术语“清洁”指的是用于用于促使或者帮助污垢除去，漂白，微生物数量降低及其任意组合的方法。As used herein, the term "alkoxy" refers to --O--alkyl, wherein alkyl is as defined above. As used herein, the term "cleaning" refers to methods used to facilitate or facilitate soil removal, bleaching, microbial population reduction, and any combination thereof.
作为本文使用的，术语“通常公认为安全的”或者“GRAS”指的是被美国食品药品局归类为对于直接人食品消耗来说安全的成分或者基于目前的食品制造实际使用条件的成分，如21C.F.R.第1章，§170.38和/或570.38所定义的。As used herein, the term "generally recognized as safe" or "GRAS" refers to an ingredient classified by the U.S. Food and Drug Administration as safe for direct human food consumption or based on current food manufacturing practice for use, As defined in 21 C.F.R. Title 1, §170.38 and/or 570.38.
作为本文使用的，术语“污垢”或“污点”指的是极性或非极性物质，其可以或者可以不包含微粒物质例如但不限于矿物粘土，沙子，天然矿物，炭黑，石墨，高岭土，环境灰尘和食物污垢例如多酚淀粉，蛋白质，油和脂肪等。As used herein, the term "dirt" or "stain" refers to polar or non-polar matter which may or may not contain particulate matter such as but not limited to mineral clay, sand, natural minerals, carbon black, graphite, kaolin , environmental dust and food dirt such as polyphenolic starch, protein, oil and fat, etc.
作为本文使用的，术语“基本上不含”指的是组合物完全缺乏所述组分或者具有少量该组分，以使得该组分不影响组合物的性能。该组分可以作为杂质或者作为污染物存在，并且应当小于0.5wt％。在另外一种实施方案中，该组分的量小于0.1wt％和在仍然另一实施方案中，该组分量小于0.01wt％。As used herein, the term "substantially free" means that the composition is completely devoid of the component or has such a small amount of the component that the component does not affect the properties of the composition. This component may be present as an impurity or as a contaminant and should be less than 0.5 wt%. In another embodiment, the amount of this component is less than 0.1 wt% and in still another embodiment, the amount of this component is less than 0.01 wt%.
术语“基本上类似的清洁性能”通常指通过通常相同的清洁程度(或者至少不明显更低的程度)或者以通常相同的工作付出(或者至少不明显更低的付出)或者二者的替代的清洁产品或者替代的清洁体系所实现的。The term "substantially similar cleaning performance" generally refers to cleaning by generally the same degree (or at least not significantly lower degree) or with generally the same effort (or at least not significantly lower effort) or the substitution of both Achieved by cleaning products or alternative cleaning systems.
术语“阈值剂”指的是这样的化合物，其抑制了水硬度离子从溶液中结晶，但是其不需要与水硬度离子形成特定的络合物。阈值剂包括但不限于聚丙烯酸(酯/盐)，聚甲基丙烯酸(酯/盐)，烯烃/马来酸共聚物等。The term "threshold agent" refers to compounds that inhibit the crystallization of water hardness ions from solution, but which do not require the formation of specific complexes with water hardness ions. Threshold agents include, but are not limited to, polyacrylic acid (ester/salt), polymethacrylic acid (ester/salt), olefin/maleic acid copolymer, and the like.
作为本文使用的，术语“器皿”指的是物品例如食用和烹饪器皿和盘子。作为本文使用的，术语“器皿清洗”指的是清洗、清洁或者漂洗器皿。器皿也指的是塑料制成的物品。能够用本发明的组合物清洁的塑料的类型包括但不限于那些，其包括聚碳酸酯聚合物(PC)，丙烯腈-丁二烯-苯乙烯聚合物(ABS)和聚砜聚合物(PS)。其他示例性塑料(其可以使用本发明的化合物和组合物清洁)包括聚对苯二甲酸乙二醇酯(PET)和来自于蜜胺树脂的塑料。As used herein, the term "vessel" refers to items such as eating and cooking utensils and plates. As used herein, the term "warewashing" refers to washing, cleaning or rinsing dishes. Utensils also refer to items made of plastic. Types of plastics that can be cleaned with the compositions of the present invention include, but are not limited to, those that include polycarbonate polymers (PC), acrylonitrile-butadiene-styrene polymers (ABS) and polysulfone polymers (PS ). Other exemplary plastics that can be cleaned using the compounds and compositions of the present invention include polyethylene terephthalate (PET) and plastics derived from melamine resins.
作为本文使用的，“重量百分比”、“wt％”、“百分比重量”、“重量％”及其变体指的是物质的浓度，其是该物质的重量除以组合物的总重量，并且乘以100。应当理解作为本文使用的，“百分比”、“％”等目的是与“重量百分比”、“wt％”等同义的。As used herein, "weight percent", "wt%", "percent weight", "wt%" and variations thereof refer to the concentration of a substance which is the weight of the substance divided by the total weight of the composition, and Multiply by 100. It should be understood that as used herein, "percent", "%" and the like are intended to be synonymous with "weight percent", "wt%" and the like.
本发明的方法和组合物可以包含，基本组成为或者组成为本发明的组分和成分以及本文所述的其他成分。作为本文使用的，“基本组成为”表示所述方法和组合物可以包括另外的步骤，组分或者成分，但是仅仅当该另外的步骤，组分或者成分不实质性改变要求保护的方法和组合物的基本的和新的特性。The methods and compositions of the invention can comprise, consist essentially of, or consist of, the components and ingredients of the invention as well as other ingredients described herein. As used herein, "consisting essentially of" means that the methods and compositions described may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not substantially alter the claimed methods and combinations Basic and new properties of things.
碱性二合一去垢剂组合物Alkaline 2-in-1 Detergent Composition
碱度源Alkalinity source
该碱性去垢剂组合物包括碱度源。碱度源包含碱金属碳酸盐。合适的碱度源的例子包括但不限于：碱金属碳酸盐，例如碳酸钠，碳酸钾，碳酸氢盐，倍半碳酸盐及其混合物。在一方面，该碱性去垢剂组合物不包括氢氧化物碱度源。当水加入到该去垢剂组合物来形成使用溶液时，该碱度源控制了使用溶液的pH。使用溶液的pH必须保持在碱性范围来提供足够的去垢性。在一种实施方案中，使用溶液的pH是大约9-大约12。具体地，该使用溶液的pH是大约9.5-大约11.5。The alkaline detergent composition includes a source of alkalinity. The source of alkalinity comprises alkali metal carbonates. Examples of suitable alkalinity sources include, but are not limited to, alkali metal carbonates such as sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof. In one aspect, the alkaline detergent composition does not include a source of hydroxide alkalinity. When water is added to the detergent composition to form a use solution, the source of alkalinity controls the pH of the use solution. The pH of the solution used must be kept in the alkaline range to provide adequate detergency. In one embodiment, the pH of the use solution is from about 9 to about 12. Specifically, the pH of the use solution is from about 9.5 to about 11.5.
在某些实施方案中，该碱度源还可以充当了可水合的盐来形成固体组合物。该可水合的盐可以称作基本上无水的。用基本上无水表示所述组分包含小于大约2重量％的水，基于该可水合的组分的重量。水的量可以小于大约1重量％，和可以小于大约0.5重量％。作为本领域技术人员将确信的，不需要该可水合的盐是完全无水的。在某些实施方案中，还存在着用于水合碱度源(即可水合的盐)的水合水。应当理解的是提及水时包括水合水和游离水二者。措词“水合水”指的是这样的水，其吸引键合到非水分子上。吸引的一种示例性形式包括氢键。水合水还用于增加混合物在加工过程中和冷却来防止组分分离过程中的粘度。去垢剂组合物中水合水的量将取决于碱度源/可水合盐。除了水合水之外，该去垢剂组合物还可以具有游离水，其不吸引键合到非水分子上。In certain embodiments, the source of alkalinity may also serve as a hydratable salt to form a solid composition. The hydratable salt can be referred to as substantially anhydrous. By substantially anhydrous is meant that the component contains less than about 2% by weight water, based on the weight of the hydratable component. The amount of water may be less than about 1% by weight, and may be less than about 0.5% by weight. As one skilled in the art will recognize, there is no need for the hydratable salt to be completely anhydrous. In certain embodiments, water of hydration for hydrating the source of alkalinity (ie, hydratable salt) is also present. It should be understood that reference to water includes both water of hydration and free water. The expression "water of hydration" refers to water that attracts bonds to non-water molecules. One exemplary form of attraction includes hydrogen bonding. Water of hydration is also used to increase the viscosity of the mixture during processing and cooling to prevent separation of the components. The amount of water of hydration in the detergent composition will depend on the source of alkalinity/hydratable salt. In addition to water of hydration, the detergent composition may also have free water, which does not attract bonds to non-water molecules.
在一方面，该碱性去垢剂组合物包括大约10wt％-95wt％的碱度源，大约25wt％-90wt％碱度源，大约40wt％-85wt％碱度源，优选大约45wt％-75wt％碱度源。另外，不限制本发明，全部所述范围包括定义该范围的数字，并且包括所定义范围内的每个整数。In one aspect, the alkaline detergent composition comprises about 10 wt %-95 wt % alkalinity source, about 25 wt %-90 wt % alkalinity source, about 40 wt %-85 wt % alkalinity source, preferably about 45 wt %-75 wt % % Alkalinity source. Additionally, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
表面活性剂Surfactant
本发明的二合一碱性组合物使用表面活性剂的组合来提供良好的清洁性和漂洗性。在一种实施方案中，碱性去垢剂组合物的表面活性剂包括至少两种非离子表面活性剂。在实施方案中，该非离子表面活性剂包含醇烷氧基化物和烷基烷氧基化物。在仍然另外的实施方案中，该非离子表面活性剂选自醇烷氧基化物，烷基烷氧基化物，EO/PO共聚物及其组合。在一方面，该碱性去垢剂组合物包括大约0.1wt％-30wt％的表面活性剂，大约0.1wt％-25wt％的表面活性剂，大约0.1wt％-20wt％的表面活性剂，大约1wt％-15wt％的表面活性剂，大约1wt％-10wt％的表面活性剂和优选大约5wt％-10wt％的表面活性剂。另外，不限制本发明，全部所述范围包括定义该范围的数字，并且包括所定义范围内的每个整数。The 2-in-1 alkaline composition of the present invention uses a combination of surfactants to provide good cleaning and rinsing. In one embodiment, the surfactants of the alkaline detergent composition comprise at least two nonionic surfactants. In embodiments, the nonionic surfactant comprises alcohol alkoxylates and alkyl alkoxylates. In still other embodiments, the nonionic surfactant is selected from alcohol alkoxylates, alkyl alkoxylates, EO/PO copolymers, and combinations thereof. In one aspect, the alkaline detergent composition comprises about 0.1 wt %-30 wt % surfactant, about 0.1 wt %-25 wt % surfactant, about 0.1 wt %-20 wt % surfactant, about 1 wt% to 15 wt% surfactant, about 1 wt% to 10 wt% surfactant and preferably about 5 wt% to 10 wt% surfactant. Additionally, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
在一些实施方案中，醇烷氧基化物与烷基烷氧基化物的比率是大约1：5-大约5：1，大约1：3-大约3：1，大约1：2-大约2：1和优选大约1：1。在一种示例性实施方案中，该非离子表面活性剂包括下面比率的烷基烷氧基化物和醇烷氧基化物：大约1：1，大约1：5-大约5：1，大约1：3-大约3：1，或者大约1：2-大约2：1。在一个优选的方面中，该碱性去垢剂组合物包括比率大约1：1的烷基烷氧基化物和醇烷氧基化物。In some embodiments, the ratio of alcohol alkoxylate to alkyl alkoxylate is about 1:5 to about 5:1, about 1:3 to about 3:1, about 1:2 to about 2:1 and preferably about 1:1. In an exemplary embodiment, the nonionic surfactant comprises alkyl alkoxylate and alcohol alkoxylate in the following ratio: about 1:1, about 1:5 to about 5:1, about 1: 3 - about 3:1, or about 1:2 - about 2:1. In a preferred aspect, the alkaline detergent composition comprises alkyl alkoxylate and alcohol alkoxylate in a ratio of about 1:1.
醇烷氧基化物alcohol alkoxylate
本发明的二合一碱性组合物使用包括醇烷氧基化物的至少两种非离子表面活性剂。合适的醇烷氧基化物包括氧亚乙基，氧亚丙基和氧亚丁基基团及其混合物。具体的，合适的醇烷氧基化物可以具有大约1-大约30mol的烷基化氧和大约4-大约20个碳长度的碳链。在一种优选的实施方案中，该醇乙氧基化物可以是C8–C18醇烷氧基化物，具有大约10-大约40mol的烷基化氧。在一种更优选的实施方案中，该醇烷氧基化物可以是C8-C16醇烷氧基化物，具有大约10-大约30mol的烷基化氧。在一种甚至更优选的实施方案中，该醇烷氧基化物可以是C10-C12醇烷氧基化物，具有大约15-大约25mol的烷基化氧。优选的醇烷氧基化物的例子是在商标Surfonic(获自Huntsman)，Rhodasurf(获自Rhodia)，Novel(获自Sasol)，Lutensol(获自BASF)下市售的。The two-in-one alkaline composition of the present invention utilizes at least two nonionic surfactants including alcohol alkoxylates. Suitable alcohol alkoxylates include oxyethylene, oxypropylene and oxybutylene groups and mixtures thereof. In particular, suitable alcohol alkoxylates can have from about 1 to about 30 moles of alkyl oxide and carbon chains of from about 4 to about 20 carbons in length. In a preferred embodiment, the alcohol ethoxylate may be a C8-C18 alcohol alkoxylate having from about 10 to about 40 moles of alkylated oxygen. In a more preferred embodiment, the alcohol alkoxylate may be a C8-C16 alcohol alkoxylate having from about 10 to about 30 moles of alkylated oxygen. In an even more preferred embodiment, the alcohol alkoxylate may be a C10-C12 alcohol alkoxylate having from about 15 to about 25 moles of alkylated oxygen. Examples of preferred alcohol alkoxylates are commercially available under the trademarks Surfonic (ex Huntsman), Rhodasurf (ex Rhodia), Novel (ex Sasol), Lutensol (ex BASF).
在本发明的一方面，该碱性去垢剂组合物包括大约0.1wt％-大约15wt％的醇烷氧基化物，大约0.1wt％-大约10wt％的醇烷氧基化物，大约0.1wt％-大约7wt％，或者大约1wt％-大约49wt％。In one aspect of the present invention, the alkaline detergent composition comprises about 0.1 wt % to about 15 wt % alcohol alkoxylate, about 0.1 wt % to about 10 wt % alcohol alkoxylate, about 0.1 wt % - about 7 wt%, or about 1 wt% - about 49 wt%.
烷基烷氧基化物Alkyl alkoxylates
本发明的二合一碱性组合物使用烷基烷氧基化物。具有环氧乙烷和/或环氧丙烷衍生物的烷基烷氧基化物特别适于碱性组合物。在其他实施方案中，该烷基烷氧基化物包括环氧乙烷，环氧丙烷，环氧丁烷，环氧戊烷，环氧己烷，环氧庚烷，环氧辛烷，环氧壬烷，环氧癸烷及其混合物。该烷基可以是线性或支化的C8-C18。The two-in-one alkaline composition of the present invention utilizes alkyl alkoxylates. Alkyl alkoxylates with ethylene oxide and/or propylene oxide derivatives are particularly suitable for alkaline compositions. In other embodiments, the alkyl alkoxylates include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptane oxide, octene oxide, epoxy Nonane, Decane Oxide and mixtures thereof. The alkyl group can be linear or branched C8-C18.
在本发明的一种实施方案中，该烷基烷氧基化物可以是EO/PO共聚物。该EO/PO共聚物可以具有大约1-大约50mol的EO和大约1-大约50mol的PO。在一种优选的实施方案中，该EO/PO共聚物是嵌段聚合物。在本发明的另一方面，该EO/PO共聚物不包含C8-18烷基，或者甚至任何烷基。In one embodiment of the invention, the alkyl alkoxylate may be an EO/PO copolymer. The EO/PO copolymer may have from about 1 to about 50 moles of EO and from about 1 to about 50 moles of PO. In a preferred embodiment, the EO/PO copolymer is a block polymer. In another aspect of the invention, the EO/PO copolymer does not contain C8-18 alkyl groups, or even any alkyl groups.
这些EO/PO共聚物表面活性剂可以包括紧凑醇EO/PO表面活性剂，其中该EO和PO基团处于小嵌段形式或者无规形式。在其他实施方案中，该烷基烷氧基化物包括环氧乙烷，环氧丙烷，环氧丁烷，环氧戊烷，环氧己烷，环氧庚烷，环氧辛烷，环氧壬烷，环氧癸烷及其混合物。该烷基可以是线性或支化的C10-C18。在一方面，该EO/PO共聚物表面活性剂特别适用于二合一碱性组合物和相组合的醇烷氧基化物表面活性剂。示例性市售表面活性剂例如是在商标名和Pluronic R(市售自BASF)，Tetronic(获自Dow)和Surfonic(获自Huntsman)下市售的。These EO/PO copolymer surfactants may include compact alcohol EO/PO surfactants in which the EO and PO groups are in small blocks or in random form. In other embodiments, the alkyl alkoxylates include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptane oxide, octene oxide, epoxy Nonane, Decane Oxide and mixtures thereof. The alkyl group can be linear or branched C10-C18. In one aspect, the EO/PO copolymer surfactants are particularly useful in two-in-one alkaline compositions and combined alcohol alkoxylate surfactants. Exemplary commercially available surfactants are, for example, listed under the trade name and Pluronic R (commercially available from BASF), Tetronic (available from Dow) and Surfonic (available from Huntsman).
可以使用的环氧乙烷和/或环氧丙烷衍生物表面活性剂的一些例子包括聚氧乙烯-聚氧丙烯嵌段共聚物等，或者其衍生物。聚氧乙烯-聚氧丙烯嵌段共聚物的一些例子包括下式的那些：Some examples of ethylene oxide and/or propylene oxide derivative surfactants that can be used include polyoxyethylene-polyoxypropylene block copolymers, etc., or derivatives thereof. Some examples of polyoxyethylene-polyoxypropylene block copolymers include those of the formula:
(EO)x(PO)y(EO)x(EO)x(PO)y(EO)x
(PO)y(EO)x(PO)y(PO)y(EO)x(PO)y
(PO)y(EO)x(PO)y(EO)x(PO)y(PO)y (EO)x (PO)y (EO)x (PO)y
其中EO代表氧亚乙基基团，PO代表氧亚丙基基团，和x和y反映了在整个嵌段共聚物组合物中，每种氧亚烷基单体的平均分子比例。在本发明的一方面，一种优选的EO/PO共聚物是式(EO)x(PO)y(EO)x所示的。在本发明的另一方面，一种优选的EO/PO共聚物是式(PO)y(EO)x(PO)y所示的。在一些实施方案中，x是大约5-大约50，y是大约1-大约50，和x+y是大约6-大约200。应当理解分子中每个x和y可以是不同的。在一些实施方案中，该材料的分子量可以大于大约200和小于大约25000。例如在一些实施方案中，该材料的分子量可以是大约500-大约25000，或者大约1000-大约20000。where EO represents an oxyethylene group, PO represents an oxypropylene group, and x and y reflect the average molecular ratio of each oxyalkylene monomer in the overall block copolymer composition. In one aspect of the invention, a preferred EO/PO copolymer is of the formula (EO)x(PO)y(EO)x. In another aspect of the invention, a preferred EO/PO copolymer is of the formula (PO)y(EO)x(PO)y. In some embodiments, x is about 5 to about 50, y is about 1 to about 50, and x+y is about 6 to about 200. It should be understood that each x and y may be different in the numerator. In some embodiments, the molecular weight of the material can be greater than about 200 and less than about 25,000. For example, in some embodiments, the molecular weight of the material may be from about 500 to about 25,000, or from about 1,000 to about 20,000.
在一些实施方案中，该EO/PO表面活性剂可以具有大约1-大约50个氧亚乙基基团和大约1-大约50个氧亚丙基基团。在一些实施方案中，该材料的分子量可以大于大约400，和在一些实施方案大于大约500。例如在一些实施方案中，该材料的分子量(g/mol)可以是大约500-大约7000或者更大，或者大约950-大约4000或更大，或者大约1000-大约3100或更大，或者大约2100-大约6700或更大，或者大约2500-大约4200或更大。In some embodiments, the EO/PO surfactant can have from about 1 to about 50 oxyethylene groups and from about 1 to about 50 oxypropylene groups. In some embodiments, the molecular weight of the material may be greater than about 400, and in some embodiments greater than about 500. For example, in some embodiments, the material may have a molecular weight (g/mol) of about 500 to about 7000 or greater, or about 950 to about 4000 or greater, or about 1000 to about 3100 or greater, or about 2100 - about 6700 or greater, or about 2500 - about 4200 or greater.
论文Nonionic Surfactants，由Schick，M.J.编辑，Surfactant Science Series第1卷，Marcel Dekker，Inc.，纽约，1983提供了通常用于本发明实践中的非离子化合物的进一步的说明。一种典型的非离子种类的列表和这些表面活性剂的物质是在1975年12月30日授予Laughlin和Heuring的美国专利No.3929678中给出的。另外的例子在“SurfaceActive Agents and detergents”(第I和II卷，Schwartz，Perry和Berch)中给出。每个这些参考文献在此以其全部引入作为参考。The paper Nonionic Surfactants, edited by Schick, M.J., Surfactant Science Series Vol. 1, Marcel Dekker, Inc., New York, 1983 provides further description of nonionic compounds generally used in the practice of this invention. A list of typical nonionic species and species of such surfactants is given in US Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Additional examples are given in "Surface Active Agents and detergents" (Volumes I and II, Schwartz, Perry and Berch). Each of these references is hereby incorporated by reference in its entirety.
在本发明的一方面，该碱性去垢剂组合物包括大约0.1wt％-大约15wt％的烷基烷氧基化物，大约0.1wt％-大约10wt％的烷基烷氧基化物，或者大约0.1wt％-大约7wt％的烷基烷氧基化物。In one aspect of the present invention, the alkaline detergent composition comprises from about 0.1 wt % to about 15 wt % of an alkyl alkoxylate, from about 0.1 wt % to about 10 wt % of an alkyl alkoxylate, or about 0.1 wt% to about 7 wt% alkyl alkoxylate.
聚合物polymer
本发明可以包括聚合物，其包含至少一种的聚羧酸聚合物，共聚物和/或三元共聚物。特别合适的本发明的聚羧酸聚合物包括但不限于聚丙烯酸聚合物和共聚物，聚马来酸聚合物和共聚物，和丙烯酸/马来酸共聚物。其他合适的聚羧酸聚合物包括聚马来酸均聚物，聚丙烯酸共聚物，和马来酸酐/烯烃共聚物。在一种优选的实施方案中，该聚合物包含，基本组成为或者组成为聚丙烯酸聚合物，共聚物，三元共聚物和/或其盐。The present invention may include polymers comprising at least one polycarboxylic acid polymer, copolymer and/or terpolymer. Particularly suitable polycarboxylic acid polymers of the present invention include, but are not limited to, polyacrylic acid polymers and copolymers, polymaleic acid polymers and copolymers, and acrylic acid/maleic acid copolymers. Other suitable polycarboxylic acid polymers include polymaleic acid homopolymers, polyacrylic acid copolymers, and maleic anhydride/olefin copolymers. In a preferred embodiment, the polymer comprises, consists essentially of or consists of polyacrylic acid polymers, copolymers, terpolymers and/or salts thereof.
本发明的去垢剂组合物可以使用聚丙烯酸聚合物，共聚物和/或三元共聚物。聚丙烯酸具有下面的结构式：The detergent compositions of the present invention may employ polyacrylic acid polymers, copolymers and/or terpolymers. Polyacrylic acid has the following structural formula:
这里n是任意整数。合适的聚丙烯酸聚合物，共聚物和/或三元共聚物的例子包括但不限于聚丙烯酸，(C3H4O2)n或者2-丙烯酸，丙烯酸，聚丙烯酸，丙烯酸的聚合物，共聚物和/或三元共聚物。Here n is any integer. Examples of suitable polyacrylic acid polymers, copolymers and/or terpolymers include but are not limited to polyacrylic acid, (C3 H4 O2 )n or 2-acrylic acid, acrylic acid, polyacrylic acid, polymers of acrylic acid, copolymer and/or terpolymers.
在本发明的一种实施方案中，特别合适的丙烯酸聚合物，共聚物和/或三元共聚物的分子量是大约100-大约10000，在一种优选的实施方案中是大约500-大约7000，在一种甚至更优选的实施方案是大约1000-大约5000，和在一种最优选的实施方案中是大约1500-大约4500。In one embodiment of the invention, particularly suitable acrylic polymers, copolymers and/or terpolymers have a molecular weight of from about 100 to about 10,000, in a preferred embodiment from about 500 to about 7,000, From about 1000 to about 5000 in an even more preferred embodiment, and from about 1500 to about 4500 in a most preferred embodiment.
聚马来酸(C4H2O3)x或者水解的聚马来酸酐或者顺式-2-丁烯二酸均聚物具有结构式：Polymaleic acid (C4 H2 O3 )x or hydrolyzed polymaleic anhydride or cis-2-butenedioic acid homopolymer has the formula:
这里n和m是任意整数。可以用于本发明的聚马来酸均聚物，共聚物和/或三元共聚物(及其盐)的例子特别优选是那些，其分子量是大约100-大约10000，更优选大约500-大约7000，在一种甚至更优选的实施方案中是大约1000-大约5000和在一种最优选的实施方案中是大约1500-大约4500。市售的聚马来酸均聚物包括Belclene 200系列的马来酸均聚物(来自BWATM Water Additives，979Lakeside Parkway，Suite 925Tucker，GA 30084，美国)和Aquatreat AR-801(获自AkzoNobel)。Here n and m are arbitrary integers. Polymaleic acid homopolymer that can be used in the present invention, the example of multipolymer and/or terpolymer (and salt thereof) are particularly preferably those, and its molecular weight is about 100-about 10000, more preferably about 500-about 7000, in an even more preferred embodiment from about 1000 to about 5000 and in a most preferred embodiment from about 1500 to about 4500. Commercially available polymaleic acid homopolymers include Belclene 200 series of maleic acid homopolymers (from BWA™ Water Additives, 979 Lakeside Parkway, Suite 925 Tucker, GA 30084, USA) and Aquatreat AR-801 (available from AkzoNobel).
在一种优选的实施方案中，该聚合物是丙烯酸和马来酸的共聚物。优选丙烯酸/马来酸共聚物的分子量是大约1000-大约10000g/mol，优选分子量是大约1000-大约5000g/mol。合适的丙烯酸/马来酸共聚物的例子包括但不限于Acusol 448，来自于The DowChemical Company，Wilmington Delaware，美国。In a preferred embodiment, the polymer is a copolymer of acrylic acid and maleic acid. Preferred acrylic acid/maleic acid copolymers have a molecular weight of about 1000 to about 10000 g/mol, preferably a molecular weight of about 1000 to about 5000 g/mol. Examples of suitable acrylic/maleic copolymers include, but are not limited to, Acusol 448, ex The Dow Chemical Company, Wilmington Delaware, USA.
在使用聚合物的实施方案中，可以预期该组合物将包括下面量的聚合物：大约0.1wt％-大约50wt％，大约0.1wt％-大约40wt％，大约0.1wt％-大约30wt％，或者1wt％-大约20wt％。全部所述范围包括其中所含的数。本发明的聚合物可以包含，基本组成为或者组成为至少一种聚丙烯酸聚合物，共聚物和/或三元共聚物。另外，不限制本发明，全部所述范围包括定义所述范围的数和包括所定义范围内的每个整数。In embodiments using polymers, it is contemplated that the composition will include polymers in an amount of: about 0.1 wt% to about 50 wt%, about 0.1 wt% to about 40 wt%, about 0.1 wt% to about 30 wt%, or 1 wt% - about 20 wt%. All stated ranges are inclusive of the numbers subsumed therein. The polymers of the present invention may comprise, consist essentially of or consist of at least one polyacrylic acid polymer, copolymer and/or terpolymer. Further, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
另外的功能成分additional functional ingredients
本发明的二合一碱性组合物可以与适用于工业器皿清洗应用的不同的功能组分进一步组合。在一些实施方案中，该包括碳酸盐基碱度源和非离子表面活性剂(和/或聚合物)的碱性去垢和漂洗助剂组合物构成了去垢剂组合物的大量，或者甚至基本上全部的总重量。例如在一些实施方案中，几种或者没有另外的功能成分位于其中。The 2-in-1 alkaline composition of the present invention can be further combined with different functional components suitable for industrial warewashing applications. In some embodiments, the alkaline detergent and rinse aid composition comprising a source of carbonate-based alkalinity and a nonionic surfactant (and/or polymer) constitutes a majority of the detergent composition, or Even basically all of the total weight. For example, in some embodiments, few or no additional functional ingredients are located therein.
在其他实施方案中，另外的功能成分可以包括在该组合物中。该功能成分为组合物提供了期望的性能和功能。为了本申请的目的，术语“功能成分”包括这样的材料，其当分散或者溶解在使用和/或浓缩溶液例如水溶液中时，提供了在具体使用中有益的性能。功能材料的一些具体例子在下面更详细讨论，虽然所讨论的具体材料是仅仅作为例子给出的，且可以使用宽泛的多种其他功能成分。例如下面所讨论的许多功能材料涉及用于清洁，特别是器皿清洗应用中的材料。但是，其他实施方案可以包括用于其他应用的功能成分。In other embodiments, additional functional ingredients may be included in the composition. The functional ingredient provides the desired properties and functionality to the composition. For the purposes of this application, the term "functional ingredient" includes materials which, when dispersed or dissolved in a use and/or concentrated solution, such as an aqueous solution, provide beneficial properties in a particular use. Some specific examples of functional materials are discussed in more detail below, although the specific materials discussed are given as examples only and a wide variety of other functional ingredients can be used. For example, many of the functional materials discussed below relate to materials used in cleaning, particularly warewashing applications. However, other embodiments may include functional ingredients for other applications.
在优选的实施方案中，该组合物不包括另外的碱度源，即，碱金属氢氧化物。在另一优选的实施方案中，该组合物不包括漂洗助剂。In preferred embodiments, the composition does not include an additional source of alkalinity, ie, an alkali metal hydroxide. In another preferred embodiment, the composition does not include rinse aid.
在其他实施方案中，该组合物可以包括增效剂，水调节剂，稳定剂，消泡剂，抗再沉积剂，漂白剂，杀菌剂，溶解度改变剂，分散剂，抗腐蚀剂和金属保护剂，稳定剂，腐蚀抑制剂，酶，另外的多价螯合剂和/或螯合剂，香味剂和/或染料，流变改性剂或者增稠剂，助水溶剂或者偶联剂，缓冲剂，溶剂，固化剂等。In other embodiments, the composition may include builders, water conditioners, stabilizers, defoamers, anti-redeposition agents, bleaches, bactericides, solubility modifiers, dispersants, anti-corrosion agents, and metal protectants , stabilizers, corrosion inhibitors, enzymes, additional sequestrants and/or chelating agents, fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes or coupling agents, buffers, Solvents, curing agents, etc.
增效剂synergist
该碱性去垢剂组合物可以包括一种或多种增效剂，也称为螯合剂或者多价螯合剂(例如增效剂)，来处理或者软化水和防止形成沉淀物或者其他盐。它们可以包括但不限于：缩合的磷酸盐，碱金属碳酸盐，碱金属硅酸盐和偏硅酸盐，膦酸(盐)，氨基羧酸，和/或聚羧酸聚合物。通常，螯合剂是这样的分子，其能够配位(即，结合)天然水中通常存在的金属离子，来防止金属离子干扰清洁组合物的其他清洁成分的作用。优选的增效剂的加入量(其也可以是螯合剂或者多价螯合剂)是大约0.1-大约70重量％，大约1-大约60重量％，大约5-大约50重量％，或者大约20-大约50重量％。如果该固体去垢剂是作为浓缩物提供的，则该浓缩物可以包括大约1重量％-大约60重量％，大约3重量％-大约50重量％和大约6重量％-大约45重量％的增效剂。增效剂另外的范围包括大约3重量％-大约20重量％，大约6重量％-大约15重量％和大约25重量％-大约50重量％。另外，不限制本发明，全部所述范围包括定义该范围的数和包括所定义的范围内的每个整数。The alkaline detergent composition may include one or more builders, also known as chelating agents or sequestrants (eg, builders), to treat or soften water and prevent the formation of precipitates or other salts. They may include, but are not limited to: condensed phosphates, alkali metal carbonates, alkali metal silicates and metasilicates, phosphonic acids, aminocarboxylic acids, and/or polycarboxylic acid polymers. In general, chelating agents are molecules that are capable of coordinating (ie, binding) metal ions normally present in natural water to prevent the metal ions from interfering with the action of other cleaning ingredients of the cleaning composition. Preferred builder levels (which may also be chelating or sequestering agents) are from about 0.1 to about 70% by weight, from about 1 to about 60% by weight, from about 5 to about 50% by weight, or from about 20- About 50% by weight. If the solid detergent is provided as a concentrate, the concentrate can include about 1% by weight to about 60% by weight, about 3% by weight to about 50% by weight and about 6% by weight to about 45% by weight of additives. potency. Additional ranges for builders include about 3% to about 20% by weight, about 6% to about 15% by weight and about 25% to about 50% by weight. Further, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
缩合磷酸盐的例子包括但不限于：正磷酸钠和钾，焦磷酸钠和钾，三聚磷酸钠和六偏磷酸钠。缩合的磷酸盐还可以通过将该组合物中存在的游离水作为水合水固定，来在有限程度上帮助固化该去垢剂组合物。一种优选的增效剂是无水三聚磷酸钠。Examples of condensed phosphates include, but are not limited to, sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate. Condensed phosphates can also help to set the detergent composition to a limited extent by immobilizing free water present in the composition as water of hydration. A preferred builder is anhydrous sodium tripolyphosphate.
膦酸(盐)的例子包括但不限于：2-膦丁烷-1,2,4-三羧酸(PBTC)，1-羟基乙烷-1,1-二膦酸，CH2C(OH)[PO(OH)2]2；氨基三(亚甲基膦酸)，N[CH2PO(OH)2]3；氨基三(亚甲基膦酸)钠盐(ATMP)，N[CH2PO(ONa)2]3；2-羟基乙基亚氨基双(亚甲基膦酸)，HOCH2CH2N[CH2PO(OH)2]2；二亚乙基三胺五(亚甲基膦酸)，(HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2；二亚乙基三胺五(亚甲基膦酸)钠盐(DTPMP)，C9H(28-x)N3NaxO15P5(x＝7)；六亚甲基二胺(四亚甲基膦酸)钾盐C10H(28-x)N2KxO12P4(x＝6)；双(六亚甲基)三胺(五亚甲基膦酸)，(HO2)POCH2N[(CH2)2N[CH2PO(OH)2]2]2；和亚磷酸，H3PO3。一种优选的膦酸(盐)组合是ATMP和HEDP。优选的是在加入混合物中之前中和的或者碱性膦酸(盐)，或者膦酸(盐)与碱源的组合，以使得当加入膦酸盐时中和反应产生很少的或者不产生热或者气体。但是在一种实施方案中，该去垢剂组合物是无磷的。Examples of phosphonic acids (salts) include, but are not limited to: 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-1,1-diphosphonic acid,CH2C (OH )[PO(OH)2 ]2 ; aminotris(methylenephosphonic acid), N[CH2 PO(OH)2 ]3 ; aminotris(methylenephosphonic acid) sodium salt (ATMP), N[CH2 PO(ONa)2 ]3 ; 2-hydroxyethyliminobis(methylene phosphonic acid), HOCH2 CH2 N[CH2 PO(OH)2 ]2 ; methylphosphonic acid), (HO)2 POCH2 N[CH2 CH2 N[CH2 PO(OH)2 ]2 ]2 ; diethylenetriaminepenta(methylenephosphonic acid) sodium salt (DTPMP ), C9 H(28-x) N3 Nax O15 P5 (x=7); hexamethylenediamine (tetramethylene phosphonic acid) potassium salt C10 H(28-x) N2 KxO12 P4 (x=6); bis(hexamethylene)triamine (pentamethylenephosphonic acid), (HO2 )POCH2 N[(CH2 )2 N[CH2 PO(OH)2 ]2 ]2 ; and phosphorous acid, H3 PO3 . A preferred phosphonic acid combination is ATMP and HEDP. It is preferred to neutralize either an alkaline phosphonic acid (salt), or a combination of a phosphonic acid (salt) and a source of alkalinity, prior to addition to the mixture so that little or no neutralization occurs when the phosphonate is added. heat or gas. In one embodiment, however, the detergent composition is phosphorus-free.
含有很少或者没有NTA的有用的氨基羧酸材料包括但不限于：N-羟基乙基氨基二乙酸，乙二胺四乙酸(EDTA)，羟基乙二胺四乙酸，二亚乙基三胺五乙酸，N-羟基乙基-乙二胺三乙酸(HEDTA)，二亚乙基三胺五乙酸(DTPA)，天冬氨酸-N,N-二乙酸(ASDA)，甲基氨基乙酸二乙酸(MGDA)，谷氨酸-N,N-二乙酸(GLDA)，乙二胺琥珀酸(EDDS)，2-羟基乙基亚氨基二乙酸(HEIDA)，亚氨基二琥珀酸(IDS)，3-羟基-2-2'-亚氨基二琥珀酸(HIDS)和其他类似的酸或者其盐，其具有氨基和羧酸取代基。但是在一种实施方案中，该组合物没有氨基羧酸(盐)。Useful aminocarboxylic acid materials that contain little or no NTA include, but are not limited to: N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepenta Acetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), aspartic acid-N,N-diacetic acid (ASDA), methylglycine diacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic acid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS), 3 -Hydroxy-2-2'-iminodisuccinic acid (HIDS) and other similar acids or salts thereof, which have amino and carboxylic acid substituents. In one embodiment, however, the composition is free of aminocarboxylic acids (salts).
水调节聚合物也可以用作不含磷的增效剂。示例性水调节聚合物包括但不限于：聚羧酸(酯/盐)。可以用作增效剂和/或水调节聚合物的示例性聚羧酸(酯/盐)包括但不限于：具有侧基羧酸根(-CO2-)基团的那些例如聚丙烯酸，马来酸，马来酸/烯烃共聚物，磺酸化的共聚物或者三元共聚物，丙烯酸/马来酸共聚物，聚甲基丙烯酸，丙烯酸-甲基丙烯酸共聚物，水解的聚丙烯酰胺，水解的聚甲基丙烯酰胺，水解的聚酰胺-甲基丙烯酰胺共聚物，水解的聚丙烯腈，水解的聚甲基丙烯腈和水解的丙烯腈-甲基丙烯腈共聚物。其他合适的水调节聚合物包括淀粉，糖或者多元醇(其包含羧酸或者酯官能团)。示例性羧酸包括但不限于马来酸，丙烯酸，甲基丙烯酸和衣康酸或者其盐。示例性酯官能团包括芳基，环状的，芳族和C1-C10线性，支化或者取代的酯。对于螯合剂/多价螯合剂进一步的讨论，参见Kirk-Othmer，Encyclopedia of Chemical Technology，第三版，第5卷，第339-366页和第23卷，第319-320页，其公开内容在此引入作为参考。这些材料还可以以不足化学计量比水平使用来用作晶体改性剂。Water conditioning polymers can also be used as phosphorus-free builders. Exemplary water conditioning polymers include, but are not limited to: polycarboxylates (esters/salts). Exemplary polycarboxylates that may be used as builders and/or water conditioning polymers include, but are not limited to: those with pendant carboxylate (-CO2- ) groups such as polyacrylic acid, maleic acid Acid, maleic/olefin copolymer, sulfonated copolymer or terpolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic-methacrylic acid copolymer, hydrolyzed polyacrylamide, hydrolyzed Polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymer, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile and hydrolyzed acrylonitrile-methacrylonitrile copolymer. Other suitable water regulating polymers include starches, sugars or polyols (which contain carboxylic acid or ester functional groups). Exemplary carboxylic acids include, but are not limited to, maleic acid, acrylic acid, methacrylic acid, and itaconic acid or salts thereof. Exemplary ester functional groups include aryl, cyclic, aromatic and C1 -C10 linear, branched or substituted esters. For further discussion of chelating agents/sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 5, Pages 339-366 and Volume 23, Pages 319-320, the disclosure of which is at This is incorporated by reference. These materials can also be used at substoichiometric levels as crystal modifiers.
水调节剂water conditioner
该碱性去垢剂组合物可以包括一种或多种水调节剂。在一方面，可以使用膦酸。膦酸可以以水溶性酸盐，特别是碱金属盐，例如钠或钾；铵盐；或者烷基醇胺盐的形式来使用，这里该烷基醇具有2-3个碳原子，例如单-，二-或者三乙醇胺盐。优选的膦酸(盐)包括有机膦酸(盐)。优选的有机膦酸(盐)包括膦丁烷三羧酸(PBTC)，其在商标名BAYHIBITTM下获自Pittsburgh Pa.的Bayer Corp.，和羟亚乙基二膦酸(HEDP)，例如其是在商标名DEQUESTTM2010下获自Monsanto Chemical Co的。用于本发明的合适的水调节剂另外的说明描述在美国专利No.6436893中，其在此以其全部引入作为参考。The alkaline detergent composition may include one or more water conditioners. In one aspect, phosphonic acid can be used. Phosphonic acids can be used in the form of water-soluble acid salts, especially alkali metal salts, such as sodium or potassium; ammonium salts; or alkyl alcohol amine salts, where the alkyl alcohol has 2-3 carbon atoms, such as mono- , Di- or triethanolamine salt. Preferred phosphonic acids (salts) include organic phosphonic acids (salts). Preferred organic phosphonic acids (salts) include phosphinobutane tricarboxylic acid (PBTC), which is available under the trade name BAYHIBIT™ from Bayer Corp. of Pittsburgh Pa., and hydroxyethylene diphosphonic acid (HEDP), such as its is available from Monsanto Chemical Co under the trade name DEQUEST™ 2010. Additional descriptions of suitable water conditioners for use in the present invention are described in US Patent No. 6,436,893, which is hereby incorporated by reference in its entirety.
在一方面，该组合物包括大约0.1wt％-50wt％的水调节剂，大约1wt％-40wt％水调节剂，大约1wt％-30wt％水调节剂，优选大约5wt％-20wt％水调节剂。另外，不限制根据本发明，全部所述范围包括定义该范围的数和包括所定义的范围内的每个整数。In one aspect, the composition comprises about 0.1 wt% to 50 wt% water conditioner, about 1 wt% to 40 wt% water conditioner, about 1 wt% to 30 wt% water conditioner, preferably about 5 wt% to 20 wt% water conditioner . Additionally, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
中和剂Neutralizer
该碱性去垢剂组合物还可以包括中和剂。例如在某些实施方案中，碱性中和剂可以用于中和酸性组分例如水调节剂。合适的碱性中和剂可以包括例如碱金属氢氧化物，包括但不限于：氢氧化钠，氢氧化钾，氢氧化锂及其组合。碱金属氢氧化物中和剂可以以本领域已知的任何形式加入该组合物中，包括作为固体珠，溶解在水溶液中或者其组合。另外，根据某些实施方案可以使用大于一种的中和剂。在本发明的一方面，本发明的组合物不包括氢氧化物作为碱度源，而仅仅中和该组合物中的酸性成分，包括例如水调节剂例如HEDP。The alkaline detergent composition may also include a neutralizing agent. For example, in certain embodiments, alkaline neutralizers may be used to neutralize acidic components such as water conditioners. Suitable alkaline neutralizing agents may include, for example, alkali metal hydroxides including, but not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, and combinations thereof. The alkali metal hydroxide neutralizing agent can be added to the composition in any form known in the art, including as solid beads, dissolved in an aqueous solution, or a combination thereof. Additionally, more than one neutralizing agent may be used according to certain embodiments. In one aspect of the invention, the compositions of the invention do not include hydroxide as a source of alkalinity, but merely neutralize acidic components in the composition, including, for example, water conditioners such as HEDP.
在一方面，该组合物包括大约0.1wt％-50wt％中和剂，大约0.1wt％-30wt％中和剂，大约1wt％-25wt％中和剂，优选大约10wt％-25wt％中和剂。在本发明的一种实施方案中，该中和剂包含高达大约10wt％，优选大约0.01wt％-大约10wt％量的碱金属氢氧化物。另外，不限制根据本发明，全部所述范围包括定义该范围的数和包括所定义的范围内的每个整数。In one aspect, the composition comprises about 0.1 wt%-50 wt% neutralizing agent, about 0.1 wt%-30 wt% neutralizing agent, about 1 wt%-25 wt% neutralizing agent, preferably about 10 wt%-25 wt% neutralizing agent . In one embodiment of the invention, the neutralizing agent comprises alkali metal hydroxide in an amount up to about 10 wt%, preferably from about 0.01 wt% to about 10 wt%. Additionally, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
抗蚀刻剂Anti-etch agent
该碱性去垢剂组合物还可以包括抗蚀刻剂，其能够防止玻璃中的蚀刻。合适的抗蚀刻剂的例子包括加入到组合物的金属离子例如锌，氯化锌，葡糖酸锌，铝和铍。该腐蚀抑制剂可以指的是铝离子源和锌离子源的组合。当该固体去垢剂组合物是以使用溶液的形式提供时，该铝离子源和锌离子源分别提供了铝离子和锌离子。该腐蚀抑制剂的量是基于铝离子源和锌离子源的合计量来计算的。在使用溶液中提供铝离子的任何物质可以称作铝离子源，和当提供在使用溶液中时提供锌离子的任何物质可以称作锌离子源。铝离子源和/或锌离子源不必需反应来形成铝离子和/或锌离子。铝离子可以认为是铝离子源，和锌离子可以认为是锌离子源。铝离子源和锌离子源可以作为有机盐，无机盐及其混合物来提供。示例性的铝离子源包括但不限于：铝盐例如铝酸钠，溴化铝，氯酸铝，氯化铝，碘化铝，硝酸铝，硫酸铝，乙酸铝，甲酸铝，酒石酸铝，乳酸铝，油酸铝，溴酸铝，硼酸铝，硫酸铝钾，硫酸铝锌和磷酸铝。示例性的锌离子源包括但不限于：锌盐例如氯化锌，硫酸锌，硝酸锌，碘化锌，硫氰酸锌，氟硅酸锌，重铬酸锌，氯酸锌，锌酸钠，葡糖酸锌，乙酸锌，苯甲酸锌，柠檬酸锌，乳酸锌，甲酸锌，溴酸锌，溴化锌，氟化锌，氟硅酸锌和水杨酸锌。The alkaline detergent composition may also include an etch resist, which is capable of preventing etching in glass. Examples of suitable etch resists include metal ions such as zinc, zinc chloride, zinc gluconate, aluminum and beryllium added to the composition. The corrosion inhibitor may refer to a combination of a source of aluminum ions and a source of zinc ions. When the solid detergent composition is provided in the form of a use solution, the source of aluminum ions and the source of zinc ions provide aluminum ions and zinc ions, respectively. The amount of the corrosion inhibitor is calculated based on the total amount of the source of aluminum ions and the source of zinc ions. Any substance that provides aluminum ions in a use solution may be referred to as a source of aluminum ions, and any substance that provides zinc ions when provided in a use solution may be referred to as a source of zinc ions. The source of aluminum ions and/or the source of zinc ions does not have to react to form aluminum ions and/or zinc ions. Aluminum ions may be considered a source of aluminum ions, and zinc ions may be considered a source of zinc ions. The source of aluminum ions and the source of zinc ions can be provided as organic salts, inorganic salts and mixtures thereof. Exemplary sources of aluminum ions include, but are not limited to: aluminum salts such as sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, lactic acid Aluminum, aluminum oleate, aluminum bromate, aluminum borate, aluminum potassium sulfate, aluminum zinc sulfate, and aluminum phosphate. Exemplary sources of zinc ions include, but are not limited to: zinc salts such as zinc chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc fluorosilicate, zinc dichromate, zinc chlorate, sodium zincate , zinc gluconate, zinc acetate, zinc benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc bromide, zinc fluoride, zinc fluorosilicate, and zinc salicylate.
该组合物优选包括大约0.001wt％-大约10wt％，更优选大约0.01wt％-大约7wt％，和最优选大约0.01wt％-大约1wt％的抗蚀刻剂。另外，不限制根据本发明，全部所述范围包括定义该范围的数和包括所定义的范围内的每个整数。The composition preferably includes from about 0.001 wt% to about 10 wt%, more preferably from about 0.01 wt% to about 7 wt%, and most preferably from about 0.01 wt% to about 1 wt% of the etch resist. Additionally, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
抗腐蚀剂anti-corrosion agent
该碱性去垢剂组合物可以任选包括抗腐蚀剂。抗腐蚀剂提供了组合物，其产生这样的表面，其与没有用具有抗腐蚀剂的组合物处理的表面相比是更光亮的和不太容易产生生物膜附着。The alkaline detergent composition may optionally include an anti-corrosion agent. The anti-corrosion agent provides a composition that produces a surface that is shinier and less prone to biofilm attachment than a surface that is not treated with the composition having the anti-corrosion agent.
可以用于本发明的优选的抗腐蚀剂包括膦酸酯/盐，膦酸，三唑，有机胺，山梨聚糖酯，羧酸衍生物，肌氨酸盐，磷酸酯，锌，硝酸盐，铬，含钼酸盐的组分，和含硼酸盐的组分。示例性磷酸酯或者膦酸是在名称Dequest(即，Dequest 2000，Dequest 2006，Dequest 2010，Dequest 2016，Dequest 2054，Dequest 2060和Dequest 2066)下，由St.Louis，Mo的Solutia，Inc.市售的。示例性三唑是在名称Cobratec(即，Cobratec 100，Cobratec TT-50-S和Cobratec 99)下由的俄亥俄州辛辛那提的PMC Specialties Group，Inc.市售的。示例性有机胺包括脂肪族胺，芳族胺，单胺，二胺，三胺，多胺和它们的盐。示例性胺是在名称Amp(即Amp-95)下由Angus Chemical Company of Buffalo Grove，Ill.市售的；在WGS(即，WGS-50)下由Jacam Chemicals，LLC of Sterling，Kans.市售的；在Duomeen(即，Duomeen O和Duomeen C)下由Akzo Nobel Chemicals，Inc.of Chicago，Ill.市售的；在DeThox amine(C系列和T系列)由DeForest Enterprises，Inc.of Boca Raton，Fla.市售的；在Deriphat系列下由Henkel Corp.of Ambler，Pa.市售的；和在Maxhib(AC系列)下由Chemax，Inc.ofGreenville，S.C.市售的。示例性山梨聚糖酯是在名称Calgene(LA系列)下由CalgeneChemical Inc.of Skokie，Ill.市售的。示例性羧酸衍生物是在名称Recor(即，Recor 12)下由Ciba-Geigy Corp.of Tarrytown，N.Y.市售的。示例性肌氨酸盐是在名称Hamposyl下由Hampshire Chemical Corp.of Lexington，Mass.市售的；和在Sarkosyl下由Ciba-GeigyCorp.of Tarrytown，N.Y.市售的。Preferred corrosion inhibitors that can be used in the present invention include phosphonates, phosphonic acids, triazoles, organic amines, sorbitan esters, carboxylic acid derivatives, sarcosinates, phosphate esters, zinc, nitrates, chromium , molybdate-containing components, and borate-containing components. Exemplary phosphates or phosphonic acids are commercially available under the name Dequest (i.e., Dequest 2000, Dequest 2006, Dequest 2010, Dequest 2016, Dequest 2054, Dequest 2060, and Dequest 2066) from Solutia, Inc. of St. Louis, Mo. of. Exemplary triazoles are commercially available from PMC Specialties Group, Inc. of Cincinnati, Ohio under the name Cobratec (ie, Cobratec 100, Cobratec TT-50-S, and Cobratec 99). Exemplary organic amines include aliphatic amines, aromatic amines, monoamines, diamines, triamines, polyamines, and salts thereof. Exemplary amines are commercially available under the designations Amp (i.e., Amp-95) from the Angus Chemical Company of Buffalo Grove, Ill.; under WGS (i.e., WGS-50) from Jacam Chemicals, LLC of Sterling, Kans. commercially available under Duomeen (i.e., Duomeen O and Duomeen C) from Akzo Nobel Chemicals, Inc. of Chicago, Ill.; under DeThox amines (Series C and T) from DeForest Enterprises, Inc. of Boca Raton, commercially available from Fla.; under the Deriphat series by Henkel Corp. of Ambler, Pa.; and under the Maxhib (AC series) by Chemax, Inc. of Greenville, S.C. Exemplary sorbitan esters are commercially available from Calgene Chemical Inc. of Skokie, Ill. under the designation Calgene (LA series). Exemplary carboxylic acid derivatives are commercially available from Ciba-Geigy Corp. of Tarrytown, N.Y. under the name Recor (ie, Recor 12). Exemplary sarcosinates are commercially available under the name Hamposyl from Hampshire Chemical Corp. of Lexington, Mass.; and Sarkosyl from Ciba-Geigy Corp. of Tarrytown, N.Y.
该组合物任选包括抗腐蚀剂来为洗碗机的金属部分提供增强的光泽和/或提供更亮的表面。当抗腐蚀剂引入该组合物时，优选以大约0.01wt％-大约7.5wt％，大约0.01wt％-大约5wt％和大约0.01wt％-大约3wt％的量包括它。The composition optionally includes an anti-corrosion agent to provide enhanced gloss and/or to provide a shinier surface to metal parts of the dishwasher. When an anti-corrosion agent is introduced into the composition, it is preferably included in an amount of about 0.01 wt% to about 7.5 wt%, about 0.01 wt% to about 5 wt%, and about 0.01 wt% to about 3 wt%.
抗再沉积剂anti redeposition agent
所述碱性去垢剂组合物还可以包括抗再沉积剂，其能够促进污垢在清洁溶液中的持久悬浮和防止所除去的污垢重新沉积到所清洁的基底上。合适的抗再沉积剂的例子包括脂肪酸酰胺，络合的磷酸酯，苯乙烯马来酸酐共聚物，和纤维素衍生物例如羟乙基纤维素，羟丙基纤维素等。该组合物优选包括大约0.5wt％-大约10wt％和更优选大约1wt％-大约5wt％的抗再沉积剂。The alkaline detergent compositions may also include anti-redeposition agents which promote durable suspension of soils in the cleaning solution and prevent redeposition of removed soils onto the substrate being cleaned. Examples of suitable anti-redeposition agents include fatty acid amides, complex phosphate esters, styrene-maleic anhydride copolymers, and cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, and the like. The composition preferably includes from about 0.5% to about 10% by weight and more preferably from about 1% to about 5% by weight of the anti-redeposition agent.
酶enzyme
该碱性去垢剂组合物可以包括一种或多种酶，其可以提供令人期望的活性来从基底例如平器皿，杯子和碗，和罐子和盘子除去蛋白质基，碳水化合物基或者甘油三酸酯基污垢。适于本发明组合物的酶可以通过降解或者改变在表面上所遇到的一种或多种类型的污垢残留物来发挥作用，因此除去该污垢或者使得该污垢可以通过表面活性剂或者清洁组合物的其他组分来更多地除去。污垢残留物的降解和改变二者可以通过减少污垢结合到清洁的表面或者纺织品上的物理化学作用力来改进去垢性，即，该污垢变成更大水溶性的。例如一种或多种蛋白酶可以将存在于污垢残留物中的复杂的，大分子蛋白质结构分解成更简单的短链分子，其本身是更容易从表面上解吸，溶解或者更容易通过含有所述蛋白酶的清洁溶液来除去的。The alkaline detergent composition can include one or more enzymes that can provide the desired activity to remove protein-based, carbohydrate-based or triglycerides from substrates such as flatware, cups and bowls, and jars and dishes Acid based dirt. Enzymes suitable for the compositions of the present invention may act by degrading or altering one or more types of soil residues encountered on a surface, thereby removing the soil or rendering the soil accessible to a surface active agent or cleaning combination other components of the substance to remove more. Both the degradation and modification of soil residues can improve soil removal by reducing the physicochemical forces that bind soils to cleaned surfaces or textiles, ie, the soils become more water soluble. For example one or more proteases can break down the complex, macromolecular protein structures present in the dirt residue into simpler short-chain molecules, which are themselves easier to desorb from surfaces, dissolve or be more easily obtained by containing the Protease cleaning solution to remove.
合适的酶包括任何合适的来源的蛋白酶，淀粉酶，脂肪酶，葡糖酶，纤维酶，过氧化物酶或者其混合物，例如植物，动物，细菌，真菌或者酵母来源的。优选的选择受到因素例如pH活性和/或稳定性优化，热稳定性和对于活化去垢剂，增效剂等的稳定性的影响。在这方面，细菌或者真菌酶是优选的，例如细菌淀粉酶和蛋白酶，和真菌纤维酶。在一些实施方案中，优选该酶是蛋白酶，脂肪酶，淀粉酶或者其组合。一个关于酶的有价值的参考文献(其在此引入作为参考)是“Industrial Enzymes，”Scott，D.，Kirk-Othmer Encyclopedia ofChemical Technology，第3版(编辑Grayson，M.和EcKroth，D.)第9卷第173-224页，JohnWiley&Sons，纽约，1980。Suitable enzymes include proteases, amylases, lipases, glucosidases, cellulases, peroxidases or mixtures thereof of any suitable origin, eg of vegetable, animal, bacterial, fungal or yeast origin. Preferred selection is influenced by factors such as pH activity and/or stability optimization, thermal stability and stability to activated detergents, builders and the like. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. In some embodiments, it is preferred that the enzyme is a protease, lipase, amylase or a combination thereof. A valuable reference on enzymes (which is hereby incorporated by reference) is "Industrial Enzymes," Scott, D., Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition (Editors Grayson, M. and EcKroth, D.) Vol. 9, pp. 173-224, John Wiley & Sons, New York, 1980.
在使用酶的实施方案中，该组合物优选包括大约0.001wt％-大约10wt％，大约0.01wt％-大约10wt％，大约0.05wt％-大约5wt％和更优选大约0.1wt％-大约1wt％的酶。In embodiments using enzymes, the composition preferably comprises about 0.001 wt% to about 10 wt%, about 0.01 wt% to about 10 wt%, about 0.05 wt% to about 5 wt% and more preferably about 0.1 wt% to about 1 wt% enzymes.
抗菌剂Antibacterial agents
该碱性去垢剂组合物可以任选包括抗菌剂或防腐剂。抗菌剂是化学组合物，其可以用于组合物中来防止微生物污染和劣化市售产品材料系统，表面等。抗菌剂也可以是消毒剂。通常，这些材料落入具体种类中，包括酚类，卤素化合物，季铵化合物，金属衍生物，胺，烷醇胺，硝基衍生物，analides，有机硫和硫-氮化合物和多种化合物。根据化学组成和浓度所给定的抗菌剂可以简单地限制微生物数目的进一步增殖或者可以破坏全部的或者大部分的微生物群。术语“微生物(microbes)”和“微有机体(microorganisms)”典型地主要指的是细菌和真菌微生物。在使用中，该抗菌剂形成最终产物，其当使用含水流稀释和分配时形成了含水消毒或灭菌组合物，其可以与多种表面接触，导致防止大部分微生物群生长或者杀灭它们。可以使用的常规抗微生物剂包括酚抗微生物剂例如五氯酚，邻苯酚；可以使用的含卤素抗菌剂包括三氯异氰尿酸钠，二氯异氰尿酸钠(无水的或者二水合物)，碘-聚(乙烯基吡咯烷酮(vinylpyrolidin-onen))络合物，溴化合物例如2-溴-2-硝基丙-1，3-二醇；季化抗微生物剂例如苯扎氯铵，氯化十六烷基吡啶鎓；胺和含硝基抗微生物组合物例如六氢-1,3,5-三(2-羟乙基)-s-三嗪，二硫代氨基甲酸盐例如二甲基二硫代氨基甲酸钠，和在本领域中由于它们的微生物性质而已知的多种其他材料。抗微生物剂可以胶囊化来改进稳定性和/或降低与去垢剂组合物中的其他材料的反应性。The alkaline detergent composition may optionally include an antimicrobial or preservative. Antimicrobial agents are chemical compositions that can be used in compositions to prevent microbial contamination and deterioration of commercially available product material systems, surfaces, and the like. Antiseptics can also be disinfectants. Generally, these materials fall into specific classes including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, analides, organosulfur and sulfur-nitrogen compounds, and various compounds. A given antimicrobial agent, depending on chemical composition and concentration, may simply limit the further proliferation of the microbial population or may destroy all or a substantial part of the microbial population. The terms "microbes" and "microorganisms" typically refer primarily to bacterial and fungal microorganisms. In use, the antiseptic forms an end product that when diluted and dispensed with an aqueous stream forms an aqueous disinfecting or sanitizing composition that can come into contact with a variety of surfaces resulting in the prevention of growth or the killing of most microbial populations. Conventional antimicrobials that can be used include phenolic antimicrobials such as pentachlorophenol, o-phenol; halogenated antimicrobials that can be used include sodium trichloroisocyanurate, sodium dichloroisocyanurate (anhydrous or dihydrate) , iodine-poly(vinylpyrolidin-onen) complexes, bromine compounds such as 2-bromo-2-nitropropane-1,3-diol; quaternary antimicrobial agents such as benzalkonium chloride, chloride cetylpyridinium; amine and nitro-containing antimicrobial compositions such as hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates such as di Sodium methyl dithiocarbamate, and various other materials known in the art for their microbial properties. Antimicrobial agents can be encapsulated to improve stability and/or reduce reactivity with other materials in the detergent composition.
当抗微生物剂或者防腐剂引入组合物时，优选以大约0.01wt％-大约5wt％，大约0.01wt％-大约2wt％和大约0.1wt％-大约1.0wt％的量包括它。When an antimicrobial or preservative is incorporated into the composition, it is preferably included in an amount of about 0.01 wt% to about 5 wt%, about 0.01 wt% to about 2 wt%, and about 0.1 wt% to about 1.0 wt%.
泡沫抑制剂Foam inhibitor
除了非离子表面活性剂之外，泡沫抑制剂可以包括在该碱性清洁组合物中来降低所形成的任何泡沫的稳定性。泡沫抑制剂的例子包括有机硅化合物例如分散在聚二甲基硅氧烷中的二氧化硅，脂肪酰胺，烃蜡，脂肪酸，脂肪酯，脂肪醇，脂肪酸皂，乙氧基化物，矿物油，聚乙二醇酯，聚氧乙烯-聚氧丙烯嵌段共聚物，烷基磷酸酯例如磷酸单硬脂酯等。泡沫抑制剂的讨论可以在例如Martin等人的美国专利No.3048548，Brunelle等人的美国专利No.3334147和Rue等人的美国专利No.3442242中找到，其公开内容在此引入作为参考。该组合物优选包括大约0.0001wt％-大约5wt％和更优选大约0.01wt％-大约3wt％的泡沫抑制剂。In addition to nonionic surfactants, suds suppressors may be included in the alkaline cleaning composition to reduce the stability of any suds formed. Examples of suds suppressors include organosilicon compounds such as silica dispersed in polydimethylsiloxane, fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, Polyethylene glycol esters, polyoxyethylene-polyoxypropylene block copolymers, alkyl phosphates such as monostearyl phosphate, and the like. A discussion of suds suppressors can be found, for example, in US Patent No. 3,048,548 to Martin et al., US Patent No. 3,334,147 to Brunelle et al., and US Patent No. 3,442,242 to Rue et al., the disclosures of which are incorporated herein by reference. The composition preferably includes from about 0.0001 wt% to about 5 wt% and more preferably from about 0.01 wt% to about 3 wt% of the suds suppressor.
另外的表面活性剂additional surfactant
本发明的组合物可以包括另外的表面活性剂。特别合适的表面活性剂包括非离子表面活性剂，两性表面活性剂和两性离子表面活性剂。在一种优选的实施方案中，该组合物基本上不含阳离子和/或阴离子表面活性剂。在一方面，该组合物可以包括大约0.01wt％-40wt％的另外的表面活性剂，优选大约0.1wt％-30wt％另外的表面活性剂，更优选大约1wt％-25wt％另外的表面活性剂。另外，不限制根据本发明，全部所述范围包括定义该范围的数和包括所定义的范围内的每个整数。Compositions of the present invention may include additional surfactants. Particularly suitable surfactants include nonionic surfactants, amphoteric surfactants and zwitterionic surfactants. In a preferred embodiment, the composition is substantially free of cationic and/or anionic surfactants. In one aspect, the composition may comprise from about 0.01 wt % to 40 wt % additional surfactant, preferably from about 0.1 wt % to 30 wt % additional surfactant, more preferably from about 1 wt % to 25 wt % additional surfactant . Additionally, without limiting the invention, all stated ranges include the numbers defining the range and include each integer within the defined range.
非离子表面活性剂nonionic surfactant
适用于本发明组合物的合适的非离子表面活性剂包括烷氧基化的表面活性剂。合适的烷氧基化的表面活性剂包括EO/PO共聚物，封端的EO/PO共聚物，醇烷氧基化物，封端的醇烷氧基化物，其混合物等。用作溶剂的合适的烷氧基化的表面活性剂包括EO/PO嵌段共聚物，例如Pluronic和逆转Pluronic表面活性剂；醇烷氧基化物，例如Dehypon LS-54(R-(EO)5(PO)4)和Dehypon LS-36(R-(EO)3(PO)6)；和封端的醇烷氧基化物，例如PlurafacLF221和Tegoten EC11；其混合物等。Suitable nonionic surfactants for use in the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO/PO copolymers, blocked EO/PO copolymers, alcohol alkoxylates, blocked alcohol alkoxylates, mixtures thereof, and the like. Suitable alkoxylated surfactants for use as solvents include EO/PO block copolymers such as Pluronic and inverse Pluronic surfactants; alcohol alkoxylates such as Dehypon LS-54 (R-(EO)5 (PO)4 ) and Dehypon LS-36 (R-(EO)3 (PO)6 ); and blocked alcohol alkoxylates such as PlurafacLF221 and Tegoten EC11 ; mixtures thereof, and the like.
半极性类型的非离子表面活性剂是可用于本发明组合物的另一类非离子表面活性剂。半极性非离子表面活性剂包括胺氧化物，膦氧化物，亚砜和它们的烷氧基化衍生物。Nonionic surfactants of the semi-polar type are another class of nonionic surfactants useful in the compositions of the present invention. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.
胺氧化物是对应于下面的通式的叔胺氧化物：Amine oxides are tertiary amine oxides corresponding to the general formula:
其中该箭头是半极性键的常规表示；和R1，R2和R3可以是脂肪族，芳族，杂环，脂环族或者其组合。通常对于去垢剂所关注的胺氧化物，R1是具有大约8-大约24个碳原子的烷基；R2和R3是1-3个碳原子的烷基或者羟烷基或者其混合物；R2和R3可以彼此例如通过氧或者氮原子连接，来形成环结构；R4是含有2-3个碳原子的亚烷基或者羟基亚烷基；和n是0-大约20。胺氧化物可以由相应的胺和氧化剂例如过氧化氢来产生。wherein the arrow is a conventional representation of a semipolar bond; and R1 , R2 and R3 may be aliphatic, aromatic, heterocyclic, cycloaliphatic or combinations thereof. Typically for amine oxides of detergent interest, R isan alkyl group having from about 8 to about 24 carbon atoms; R and R are alkyl or hydroxyalkyl groups of1 to3 carbon atoms or mixtures thereof R2 and R3 can be connected to each other, for example, through an oxygen or nitrogen atom, to form a ring structure; R4 is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms; and n is 0-about 20. Amine oxides can be produced from the corresponding amines and an oxidizing agent such as hydrogen peroxide.
有用的水溶性胺氧化物表面活性剂选自辛基，癸基，十二烷基，异十二烷基，椰子，或者牛脂烷基二-(低级烷基)胺氧化物，其具体例子是辛基二甲基氧化胺，壬基二甲基氧化胺，癸基二甲基氧化胺，十一烷基二甲基氧化胺，十二烷基二甲基氧化胺，异十二烷基二甲基氧化胺，十三烷基二甲基氧化胺，十四烷基二甲基氧化胺，十五烷基二甲基氧化胺，十六烷基二甲基氧化胺，十七烷基二甲基氧化胺，十八烷基二甲基氧化胺，十二烷基二丙基氧化胺，十四烷基二丙基氧化胺，十六烷基二丙基氧化胺，十四烷基二丁基氧化胺，十八烷基二丁基氧化胺，双(2-羟基乙基)十二烷基氧化胺，双(2-羟基乙基)-3-十二烷氧基-1-羟基丙基氧化胺，二甲基-(2-羟基十二烷基)氧化胺，3,6,9-三十八烷基二甲基氧化胺和3-十二烷氧基-2-羟基丙基二-(2-羟基乙基)氧化胺。Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are Octyl dimethyl amine oxide, nonyl dimethyl amine oxide, decyl dimethyl amine oxide, undecyl dimethyl amine oxide, dodecyl dimethyl amine oxide, isododecyl di Methylamine Oxide, Tridecyl Dimethyl Amine Oxide, Tetradecyl Dimethyl Amine Oxide, Pentadecyl Dimethyl Amine Oxide, Hexadecyl Dimethyl Amine Oxide, Heptadecyl Dimethyl Amine Oxide Methyl Amine Oxide, Octadecyl Dimethyl Amine Oxide, Dodecyl Dipropyl Amine Oxide, Tetradecyl Dipropyl Amine Oxide, Hexadecyl Dipropyl Amine Oxide, Tetradecyl Dipropyl Amine Oxide Butylamine Oxide, Octadecyldibutylamine Oxide, Bis(2-Hydroxyethyl)Dodecylamine Oxide, Bis(2-Hydroxyethyl)-3-Dodecyloxy-1-Hydroxy Propyl amine oxide, dimethyl-(2-hydroxydodecyl) amine oxide, 3,6,9-trioctadecyl dimethyl amine oxide and 3-dodecyloxy-2-hydroxypropane Di-(2-hydroxyethyl)amine oxide.
两性表面活性剂amphoteric surfactant
两性或者两性电解质表面活性剂包含碱性和酸性亲水基团和有机疏水基团二者。这些离子实体可以是本文所述的用于其他类型的表面活性剂的任何阴离子或者阳离子基团。碱性氮和酸性羧酸根基团是用作该碱性和酸性亲水基团的典型的官能团。在几个表面活性剂中，磺酸根，硫酸根，膦酸根或者磷酸根提供了负电荷。Amphoteric or ampholyte surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups. These ionic entities can be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as the basic and acidic hydrophilic groups. In several surfactants, sulfonate, sulfate, phosphonate or phosphate groups provide the negative charge.
两性表面活性剂可以宽泛地描述为脂肪族仲和叔胺的衍生物，在其中该脂肪族基团可以是直链或者支化的，并且其中一个脂肪族取代基包含大约8-18个碳原子和一个包含阴离子水溶性基团例如羧基，磺基，硫酸根，磷酸根或者膦酸根。两性表面活性剂细分为本领域技术人员已知的两种主要种类，并且描述在“Surfactant Encyclopedia”Cosmetics&Toiletries，第104卷(2)69-71(1989)，其在此以其全部引入作为参考。第一类包括酰基/二烷基乙二胺衍生物(例如2-烷基羟乙基咪唑啉衍生物)和它们的盐。第二类包括N-烷基氨基酸和它们的盐。可以想到一些两性表面活性剂适于两种种类。Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic group can be straight-chain or branched and in which one of the aliphatic substituents contains about 8-18 carbon atoms and one containing an anionic water-soluble group such as carboxyl, sulfo, sulfate, phosphate or phosphonate. Amphoteric surfactants are subdivided into two main classes known to those skilled in the art and are described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104(2) 69-71 (1989), which is hereby incorporated by reference in its entirety . The first class includes acyl/dialkylethylenediamine derivatives (eg 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second class includes N-alkyl amino acids and their salts. It is conceivable that some amphoteric surfactants are suitable for both classes.
两性表面活性剂可以通过本领域技术人员已知的方法来合成。例如2-烷基羟乙基咪唑啉是通过长链羧酸(或衍生物)与二烷基乙二胺的缩合和闭环来合成的。市售两性表面活性剂是通过通过烷基化例如与氯乙酸或者乙酸乙酯，通过咪唑啉环随后的水解和开环而衍生的。在烷基化过程中，一个或者两个羧基-烷基反应来形成叔胺和与不同烷基化剂的醚连接，产生不同的叔胺。Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethylimidazolines are synthesized by condensation and ring closure of long-chain carboxylic acids (or derivatives) with dialkylethylenediamines. Commercially available amphoteric surfactants are derivatized by alkylation, eg with chloroacetic acid or ethyl acetate, by subsequent hydrolysis and ring opening of the imidazoline ring. During alkylation, one or two carboxy-alkyl groups react to form tertiary amines and are linked to ethers of different alkylating agents to produce different tertiary amines.
可用于本发明的长链咪唑衍生物通常具有通式：The long-chain imidazole derivatives useful in the present invention generally have the general formula:
中性pH-两性离子Neutral pH - Zwitterion
其中R是含有大约8-18个碳原子的非环疏水基团和M是中和阴离子电荷的阳离子，通常是钠。可以用于本发明组合物的市售的主要咪唑啉衍生的两性离子包括例如：椰油两性丙酸盐，椰油两性羧基丙酸盐，椰油两性甘氨酸盐，椰油两性羧基甘氨酸盐，椰油两性丙基磺酸盐和椰油两性羧基-丙酸。两性羧酸可以由脂肪咪唑啉来生产，在其中两性二羧酸的二羧酸官能度是二乙酸和/或二丙酸。wherein R is an acyclic hydrophobic group containing about 8-18 carbon atoms and M is an anionic charge neutralizing cation, usually sodium. Commercially available primary imidazoline-derived zwitterions that can be used in the compositions of the present invention include, for example: cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropionate, Oleamphopropylsulfonate and Cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be produced from fatty imidazolines in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
上述羧甲基化的化合物(甘氨酸(盐/酯))经常称作甜菜碱。甜菜碱是在下面的标题为两性离子表面活性剂的段落中所讨论的一种具体种类的两性表面活性剂。The aforementioned carboxymethylated compounds (glycine (salts/esters)) are often referred to as betaines. Betaines are a specific class of amphoteric surfactants discussed below in the section entitled Zwitterionic Surfactants.
长链N-烷基氨基酸容易通过将RNH2(在其中R＝C8-C18直链或者支链烷基)，脂肪胺与卤代羧酸反应来制备。氨基酸的伯氨基的烷基化产生了仲和叔胺。烷基取代基可以具有另外的氨基，其提供了大于一个的反应性氮中心。大部分市售的N-烷基胺酸是β-丙胺酸或者β-N(2-羧乙基)丙胺酸的烷基衍生物。可用于本发明的市售N-烷基氨基酸两性电解质的例子包括烷基β-氨基二丙酸盐，RN(C2H4COOM)2和RNHC2H4COOM。在一种实施方案中，R可以是含有大约8-大约18个碳原子的非环疏水基团，和M是中和阴离子电荷的阳离子。Long chain N-alkylamino acids are readily prepared by reactingRNH2 (wherein R=C8 -C18 straight or branched chain alkyl), aliphatic amines with halocarboxylic acids. Alkylation of primary amino groups of amino acids produces secondary and tertiary amines. Alkyl substituents may have additional amino groups which provide more than one reactive nitrogen center. Most commercially available N-alkylamine acids are β-alanine or alkyl derivatives of β-N(2-carboxyethyl)alanine. Examples of commercially available N-alkyl amino acid ampholytes that can be used in the present invention include alkyl beta- aminodipropionates, RN(C2H4COOM)2andRNHC2H4COOM. In one embodiment, R can be an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms, and M is a cation that neutralizes the anionic charge.
合适的两性表面活性剂包括衍生自椰子产品例如椰油或者椰子脂肪酸的那些。另外的合适的椰子来源的表面活性剂包括作为它们的结构的一部分的乙二胺部分，烷醇酰胺部分，氨基酸部分例如氨基乙酸或者其组合；和大约8-18(例如12)个碳原子的脂肪族取代基。这样的表面活性剂也可以被认为是烷基两性二羧酸。这些两性表面活性剂可以包括下面所示的化学结构：C12-烷基-C(O)-NH-CH2-CH2-N+(CH2-CH2-CO2Na)2-CH2-CH2-OH或者C12-烷基-C(O)-N(H)-CH2-CH2-N+(CH2-CO2Na)2-CH2-CH2-OH。椰油两性二丙酸二钠是一种合适的两性表面活性剂，并且是在商标名Miranol–FBS下由Rhodia Inc.，Cranbury，N.J.市售的。另一种合适的椰子来源的两性表面活性剂(化学名称椰油两性二乙酸二钠)是在商标名Mirataine–JCHA下，也是由Rhodia Inc.，Cranbury，N.J.市售的。Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut-derived surfactants include as part of their structure ethylenediamine moieties, alkanolamide moieties, amino acid moieties such as glycine, or combinations thereof; and about 8-18 (e.g., 12) carbon atoms Aliphatic substituents. Such surfactants may also be considered alkyl amphodicarboxylic acids. These amphoteric surfactants may include the chemical structure shown below: C12-Alkyl-C(O)-NH-CH2 -CH2 -N+ (CH2 -CH2 -CO2Na )2-CH2 -CH2 -OH or C12 -alkyl-C(O)-N(H)-CH2 -CH2 -N+ (CH2 -CO2 Na)2 -CH2 -CH2 -OH. Disodium cocoamphodipropionate is a suitable amphoteric surfactant and is commercially available under the trade name Miranol - FBS from Rhodia Inc., Cranbury, NJ. Another suitable coconut-derived amphoteric surfactant (chemical name disodium cocoamphodiacetate) is commercially available under the trade name Mirataine - JCHA, also by Rhodia Inc., Cranbury, NJ.
一种典型的两性种类列表和这些表面活性剂物质是在1975年12月30日授予Laughlin和Heuring的美国专利No.3929678中给出的。另外的例子是在“Surface ActiveAgents and Detergents”(第I和II卷，Schwartz，Perry和Berch)中给出的。A typical list of amphoteric species and such surfactant materials is given in US Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Additional examples are given in "Surface ActiveAgents and Detergents" (Volumes I and II, Schwartz, Perry and Berch).
两性离子表面活性剂zwitterionic surfactant
两性离子表面活性剂可以被认为是两性表面活性剂的子组，并且可以包括阴离子电荷。两性离子表面活性剂可以宽泛地描述为仲和叔胺的衍生物，杂环仲和叔胺的衍生物，或者季铵，季鏻或者叔锍化合物的衍生物。典型的，两性离子表面活性剂包括带正电荷的季铵，或者在一些情况中锍或者鏻离子；带负电荷的羧基基团；和烷基。两性离子通常包含阳离子和阴离子基团，其在分子的等电位区域中电离到几乎相等的程度，并且其可以在正-负电荷中心之间形成强的“内盐”吸引力。这样的两性离子合成表面活性剂的例子包括脂肪族季铵，鏻和锍化合物的衍生物，在其中脂肪族基团可以是直链或者支化的，和其中一个脂肪族取代基包含8-18个碳原子和一个包含阴离子水溶性基团例如羧酸根，磺酸根，硫酸根，磷酸根或膦酸根。Zwitterionic surfactants may be considered a subgroup of amphoteric surfactants and may include anionic charges. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Typically, zwitterionic surfactants include positively charged quaternary ammonium, or in some cases sulfonium or phosphonium ions; negatively charged carboxyl groups; and alkyl groups. Zwitterions generally contain cationic and anionic groups that ionize to nearly equal extent in the equipotential region of the molecule, and which can form strong "inner salt" attractions between positive-negative centers of charge. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic group may be linear or branched, and in which one aliphatic substituent contains 8-18 carbon atoms and one containing anionic water-soluble groups such as carboxylate, sulfonate, sulfate, phosphate or phosphonate.
甜菜碱和磺基甜菜碱表面活性剂是用于本文的示例性两性离子表面活性剂。这些化合物的通式是：Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. The general formula of these compounds is:
其中R1包含8-18个碳原子的烷基，烯基或者羟烷基，其具有0-10个氧亚乙基部分和0-1个甘油基部分；Y选自氮，磷和硫原子；R2是烷基或者单羟基烷基，含有1-3个碳原子；当Y是硫原子时x是1和当Y是氮或者磷原子是2，R3是1-4个碳原子的亚烷基或者羟基亚烷基或者羟基亚烷基和Z是选自下面的基团：羧酸根，磺酸根，硫酸根，膦酸根和磷酸根基团。Wherein R contains 8-18 carbon atomsof alkyl, alkenyl or hydroxyalkyl, which has 0-10 oxyethylene moieties and 0-1 glyceryl moieties; Y is selected from nitrogen, phosphorus and sulfur atoms ; R2 is an alkyl or monohydroxyalkyl group, containing 1-3 carbon atoms; when Y is a sulfur atom, x is 1 and when Y is nitrogen or a phosphorus atom is 2, R3 is 1-4 carbon atoms Alkylene or hydroxyalkylene or hydroxyalkylene and Z is a group selected from carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.
具有上面所列结构的两性离子表面活性剂的例子包括：4-[N,N-二(2-羟乙基)-N-十八烷基铵]-丁烷-1-羧酸盐；5-[S-3-羟丙基-S-十六烷基硫代]-3-羟基戊烷-1-硫酸盐；3-[P,P-二乙基-P-3,6,9-三氧杂二十四烷膦基]-2-羟基丙烷-1-磷酸盐；3-[N,N-二丙基-N-3-十二烷氧基-2-羟基丙基-氨基]-丙烷-1-膦酸盐；3-(N,N-二甲基-N-十六烷基氨基)-丙烷-1-磺酸盐；3-(N,N-二甲基-N-十六烷基氨基)-2-羟基-丙烷-1-磺酸盐；4-[N,N-二(2(2-羟基乙基)-N(2-羟基十二烷基)氨基]-丁烷-1-羧酸盐；3-[S-乙基-S-(3-十二烷氧基-2-羟基丙基)硫代]-丙烷-1-磷酸盐；3-[P,P-二甲基-P-十二烷基膦基]-丙烷-1-膦酸盐；和S[N,N-二(3-羟丙基)-N-十六烷基氨基]-2-羟基-戊烷-1-硫酸盐。所述的去垢剂表面活性剂中所含的烷基可以是直链或者支化的和饱和或者不饱和的。Examples of zwitterionic surfactants having the structures listed above include: 4-[N,N-bis(2-hydroxyethyl)-N-octadecylammonium]-butane-1-carboxylate; -[S-3-Hydroxypropyl-S-hexadecylthio]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9- Trioxatetradecylphosphino]-2-hydroxypropane-1-phosphate; 3-[N,N-Dipropyl-N-3-dodecyloxy-2-hydroxypropyl-amino] -propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylamino)-propane-1-sulfonate; 3-(N,N-dimethyl-N- Hexadecylamino)-2-hydroxy-propane-1-sulfonate; 4-[N,N-bis(2(2-hydroxyethyl)-N(2-hydroxydodecyl)amino]- Butane-1-carboxylate; 3-[S-Ethyl-S-(3-dodecyloxy-2-hydroxypropyl)thio]-propane-1-phosphate; 3-[P, P-Dimethyl-P-dodecylphosphino]-propane-1-phosphonate; and S[N,N-di(3-hydroxypropyl)-N-hexadecylamino]-2 -Hydroxy-pentane-1-sulfate. The alkyl group contained in the detergent surfactant can be linear or branched and saturated or unsaturated.
适用于本发明组合物的两性离子表面活性剂包括下面通用结构的甜菜碱：Zwitterionic surfactants suitable for use in the compositions of the present invention include betaines of the following general structure:
这些表面活性剂甜菜碱典型地在极端pH时不表现出强的阳离子或者阴离子属性，它们在它们的等电位范围内也不表现出降低的水溶解度。不同于“外部”季铵盐，甜菜碱是与阴离子相容的。合适的甜菜碱的例子包括椰油酰胺丙基二甲基甜菜碱；十六烷基二甲基甜菜碱；C12-14酰胺丙基甜菜碱；C8-14酰胺己基二乙基甜菜碱；4-C14-16酰基甲基酰氨基二乙基氨基-1-羧基丁烷；C16-18酰胺二甲基甜菜碱；C12-16酰胺戊烷二乙基甜菜碱；和C12-16酰基甲基酰氨二甲基甜菜碱。These surfactant betaines typically do not exhibit strong cationic or anionic character at extreme pH, nor do they exhibit reduced water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are anion-compatible. Examples of suitable betaines include cocamidopropyl dimethyl betaine; cetyl dimethyl betaine; C12-14 amidopropyl betaine; C8-14 amidohexyl diethyl betaine; 4-C14-16 acylmethylamidodiethylamino -1-carboxybutane; C16-18 amidodimethyl betaine; C12-16 amidopentane diethyl betaine; and C12- 16 Acylmethylamidodimethylbetaine.
可用于本发明的磺基甜菜碱包括具有式(R(R1)2N+R2SO3-的那些化合物，在其中R是C6-C18烃基，每个R1典型地独立地是C1-C3烷基，例如甲基，和R2是C1-C6烃基，例如C1-C3亚烷基或者羟基亚烷基。Sultaines useful in the present invention include those compounds having the formula (R(R1 )2 N+ R2 SO3- , where R is C6 -C18 hydrocarbyl, and each R1 is typically independently C1 -C3 alkyl, such as methyl, and R2 is C1 -C6 hydrocarbon, such as C1 -C3 alkylene or hydroxyalkylene.
一种典型的两性离子种类列表和这些表面活性剂物质是在1975年12月30日授予Laughlin和Heuring的美国专利No.3929678中给出的。另外的例子是在“Surface ActiveAgents and Detergents”(第I和II卷，Schwartz，Perry和Berch)中给出的。这些参考文献的每个在此以其全部引入作为参考。A list of typical zwitterionic species and such surfactant materials is given in US Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Additional examples are given in "Surface ActiveAgents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). Each of these references is hereby incorporated by reference in its entirety.
在一种实施方案中，本发明的组合物包括甜菜碱。例如该组合物可以包括椰油酰氨丙基甜菜碱。In one embodiment, the compositions of the present invention include betaine. For example the composition may include cocamidopropyl betaine.
实施方案implementation plan
本发明的二合一碱性去垢剂组合物的示例性范围是在表1A和1B中以固体去垢剂组合物的重量百分比来显示的。Exemplary ranges for the 2-in-1 alkaline detergent compositions of the present invention are shown in Tables 1A and 1B as weight percent solid detergent compositions.
表1ATable 1A
表1BTable 1B
该去垢剂组合物可以包括浓缩物组合物或者可以稀释来形成使用组合物。通常，浓缩物指的是这样的组合物，其打算用水稀释来提供使用溶液，其与物体接触来提供期望的清洁，漂洗等。与待清洗的制品接触的去垢剂组合物可以称作浓缩物或者使用组合物(或者使用溶液)，这取决于本发明方法中使用的制剂。应当理解地是氨基羧酸酯，水调节剂，碱度，水和其他任选的功能成分在去垢剂组合物中的浓度将根据去垢剂组合物是否作为浓缩物或者使用溶液提供来变化。The detergent composition may comprise a concentrate composition or may be diluted to form a use composition. In general, concentrates refer to compositions which are intended to be diluted with water to provide a use solution which comes into contact with objects to provide the desired cleaning, rinsing, and the like. Detergent compositions that come into contact with articles to be cleaned can be referred to as concentrates or use compositions (or use solutions), depending on the formulation used in the method of the invention. It should be understood that the concentration of aminocarboxylate, water conditioner, alkalinity, water and other optional functional ingredients in the detergent composition will vary depending on whether the detergent composition is provided as a concentrate or a use solution .
使用溶液可以由浓缩物如下来制备：以这样的稀释率来用水稀释该浓缩物，即，其提供了具有期望的清洁性的使用溶液。用于稀释浓缩物来形成使用组合物的水可以称作稀释水或者稀释剂，并且可以在不同的位置是不同的。典型的稀释因子是大约1-大约10000，但是将取决于这样的因素，包括水硬度，待除去的污垢的量等。在一种实施方案中，浓缩物是以大约1：10-大约1：10，000的浓缩物：水的比率来稀释的。具体的，该浓缩物是以大约1：100-大约1：5000的浓缩物：水的比率来稀释的。更具体的，该浓缩物是以大约1：250-大约1：2000的浓缩物：水的比率来稀释的。Use solutions may be prepared from concentrates by diluting the concentrate with water at a dilution rate that provides a use solution with the desired cleaning properties. The water used to dilute the concentrate to form the use composition may be referred to as water of dilution or diluent, and may be different at different locations. Typical dilution factors are from about 1 to about 10,000, but will depend on such factors as water hardness, amount of soil to be removed, etc. In one embodiment, the concentrate is diluted at a concentrate:water ratio of about 1:10 to about 1:10,000. Specifically, the concentrate is diluted at a concentrate:water ratio of about 1:100 to about 1:5000. More specifically, the concentrate is diluted at a concentrate:water ratio of about 1:250 to about 1:2000.
使用方法-清洁洗碗机中的制品How to use - cleaning products in the dishwasher
在一种实施方案中，本发明的方法包括使用步骤：提供本文公开的碱性二合一去垢剂组合物。具体的，使用方法优选使用固体碱性二合一去垢剂组合物，其中将固体组合物添加入洗碗机中或者与洗碗机相连的分配器中，特别是工业洗碗机。在本发明的一种实施方案中，该固体组合物可以作为多用途剂量来提供，其具有大约10-大约10000剂量/固体组合物。在本发明另一方面，该固体组合物可以以单用途组合物来配制，这里它在清洗中一次使用。该方法还包括用碱性二合一去垢剂组合物和水形成清洗溶液，将洗碗机中制品上的污垢与该清洗溶液接触，除去该污垢，和用饮用水漂洗该制品，无需使用单独的漂洗助剂组合物。该漂洗仅仅使用饮用水。In one embodiment, the method of the present invention comprises the step of using: providing an alkaline 2-in-1 detergent composition disclosed herein. Specifically, the method of use preferably uses a solid alkaline two-in-one detergent composition, wherein the solid composition is added into a dishwasher or a dispenser connected to the dishwasher, especially an industrial dishwasher. In one embodiment of the invention, the solid composition may be provided as a multi-purpose dose having from about 10 to about 10,000 doses per solid composition. In another aspect of the invention, the solid composition may be formulated as a single use composition, where it is used once in cleaning. The method also includes forming a cleaning solution with an alkaline 2-in-1 detergent composition and water, contacting the soil on the article in the dishwasher with the cleaning solution, removing the soil, and rinsing the article with potable water without using Separate rinse aid composition. Only potable water is used for this rinse.
在另一实施方案中，本发明的方法可以包括分别提供二合一去垢剂组合物的单个组分，并且将该单个组分与水原位混合来形成期望的清洗溶液。In another embodiment, the method of the present invention may comprise providing the individual components of the 2-in-1 detergent composition separately, and mixing the individual components with water in situ to form the desired cleaning solution.
当进行本发明的方法时，上述二合一去垢剂组合物添加入洗碗机的分配器中。该分配器可以选自多种不同的分配器，其取决于该组合物的物理形式。例如液体组合物可以使用泵(例如蠕动或者膜盒泵)，注射器/活塞注射，重力供料，虹吸管供料，吸气器，单元计量，例如使用水溶性包装例如聚乙烯醇，或者箔小包，从加压室排出，或者扩散穿过隔膜或者可透过表面来分配。如果该组合物是凝胶或者稠液体，则它可以使用泵例如蠕动泵或者膜盒泵，注射器/活塞注射，堵漏枪，单元计量，例如使用水溶性包装例如聚乙烯醇，或者箔小包，从加压室排出，或者扩散穿过隔膜或者可透过表面来分配。优选当该组合物是固体或粉末时，该组合物可以使用喷射，溢出，螺丝钻，摇动器，台式分配器，使用水溶性包装例如聚乙烯醇或者箔小包的单元计量，或者扩散穿过隔膜或者可透过表面来分配。该分配器还可以是双分配器，在其中一种组分分配到一侧上，和另一组分分配到另一侧上。这些示例性分配器可以位于多种洗碗机中或者与之相连，包括台下洗碗机，棒清洗器，门式机器，传送机或者飞行器。该分配器可以位于洗碗机内，远离或者安装在洗碗机之外。单个分配器可以供给一种或多种洗碗机。When carrying out the method of the present invention, the above-mentioned 2-in-1 detergent composition is added to the dispenser of the dishwasher. The dispenser may be selected from a variety of different dispensers, depending on the physical form of the composition. For example liquid compositions can be injected using a pump (e.g. peristaltic or bellows pump), syringe/piston injection, gravity feed, siphon feed, aspirator, unit metering, e.g. using water soluble packaging such as polyvinyl alcohol, or foil packets, Discharge from a pressurized chamber, or diffuse through a septum or permeable surface to dispense. If the composition is a gel or viscous liquid, it can be injected using a pump such as a peristaltic pump or a bellows pump, a syringe/plunger, a plug gun, unit metered, for example using a water soluble pack such as polyvinyl alcohol, or a foil packet, Discharge from a pressurized chamber, or diffuse through a septum or permeable surface to dispense. Preferably when the composition is a solid or powder, the composition can be dosed using a squirt, spill, auger, shaker, bench top dispenser, unit dosed using water soluble packaging such as polyvinyl alcohol or foil packets, or diffused through a septum Alternatively it can be dispensed through the surface. The dispenser can also be a double dispenser, in which one component is dispensed on one side and the other component is dispensed on the other side. These exemplary dispensers may be located in or associated with a variety of dishwashers, including undercounter dishwashers, bar washers, portal machines, conveyors, or aircraft. The dispenser can be located inside the dishwasher, remote or mounted outside the dishwasher. A single dispenser can feed one or more types of dishwashers.
一旦该二合一去垢剂组合物添加入分配器中，则开始该洗碗机的清洗周期，并且形成清洗溶液。该清洗溶液包含碱性二合一去垢剂组合物和来自于洗碗机的水。该水可以任何类型的水，包括硬水，软水，净水或者污水。最优选的清洗溶液是保持在优选的pH范围大约7-大约11.5，更优选大约9.5-大约11.5的溶液，其是通过pH探针，基于16加仑洗碗机中的组合物溶液来测量的。如果该探针通过将该探针从pH简单地切换到毫伏而允许两种功能，则相同的探针可以用于测量毫伏特。该分配器或洗碗机可以任选包括pH探针来在整个清洗周期中测量清洗溶液的pH。实际的浓度或者水与去垢剂比率取决于所用的具体表面活性剂。示例性浓度范围可以包括高到3000ppm，优选1-3000ppm，更优选100-3000ppm和最优选300-2000ppm。同样，所用实际浓度取决于所选择的表面活性剂。Once the 2-in-1 detergent composition is added to the dispenser, the dishwasher's wash cycle begins and a wash solution is formed. The cleaning solution comprises an alkaline 2-in-1 detergent composition and water from a dishwasher. The water can be any type of water, including hard water, soft water, clean water or sewage. The most preferred cleaning solution is one maintained at a preferred pH range of about 7 to about 11.5, more preferably about 9.5 to about 11.5, as measured by a pH probe, based on a solution of the composition in a 16 gallon dishwasher. The same probe can be used to measure millivolts if the probe allows both functions by simply switching the probe from pH to millivolts. The dispenser or dishwasher may optionally include a pH probe to measure the pH of the cleaning solution throughout the cleaning cycle. The actual concentration or water to detergent ratio will depend on the particular surfactant used. Exemplary concentration ranges may include up to 3000 ppm, preferably 1-3000 ppm, more preferably 100-3000 ppm and most preferably 300-2000 ppm. Again, the actual concentration used will depend on the surfactant chosen.
当用于本发明的方法时，使用溶液可以具有升高的温度(即加热到升高的温度)。在一个例子中，将温度为大约120°F-大约185°F，大约140°F-大约185°F的使用溶液与待清洁的基底接触。在另一例子中，将温度为大约150°F-大约160°F的使用溶液与待清洁的基底接触。When used in the methods of the invention, the use solution may have an elevated temperature (ie, be heated to an elevated temperature). In one example, a use solution having a temperature of about 120°F to about 185°F, about 140°F to about 185°F is contacted with the substrate to be cleaned. In another example, a use solution at a temperature of about 150°F to about 160°F is contacted with the substrate to be cleaned.
在形成清洗溶液之后，该清洗溶液与洗碗机中制品上的污垢接触。污垢的例子包括在食品中通常遇到的污垢例如含蛋白质的污垢，疏水脂肪污垢，与碳水化合物和简单的糖相关的淀粉和糖类污垢，来自于牛奶和奶制品的污垢，水果和蔬菜污垢等。污垢还可以包括来自于硬水的矿物例如诸如钾，钙，镁和钠。可以接触的制品包括由玻璃，塑料，铝，钢，铜，黄铜，银，橡胶，木材，陶瓷等制成的制品。制品包括通常存在于洗碗机中的物质例如玻璃，碗，平板，杯子，罐和盘子，焙烤器皿例如烹饪盘，蛋糕盘，松饼盘等，银器皿例如叉子，勺子，刀子，烹饪用具例如木制勺子，刮刀，橡胶铲，通用刀具，钳子，格栅用具，上菜用具等。清洗溶液可以与污垢以许多方式接触，包括喷涂，浸涂，水浸泡溶液，薄雾和雾化。After the cleaning solution is formed, the cleaning solution contacts the soil on the articles in the dishwasher. Examples of soils include soils commonly encountered in food products such as protein-containing soils, hydrophobic fatty soils, starch and sugar soils associated with carbohydrates and simple sugars, soils from milk and milk products, fruit and vegetable soils Wait. Dirt may also include minerals from hard water such as potassium, calcium, magnesium and sodium, for example. Articles that can be touched include those made of glass, plastic, aluminum, steel, copper, brass, silver, rubber, wood, ceramics, and more. Articles include substances commonly found in dishwashers such as glasses, bowls, plates, cups, pots and plates, bakeware such as cooking pans, cake pans, muffin pans, etc., silverware such as forks, spoons, knives, cooking utensils such as Wooden spoons, spatulas, rubber spatulas, all-purpose knives, tongs, grating utensils, serving utensils, etc. Cleaning solutions can come into contact with soils in many ways, including spraying, dipping, water soaking solutions, misting and atomizing.
一旦该清洗溶液已经接触污垢，则将污垢从制品上除去。污垢从制品上除去是通过清洗溶液和污垢之间的化学反应以及清洗溶液在制品上的机械作用来完成的，这取决于清洗溶液如何接触制品。Once the cleaning solution has contacted the soil, the soil is removed from the article. Soil removal from articles is accomplished through chemical reactions between the cleaning solution and the soil, as well as mechanical action of the cleaning solution on the article, depending on how the cleaning solution contacts the article.
一旦除去了污垢，则作为洗碗机清洗周期的一部分，用饮用水漂洗该制品，而不使用分别的或者另外的漂洗助剂组合物。Once the soil is removed, the article is rinsed with potable water as part of a dishwasher wash cycle without the use of a separate or additional rinse aid composition.
该方法可以包括比此处所述更多步骤或者更少的步骤。例如该方法可以包括另外的步骤，其通常与洗碗机清洗周期相关。例如该方法还可以任选包括使用酸性去垢剂。例如该方法可以任选包括交替的酸性去垢剂和所述的碱性去垢剂。The method may include more or fewer steps than described herein. For example the method may comprise further steps which are normally associated with a dishwasher wash cycle. For example, the method may also optionally include the use of acidic detergents. For example the method may optionally include alternating acidic detergents and said alkaline detergents.
制造组合物的方法method of making the composition
本发明的组合物可以包括液体产品，增稠的液体产品，凝胶化的液体产品，糊，粒状的和粒化的固体组合物，粉末，固体块组合物，浇铸固体块组合物，挤出的固体块组合物和其他。Compositions of the present invention may include liquid products, thickened liquid products, gelled liquid products, pastes, granular and granulated solid compositions, powders, solid block compositions, cast solid block compositions, extruded Solid Block Compositions and others.
固体颗粒材料可以通过仅仅将干燥固体成分以适当的比率混合或者将该材料在适当的聚集系统中聚集来制造。粒化材料可以通过将固体粒状的或者聚集的材料在适当的粒化装置中压缩来产生适当尺寸化的粒化材料来制造。固体块和浇铸固体块材料可以通过向容器中引入预硬化的材料块或者可浇铸的液体(其在容器中硬化成固体块)来制造。优选的容器包括一次性塑料容器或者水溶性膜容器。用于所述组合物的其他合适的包装包括挠性袋，包裹，热缩塑料包和水溶性膜例如聚乙烯醇。Solid particulate material can be produced by simply mixing dry solid ingredients in suitable ratios or aggregating the material in a suitable agglomeration system. Granulated material may be produced by compressing solid granular or aggregated material in a suitable granulating device to produce suitably sized granulated material. Solid blocks and cast solid block materials can be produced by introducing into a container a pre-hardened block of material or a castable liquid which hardens into a solid block in the container. Preferred containers include disposable plastic containers or water soluble film containers. Other suitable packaging for the compositions include flexible bags, wraps, shrink wrap and water soluble films such as polyvinyl alcohol.
该固体去垢剂组合物可以使用批次的或者连续的混合系统来形成。在一种示例性实施方案中，单或双螺杆挤出机用于以高剪切力来组合和混合一种或多种组分来形成均匀的混合物。在一些实施方案中，加工温度处于或者低于组分的熔融温度。该加工的混合物可以从混合器通过成形，浇铸或者其他合适的手段来分配，在此该去垢剂组合物硬化成固体形式。基质的结构可以根据它的硬度，熔点，材料分布，晶体结构和其他类似性能，根据本领域已知的方法来表征。通常，根据本发明方法加工的固体去垢剂组合物在成分在它的整个质量中分布方面是基本均匀的，并且是尺寸稳定的。The solid detergent composition can be formed using a batch or continuous mixing system. In an exemplary embodiment, a single or twin screw extruder is used to combine and mix one or more components at high shear to form a homogeneous mixture. In some embodiments, the processing temperature is at or below the melting temperature of the components. The processed mixture may be dispensed from the mixer by shaping, casting or other suitable means where the detergent composition hardens into a solid form. The structure of the matrix can be characterized according to its hardness, melting point, material distribution, crystal structure and other similar properties according to methods known in the art. Generally, a solid detergent composition processed according to the method of the present invention will be substantially uniform in distribution of ingredients throughout its mass and will be dimensionally stable.
在一种挤出方法中，将液体和固体组分引入最终的混合系统中，并且连续混合，直到该组分形成基本上均匀的半固体混合物，在其中组分分布在整个它的质量中。该混合物然后从混合系统排入或者排过口模或者其他成形装置。该产品然后包装。在一种示例性实施方案中，所形成的组合物在大约1分钟-大约3小时开始硬化成固体形式。具体的，所形成的组合物在大约1分钟-大约2小时开始硬化成固体形式。更具体的，所形成的组合物在大约1分钟-大约20分钟开始硬化成固体形式。In one extrusion process, liquid and solid components are introduced into a final mixing system and mixed continuously until the components form a substantially homogeneous semi-solid mixture in which the components are distributed throughout its mass. The mixture is then discharged from the mixing system into or through a die or other forming device. The product is then packaged. In an exemplary embodiment, the formed composition begins to harden into a solid form between about 1 minute and about 3 hours. Specifically, the formed composition begins to harden into a solid form within about 1 minute to about 2 hours. More specifically, the formed composition begins to harden into a solid form between about 1 minute and about 20 minutes.
在浇铸方法中，将所述液体和固体组分引入最终混合系统中，并且连续混合，直到该组分形成基本上均匀的液体混合物，在其中组分分布在它的整个质量中。在一种示例性实施方案中，该组分在混合系统中混合至少大约60秒。一旦完成该混合，在将该产品转移到包装容器，在这里进行固化。在一种示例性实施方案中，该浇铸组合物在大约1分钟-大约3小时开始硬化成固体形式。具体的，该浇铸组合物在大约1分钟-大约2小时开始硬化成固体形式。更具体的，该浇铸组合物在大约1分钟-大约20分钟开始硬化成固体形式。In the casting process, the liquid and solid components are introduced into the final mixing system and mixed continuously until the components form a substantially homogeneous liquid mixture in which the components are distributed throughout its mass. In an exemplary embodiment, the components are mixed in the mixing system for at least about 60 seconds. Once the mixing is complete, the product is transferred to packaging containers where it cures. In an exemplary embodiment, the casting composition begins to harden into a solid form between about 1 minute and about 3 hours. Specifically, the casting composition begins to harden into a solid form in about 1 minute to about 2 hours. More specifically, the casting composition begins to harden into a solid form between about 1 minute and about 20 minutes.
在压缩的固体方法中，可流动固体例如粒状的固体或者其他粒子固体(包括粘合剂，例如水合螯合剂，例如水合氨基羧酸(盐)，水合聚羧酸(盐)或者水合阴离子聚合物，水合柠檬酸盐或者水合酒石酸盐等以及碱金属碳酸盐一起)是在压力下组合的。在压缩的固体方法中，该组合物的可流动固体放入成形体(例如模具或容器)中。该方法可以包括轻压该一定形式的可流动固体来生产固体清洁组合物。压力可以通过砌块机或者转盘压机等来施加。压力可以以大约1-大约2000psi，大约1-大约300psi，大约5psi-大约200psi，或者大约10psi-大约100psi来施加。在某些实施方案中，该方法可以使用低到大于或等于大约1psi，大于或等于大约2，大于或等于大约5psi，或者大于或等于大约10psi的压力。作为本文使用的，术语“psi”或者“磅/平方英寸”指的是施加到被压缩的可流动固体的实际压力，并且不指的是在进行压缩的设备中一个点所测量的表压或者水力压力。该方法可以包括固化步骤来生产固体清洁组合物。作为本文提及的，将包括可流动固体的未固化组合物压缩来提供构成可流动固体的粒子间足够的表面接触，这样该未固化的组合物将固化成稳定的固体清洁组合物。足够量的粒子(例如颗粒)彼此接触提供了粒子的彼此有效结合来制造稳定的固体组合物。包括固化步骤可以包括使得压缩的固体固化一段时间，例如几小时，或者大约1天(或更长)。在另外的方面，该方法可以包括在成形体或模具中振动该可流动固体，例如公开在美国专利No.8889048中的方法，其在此以其全部引入作为参考。In the compressed solid method, flowable solids such as granular solids or other particulate solids (including binders, such as hydrated chelating agents, such as hydrated aminocarboxylic acid (salt), hydrated polycarboxylic acid (salt), or hydrated anionic polymer , hydrated citrate or hydrated tartrate, etc. and alkali metal carbonate) are combined under pressure. In the compressed solid method, the flowable solid of the composition is placed into a shaped body such as a mold or container. The method may comprise lightly compressing the form of flowable solid to produce a solid cleaning composition. The pressure can be applied by a block machine or a turntable press or the like. Pressure may be applied at about 1 to about 2000 psi, about 1 to about 300 psi, about 5 psi to about 200 psi, or about 10 psi to about 100 psi. In certain embodiments, the method may use pressures as low as about 1 psi or greater, about 2 or greater, about 5 psi or greater, or about 10 psi or greater. As used herein, the term "psi" or "pounds per square inch" refers to the actual pressure applied to a flowable solid being compressed, and does not refer to gauge pressure or hydraulic pressure. The method may include a curing step to produce a solid cleaning composition. As referred to herein, compression of an uncured composition comprising a flowable solid provides sufficient surface contact between the particles comprising the flowable solid such that the uncured composition will cure into a stable solid cleaning composition. Contacting a sufficient number of particles (eg, granules) with each other provides effective association of the particles with each other to produce a stable solid composition. Including a curing step may include allowing the compressed solid to cure for a period of time, such as a few hours, or about 1 day (or longer). In additional aspects, the method may comprise vibrating the flowable solid in a shaped body or mold, such as the method disclosed in US Patent No. 8,889,048, which is hereby incorporated by reference in its entirety.
使用压缩的固体提供了优于常规固体块或者片状组合物(其在片式压机中需要高压，或者消耗了大量的能量的需要熔融组合物的浇铸，和/或通过需要昂贵的装置和先进的技术专门知识的挤出)的诸多益处。压缩的固体克服了其他固体配料的这样的不同的限制(对其来说需要制造固体清洁组合物)。此外，压缩的固体组合物在该组合物可以存储或者处置的条件下保持了它的形状。The use of compressed solids provides advantages over conventional solid block or tablet compositions which require high pressures in tablet presses, or require casting of molten compositions which consume large amounts of energy, and/or which require expensive equipment and The many benefits of extruding advanced technical expertise). Compressed solids overcome such different limitations of other solid formulations for which solid cleansing compositions need to be manufactured. Furthermore, a compressed solid composition retains its shape under conditions under which the composition can be stored or handled.
用术语“固体”表示硬化的组合物在中等应力或者压力或者仅仅重力下将不流动将基本上保持它的形状。固体可以处于不同的形式例如粉末，薄片，颗粒，粒料，片，菱形，压片(puck)，饼状，砖块，固体块，单位剂量或者本领域技术人员已知的另一固体形式。该固体浇铸组合物和/或压缩固体组合物的硬度程度范围可以从熔合固体产品(其是相对致密和硬的，例如混凝土)到硬化的糊所特有的稠度。另外，术语“固体”指的是去垢剂组合物在固体去垢剂组合物的存储和使用预期条件下的状态。通常，预期地是当曝露于高达大约100℉和特别是高达大约120℉的温度时，该去垢剂组合物将保持为固体形式。By the term "solid" is meant that the hardened composition will not flow and will substantially retain its shape under moderate stress or pressure or mere gravity. The solid may be in different forms such as powder, flakes, granules, pellets, flakes, lozenges, pucks, cakes, bricks, solid blocks, unit doses or another solid form known to those skilled in the art. The degree of hardness of the solid casting composition and/or compressed solid composition may range from a fused solid product (which is relatively dense and hard, such as concrete) to a consistency typical of a hardened paste. Additionally, the term "solid" refers to the state of the detergent composition under the conditions expected for storage and use of the solid detergent composition. Generally, it is expected that the detergent composition will remain in solid form when exposed to temperatures up to about 100°F, and especially up to about 120°F.
所形成的固体去垢剂组合物可以采用这样的形式，包括但不限于此：浇铸固体产品；挤出的，模制的或者形成的固体粒料，块，片，粉末，颗粒，薄片；压缩的固体；或者形成的固体可以其后研磨或者形成粉末，颗粒或者薄片。在一种示例性实施方案中，通过固化基质所形成的挤出的粒料材料的重量是大约50g-大约250g，通过所述组合物形成的挤出的固体的重量是大约100g或更大，和通过所述组合物形成的固体块去垢剂的质量是大约1-大约10kg。该固体组合物提供了稳定的功能材料源。在一些实施方案中，该固体组合物可以溶解在例如含水或者其他介质中，来产生浓缩溶液和/或使用溶液。该溶液可以导向存储容器，来用于随后的使用和/或稀释，或者可以直接用于使用位置。The formed solid detergent composition may take forms including, but not limited to: cast solid products; extruded, molded or formed solid pellets, blocks, tablets, powders, granules, flakes; compressed or the solid formed can thereafter be ground or formed into a powder, granules or flakes. In an exemplary embodiment, the weight of the extruded pellet material formed by curing the matrix is from about 50 g to about 250 g, the weight of the extruded solid formed by the composition is about 100 g or greater, And the mass of the solid block detergent formed by the composition is from about 1 to about 10 kg. The solid composition provides a stable source of functional materials. In some embodiments, the solid composition can be dissolved, for example, in an aqueous or other medium to produce a concentrated solution and/or a use solution. The solution can be directed to a storage container for subsequent use and/or dilution, or can be used directly at the point of use.
下面的专利公开固化，结合和/或硬化剂的不同组合，其可以用于本发明的固体清洁组合物。下面的美国专利在此引入作为参考：美国专利No.7153820；7094746；7087569；7037886；6831054；6730653；6660707；6653266；6583094；6410495；6258765；6177392；6156715；5858299；5316688；5234615；5198198；5078301；4595520；4680134；RE32763；和RE32818。The following patents disclose different combinations of curing, binding and/or hardening agents which can be used in the solid cleaning compositions of the present invention.下面的美国专利在此引入作为参考：美国专利No.7153820；7094746；7087569；7037886；6831054；6730653；6660707；6653266；6583094；6410495；6258765；6177392；6156715；5858299；5316688；5234615；5198198；5078301； 4595520; 4680134; RE32763; and RE32818.
液体组合物可以典型地通过在含水液体或者含水液体溶剂体系中形成组分来制造。这样的体系典型地是通过在水或者在相容性溶剂中溶解或者悬浮活性成分，然后将该产品稀释到适当的浓度，来形成浓缩物或者其使用溶液来制造。凝胶化组合物可以类似地通过在相容性含水，含水液体或者混合的含水有机体系(包括凝胶化剂)中，以适当的浓度溶解或者悬浮活性成分来制造。Liquid compositions can typically be made by forming the components in an aqueous liquid or an aqueous liquid solvent system. Such systems are typically manufactured by dissolving or suspending the active ingredient in water or in a compatible solvent and then diluting the product to the appropriate concentration to form a concentrate or a use solution thereof. Gelled compositions may similarly be prepared by dissolving or suspending the active ingredient at an appropriate concentration in a compatible aqueous, aqueous liquid or mixed aqueous organic system (including a gelling agent).
本说明书中全部公开文献和专利申请是本发明所属领域的技术人员的水平的指示。全部公开文献和专利申请在此引入，作为与每个单个的公开文献或者专利申请明确的和单独地引入作为参考所示的相同程度。All publications and patent applications in this specification are indicative of the level of those skilled in the art to which this invention pertains. All publications and patent applications are hereby incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
实施例Example
本发明的实施方案进一步在下面的非限定性实施例中定义。应当理解这些实施例虽然显示了本发明的某些实施方案，但是仅仅是作为示例来给出的。从上面的讨论和这些实施例，本领域技术人员可以确定本发明的基本特性，而不脱离其主旨和范围，可以对本发明的实施方案进行不同的改变和变化来使得它适于不同的使用和条件。因此，除了本文所示和所述的那些之外，本发明实施方案不同的改变将从前述说明书而对于本领域技术人员是显而易见的。这样的改变也打算落入附加权利要求的范围内。Embodiments of the invention are further defined in the following non-limiting examples. It should be understood that these Examples, while indicating certain embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, various changes and modifications can be made to the embodiments of the invention to adapt it to various uses and uses. condition. Accordingly, various modifications of the embodiments of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such changes are also intended to fall within the scope of the appended claims.
实施例1-4Example 1-4
此处提供了实施例1-4所用的材料：The materials used in Examples 1-4 are provided here:
25R2：一种EO/PO共聚物，获自BASF。 25R2: an EO/PO copolymer available from BASF.
II 1012GB-21：一种醇烷氧基化物，获自Sasol。 II 1012GB-21 : An alcohol alkoxylate ex Sasol.
另外的材料市售自多个来源，包括：碳酸钠，灰单水合物，三聚磷酸钠(无水)，氯化锌，HEDP和KOH。Additional materials are commercially available from a variety of sources including: sodium carbonate, ash monohydrate, sodium tripolyphosphate (anhydrous), zinc chloride, HEDP and KOH.
制备了实施例1-4，其是示例性二合一去垢剂，并且是表2所示的。在实施例1-4整个中，配料被称作实验配料1(Exp.1)。Examples 1-4, which are exemplary 2-in-1 detergents, were prepared and are shown in Table 2. Throughout Examples 1-4, the formulation is referred to as Experimental formulation 1 (Exp. 1).
表2Table 2
现有的去垢剂，漂洗助剂和实验配料1是用蒸馏水来测试的。去垢剂对照物1和去垢剂对照物2是市售的去垢剂(磷酸盐基去垢剂)。漂洗助剂对照物1和漂洗助剂对照物2是两种市售的漂洗助剂(使用更高量的至少两种离子类(例如非离子和阳离子)的活性成分和表面活性剂)。下述全部实验的使用浓度提供在下表中：Existing detergents, rinse aids and test ingredient 1 were tested with distilled water. Detergent Control 1 and Detergent Control 2 are commercially available detergents (phosphate based detergents). Rinse Aid Control 1 and Rinse Aid Control 2 are two commercially available rinse aids (with higher levels of active ingredients and surfactants of at least two ionic classes (eg, non-ionic and cationic)). The concentrations used for all experiments described below are provided in the table below:
表3table 3
全部器皿清洗测试是用10盎司Libbey玻璃在Hobart AM-15洗碗机中进行的。Hobart AM-15洗碗机的规格如下：All warewash tests were performed in a Hobart AM-15 dishwasher using 10 oz Libbey glass. The specifications of the Hobart AM-15 Dishwasher are as follows:
Hobart AM-15洗碗机规格Hobart AM-15 Dishwasher Specifications
实施例1Example 1
动态表面张力dynamic surface tension
SITA科学线t60测量了高到半静态范围的液体的动态表面张力。从具有已知半径的毛细管产生了空气气泡。该气泡压力是作为气泡寿命的函数来测量的，其可以根据Young-Laplace等式与表面张力相关。动态表面张力提供了对于表面活性剂和其他表面活性化合物在动态条件下的动态行为的观察，即，表面活性剂多快可以到达表面。该动态表面张力是表面活性剂的浓度，温度和类型的函数。该表面活性剂的动态表面张力行为在这样的应用中是特别重要的，这里需要表面活性剂的快速响应，例如在自动洗碗的短漂洗周期中。The SITA Scientific Line t60 measures the dynamic surface tension of liquids in the high to semi-static range. Air bubbles are generated from capillaries with known radii. The bubble pressure is measured as a function of bubble lifetime, which can be related to surface tension according to the Young-Laplace equation. Dynamic surface tension provides insight into the dynamic behavior of surfactants and other surface active compounds under dynamic conditions, ie, how quickly a surfactant can reach a surface. This dynamic surface tension is a function of the concentration, temperature and type of surfactant. The dynamic surface tension behavior of the surfactant is particularly important in applications where a fast response of the surfactant is required, for example in the short rinse cycles of automatic dishwashing.
设备和材料：Equipment and materials:
1.SITA T60(Sita Messtechnik，德国)1. SITA T60 (Sita Messtechnik, Germany)
2.具有搅拌棒的油浴2. Oil bath with stir bar
3.加热和搅拌盘3. Heating and stirring plate
4.玻璃烧杯4. Glass beaker
5.玻璃小瓶(20mL)5. Glass vial (20mL)
该SITA科学线t60是用去离子水校正的。在校正后清洁水样品的表面张力应当是72.0±1.0mN/m(取决于水品质和温度)。在校正后，该SITA程序化来在期望的时间间隔(即，0.3，1.6，3.0和9.1秒)采集读数。对于每个待测试的组合物(描述为样品A-C)(例如Exp.1的三个样品，去垢剂对照物1的三个样品)，准备了在期望的ppm的三种分别的溶液。将10-15mL转移到20mL小瓶中，并且浸入到72℃(160°F)±2℃的加热油浴中。将该样品平衡10-15分钟。将该样品从油浴中单个移除，并且在SITA中测试。在每个样品测试后，运行SITA清洁程序，然后检查去离子水的表面张力来确保该SITA充分清洁。如果去离子水测量不是在72.0±1.0mN/m内，则再次运行清洁程序。下表4A-4F提供了在160°F的表面张力(mN/m)vs气泡寿命实验数据，其中τ：气泡寿命(s)；γ：表面张力(mN/m)。The SITA Scientific Line t60 is calibrated with deionized water. The surface tension of the clean water sample after calibration should be 72.0 ± 1.0 mN/m (depending on water quality and temperature). After calibration, the SITA was programmed to take readings at desired time intervals (ie, 0.3, 1.6, 3.0 and 9.1 seconds). For each composition to be tested (depicted as samples A-C) (eg three samples of Exp. 1, three samples of detergent control 1), three separate solutions at the desired ppm were prepared. Transfer 10-15 mL to a 20 mL vial and immerse in a heated oil bath at 72°C (160°F) ± 2°C. The sample was equilibrated for 10-15 minutes. The samples were individually removed from the oil bath and tested in SITA. After each sample test, run the SITA cleaning program, then check the surface tension of the deionized water to ensure that the SITA is sufficiently clean. If the deionized water measurement is not within 72.0 ± 1.0 mN/m, run the cleaning program again. Tables 4A-4F below provide experimental data for surface tension (mN/m) vs. bubble life at 160°F, where τ: bubble life (s); γ: surface tension (mN/m).
表4ATable 4A
表4BTable 4B
表4CTable 4C
表4DTable 4D
表4ETable 4E
表4FForm 4F
对于平均气泡寿命0.3，1.6，3.0，和9.1秒，测试了在160°F的平均表面张力。结果提供在表5中。The average surface tension at 160°F was tested for average bubble lifetimes of 0.3, 1.6, 3.0, and 9.1 seconds. The results are provided in Table 5.
表5table 5
该数据证实了实验配料1的表面张力随着气泡寿命9.1秒时的表面张力的明显下降而快速降低。这类似于公知的漂洗助剂，例如漂洗助剂对照物2。这些结果显示在图1中。The data demonstrates that the surface tension of Experimental Formulation 1 decreases rapidly with a significant drop in surface tension at a bubble lifetime of 9.1 seconds. This is similar to known rinse aids such as Rinse Aid Control 2. These results are shown in Figure 1.
实施例2Example 2
用于公共器皿清洗去垢剂的100周期膜评价100-Cycle Membrane Evaluation for Public Dishwashing Detergents
为了测定不同的去垢剂组合物除去器皿上的污点和膜的能力，通过除去玻璃表面上的全部膜和外来材料，来准备了6个Libby 10盎司大玻璃杯。然后向Hobart AM-15洗碗机中填充适量的水，并且测试该水的硬度。在记录了硬度值之后，打开槽加热器。在实验日，水硬度是17格令。打开该洗碗机，并且在该机器中运行清洗/漂洗周期，直到达到清洗温度大约150°F-大约160°F和漂洗温度大约175°F-大约190°F。然后设定控制器来将适量去垢剂分配到清洗槽中。分配该去垢剂，以使得当去垢剂在所述周期过程中与水混合来形成使用溶液时，使用溶液中的去垢剂浓度是750份/百万份(ppm)。滴定该清洗槽中的溶液来检验去垢剂浓度。该洗碗机的清洗浴体积是58升，漂洗体积2.8升，清洗时间50秒和漂洗时间9秒。To determine the ability of different detergent compositions to remove stains and film from ware, six Libby 10 oz tumblers were prepared by removing all film and foreign material from the glass surface. The Hobart AM-15 dishwasher was then filled with the appropriate amount of water and tested for hardness. After the hardness value is recorded, the bath heater is turned on. On the test day, the water hardness was 17 grains. Turn on the dishwasher and run a wash/rinse cycle in the machine until a wash temperature of about 150°F to about 160°F and a rinse temperature of about 175°F to about 190°F is reached. The controller is then programmed to dispense the proper amount of detergent into the wash tank. The detergent was dispensed such that when the detergent was mixed with water during the cycle to form the use solution, the detergent concentration in the use solution was 750 parts per million (ppm). Titrate the solution in the wash tank to check the detergent concentration. The dishwasher has a wash bath volume of 58 liters, a rinse volume of 2.8 liters, a wash time of 50 seconds and a rinse time of 9 seconds.
将6个洁净的大玻璃杯对角线置于Raburn架子上，并且将4个Newport 10盎司塑料杯远离对角线置于该Raburn架子上(见下图的排列)，并且将该架子置于洗碗机内。(P＝塑料杯；G＝大玻璃杯)。Place 6 clean tumblers diagonally on the Raburn rack and place 4 Newport 10 oz plastic cups away from the diagonal on the Raburn rack (see arrangement below) and place the rack on Inside the dishwasher. (P = plastic cup; G = tumbler).
然后开始该100周期测试。在每个清洗周期开始时，将适量去垢剂自动分配到洗碗机中来保持初始去垢剂浓度。该去垢剂浓度是通过电导率来控制的。The 100 cycle test is then started. At the start of each wash cycle, an appropriate amount of detergent is automatically dispensed into the dishwasher to maintain the initial detergent concentration. The detergent concentration is controlled by conductivity.
一旦完成100个周期，将所述架子从洗碗机中除去，并且使得该玻璃和塑料杯子干燥。然后将该玻璃和塑料杯子使用膜等级和使用分析光盒评估对污点和膜聚集进行分级。膜等级尺度提供在表6中。Once 100 cycles were completed, the rack was removed from the dishwasher and the glass and plastic cups were allowed to dry. The glass and plastic cups were then graded for staining and film accumulation using a film grade and assessed using an analytical light box. The film grade scale is provided in Table 6.
表6Table 6
该光盒测试使用了数码相机，光盒，光源，光度计和对照物计算机，其使用了“SpotAdvance”和“Image Pro Plus”商业软件。将待评估的玻璃置于光盒上它的侧面上，并且使用光度计来将光源强度调节到预定值。对该玻璃进行照相图像，并且存储到计算机。然后使用所述软件来分析该玻璃的上半部分，并且该计算机显示了柱状图，并且该图下的面积是与膜厚成比例的。The light box test uses a digital camera, light box, light source, photometer and control computer using "SpotAdvance" and "Image Pro Plus" commercial software. The glass to be evaluated is placed on its side on the light box, and a photometer is used to adjust the light source intensity to a predetermined value. A photographic image is taken of the glass and stored to a computer. The software was then used to analyze the top half of the glass and the computer displayed a histogram and the area under the graph was proportional to the film thickness.
通常，较低的光盒分数指示了更多的光能够送过所述杯子。因此，光盒分数越低，该组合物在防止杯子表面上的结垢方面越有效。洁净的，未用的玻璃杯的光盒分数是大约12000，其对于6个玻璃杯子来说对应于72000的分数，和洁净的，未用的塑料杯子的光盒分数是大约25500，其对于4个塑料杯子来说对应于大约102000的光盒分数。最小可获得的光盒分数(即，6个洁净的玻璃杯子和4个洁净的塑料杯子的总和)是大约174000。通常，如果6个玻璃杯子和4个塑料杯子的光盒分数之和是大约360000或者更低，则去垢剂组合物被认为在控制硬水结垢方面是有效的。In general, a lower light box score indicates that more light was able to be sent through the cup. Thus, the lower the light box score, the more effective the composition is at preventing fouling on the surface of the cup. The light box score for a clean, unused glass cup is approximately 12000, which corresponds to a score of 72000 for 6 glass cups, and for a clean, unused plastic cup is approximately 25500, which corresponds to a score of 72000 for a clean, unused plastic cup. This corresponds to a light box score of about 102,000 for a plastic cup. The minimum achievable light box score (ie, the sum of 6 clean glass cups and 4 clean plastic cups) is about 174000. In general, a detergent composition is considered effective in controlling hard water scaling if the sum of the light box scores for the 6 glass cups and 4 plastic cups is about 360,000 or less.
100个循环测试的结果提供在表7-8中，其提供了玻璃和塑料杯子的平均膜等级。The results of the 100 cycle tests are provided in Tables 7-8, which provide the average film ratings for glass and plastic cups.
表7Table 7
表8Table 8
实施例3Example 3
用于公共器皿清洗去垢剂的50周期再沉积实验50-Cycle Redeposition Test of Detergent for Public Utensil Cleaning
对于公共器皿清洗去垢剂，使用50周期再沉积实验进一步评价了本发明组合物和对照物的清洁效率。为了测试组合物清洁玻璃和塑料的能力，使用了6个10盎司Libby耐热玻璃杯和1个塑料杯。该玻璃杯在使用前清洁。对每个实验使用新的塑料杯。For public dishwashing detergents, the cleaning efficiency of the inventive compositions and controls was further evaluated using a 50 cycle redeposition test. To test the ability of the compositions to clean glass and plastic, six 10 oz Libby Pyrex cups and one plastic cup were used. The glass is cleaned before use. Use new plastic cups for each experiment.
使用50/50组合的炖牛肉和热点污垢和使用2000ppm污垢制备了食品污垢溶液。该污垢包括两罐Dinty Moore Beef Stew(1360g)，1大罐番茄酱(822g)，15.5根Blue BonnetMargarine(1746g)和奶粉(436.4g)。将热点污垢加入所述机器中来保持总浓度大约2000ppm。Food soil solutions were prepared using a 50/50 combination of beef stew and hot spot soils and using 2000 ppm soil. The dirt included two tins of Dinty Moore Beef Stew (1360g), 1 large tin of tomato sauce (822g), 15.5 sticks of Blue Bonnet Margarine (1746g) and milk powder (436.4g). Hot spot soil was added to the machine to maintain a total concentration of approximately 2000 ppm.
在用17格令水填充洗碗机之后，打开加热器。将清洗温度调节到大约150-160°F。将最终的漂洗温度调节到大约175-190°F。将控制器设定来显示清洗槽中的去垢剂的量。将玻璃和塑料杯子置于Raburn架子上(见下图的排列；P＝塑料杯；G＝玻璃杯)，并且将该架子置于洗碗机内。After filling the dishwasher with 17 grains of water, turn on the heater. Adjust the wash temperature to approximately 150-160°F. Adjust the final rinse temperature to approximately 175-190°F. Set the controller to display the amount of detergent in the wash tank. Place the glass and plastic cups on a Raburn rack (see arrangement below; P = plastic cups; G = glass cups) and place the rack in the dishwasher.
该洗碗机然后启动和运行自动的周期。在每个周期开始时，将适量的热点溶胶加入来保持总浓度2000ppm。该去垢剂浓度是通过电导率来控制的。The dishwasher then starts and runs an automatic cycle. At the beginning of each cycle, an appropriate amount of hot spot sol was added to maintain a total concentration of 2000 ppm. The detergent concentration is controlled by conductivity.
当50个周期结束时，使得所述玻璃干燥一整夜。其后将它们进行污点和膜聚集(目视)分级。When the 50 cycles were complete, the glass was allowed to dry overnight. Thereafter they were graded for stain and film aggregation (visual).
该玻璃和塑料杯子然后使用Commassie Brilliant Blue R污点，随后用乙酸/甲醇水溶液脱色，来进行蛋白质聚集分级。该Commassie Brilliant Blue R污点是通过将1.25g的Commassie Brilliant Blue R染料与45mL的乙酸和455mL的50％甲醇蒸馏水溶液合并来制备的。脱色溶液的组成为45％甲醇和10％乙酸的蒸馏水溶液。The glass and plastic cups were then stained using Commassie Brilliant Blue R followed by destaining with aqueous acetic acid/methanol for protein aggregation fractionation. The Commassie Brilliant Blue R stain was prepared by combining 1.25 g of Commassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water. The composition of the decolorizing solution was 45% methanol and 10% acetic acid in distilled water.
在脱色后保持在玻璃和塑料杯上的蛋白质的量以刻度1-5来目视分级的。等级1表示脱色后没有蛋白质存在–无污点/无膜。等级2表示随机区域(几乎不能察觉)在脱色后覆盖有蛋白质–随机污点(或者大约20％表面覆盖有膜)。等级3表示大约四分之一到一半的表面在脱色后覆盖有蛋白质(或者大约40％表面覆盖有膜)。等级4表示大约一半的玻璃/塑料表面在脱色后覆盖有蛋白质(或者大约60％表面覆盖有膜)。等级5表示整个表面在脱色后涂覆有蛋白质(或者至少大约80％表面覆盖有膜)。The amount of protein remaining on the glass and plastic cups after decolorization was visually graded on a scale of 1-5. Rating 1 means no protein present after destaining – no stain/no membrane. Grade 2 indicates random areas (barely perceptible) covered with protein-random stains after destaining (or approximately 20% surface covered with membrane). A rating of 3 indicates that approximately one quarter to one half of the surface is covered with protein after depigmentation (or approximately 40% of the surface is covered with a membrane). A rating of 4 means that about half of the glass/plastic surface is covered with protein after decolorization (or about 60% of the surface is covered with a film). A rating of 5 indicates that the entire surface is coated with protein after depigmentation (or at least about 80% of the surface is covered with a film).
将用于污垢除去率测试的玻璃杯子的等级平均来确定从玻璃表面的平均污垢除去等级，和将用于污垢除去率测试的塑料杯子的等级平均来确定从塑料表面的平均污垢除去等级。类似的，将用于再沉积测试的玻璃杯子的等级平均来确定对于玻璃表面的平均再沉积等级，和将用于再沉积测试的塑料杯子的等级平均来确定对于塑料表面的平均再沉积等级。The ratings of the glass cups used in the soil removal rate test were averaged to determine the average soil removal rating from the glass surface, and the ratings of the plastic cups used in the soil removal rate test were averaged to determine the average soil removal rating from the plastic surface. Similarly, the ratings of the glass cups used in the redeposition test were averaged to determine the average redeposition rating for the glass surface, and the ratings of the plastic cups used for the redeposition test were averaged to determine the average redeposition rating for the plastic surface.
结果显示在下表中，其证实了与市售产品相比，本发明的去垢剂组合物提供至少基本上类似的清洁效率和在不同的实施方案提供更优的效率。The results, shown in the table below, demonstrate that the detergent compositions of the present invention provide at least substantially similar cleaning efficiencies and in various embodiments superior efficiencies compared to commercially available products.
等级刻度显示在表9中。The rating scale is shown in Table 9.
表9Table 9
50周期测试的结果提供在表10-11中。The results of the 50 cycle tests are provided in Tables 10-11.
表10Table 10
表11Table 11
实施例4Example 4
公用器皿清洗去垢剂或者漂洗助剂的7个周期污点，膜和污垢除去评估7-Cycle Stain, Film and Soil Removal Evaluation of Utility Dishwashing Detergents or Rinse Aids
为了测试组合物清洁玻璃和塑料的能力，使用了12个10盎司Libby耐热玻璃杯和4个Newport塑料杯。该玻璃杯在使用前清洁。To test the ability of the compositions to clean glass and plastic, 12 10 oz Libby Pyrex cups and 4 Newport plastic cups were used. The glass is cleaned before use.
使用50/50组合的炖牛肉和热点污垢制备了食品污垢溶液。该溶液的浓度是大约2000ppm。该污垢包括两罐Dinty Moore Beef Stew(1360g)，1大罐番茄酱(822g)，15.5根Blue Bonnet Margarine(1746g)和奶粉(436.4g)。A food soil solution was prepared using a 50/50 combination of beef stew and hot spot soil. The concentration of this solution is about 2000 ppm. The dirt included two tins of Dinty Moore Beef Stew (1360g), 1 large tin of tomato sauce (822g), 15.5 sticks of Blue Bonnet Margarine (1746g) and milk powder (436.4g).
然后用适量水填充洗碗机。在用水填充洗碗机之后，打开加热器。将最终的漂洗温度调节到大约180°F。将该玻璃和塑料杯如下来污染：将该玻璃在1：1(体积)的Campbell的鸡汤奶：Kemp的全脂奶混合物中滚动3次。该玻璃然后置于大约160°F烘箱中大约8分钟。在该玻璃干燥的同时，将洗碗机用大约120g的食品污垢溶液涂底，其对应于泵中大约2000ppm的食品污垢。Then fill the dishwasher with an appropriate amount of water. After filling the dishwasher with water, turn on the heater. Adjust the final rinse temperature to approximately 180°F. The glass and plastic cup were soiled by rolling the glass 3 times in a 1 : 1 (volume) mixture of Campbell's Chicken Stock Milk: Kemp's Whole Milk. The glass was then placed in an oven at about 160°F for about 8 minutes. While the glass was drying, the dishwasher was primed with approximately 120 g of food soil solution, which corresponds to approximately 2000 ppm food soil in the pump.
将该污染的玻璃和塑料杯子置于Raburn架子(见下图的排列；P＝塑料杯；G＝玻璃杯)，并且将该架子置于洗碗机内。前面两列杯子测试污垢除去，而接下来的两列杯子测试再沉积。The soiled glass and plastic cups were placed in a Raburn rack (see arrangement below; P = plastic cup; G = glass cup) and the rack was placed in the dishwasher. The first two columns of cups were tested for soil removal, while the next two columns were tested for redeposition.
然后启动洗碗机和运行自动周期。当该周期结束时，用干毛巾擦拭玻璃和塑料杯顶部。移除用于测试污垢除去的玻璃和塑料杯子，并且重复汤/牛奶污垢程序。不移除再沉积玻璃和塑料杯子。Then start the dishwasher and run the automatic cycle. When the cycle is complete, wipe down glass and plastic cup tops with a dry towel. The glass and plastic cups used to test soil removal were removed and the soup/milk soil procedure was repeated. Does not remove redeposited glass and plastic cups.
在每个周期开始时，将适量的去垢剂和食品污垢加入清洗槽中来补偿漂洗稀释。该污染和清洗步骤重复7个周期。At the beginning of each cycle, the appropriate amount of detergent and food soil is added to the wash tank to compensate for rinse dilution. This contamination and cleaning step was repeated for 7 cycles.
该玻璃和塑料杯子然后使用Commassie Brilliant Blue R污点，随后用乙酸/甲醇水溶液脱色，来进行蛋白质聚集分级。该Commassie Brilliant Blue R污点是通过将大约1.25g的Commassie Brilliant Blue R染料与大约45mL的乙酸和大约455mL的50％甲醇蒸馏水溶液合并来制备的。脱色溶液的组成为45％甲醇和10％乙酸的蒸馏水溶液。在脱色后保持在玻璃和塑料杯上的蛋白质的量以刻度1-5来目视分级的。等级1表示脱色后没有蛋白质存在。等级2表示随机区域(几乎不能察觉)在脱色后覆盖有蛋白质。等级3表示大约四分之一的表面在脱色后覆盖有蛋白质。等级4表示大约一半的玻璃/塑料表面在脱色后覆盖有蛋白质。等级5表示整个表面在脱色后涂覆有蛋白质。The glass and plastic cups were then stained using Commassie Brilliant Blue R followed by destaining with aqueous acetic acid/methanol for protein aggregation fractionation. The Commassie Brilliant Blue R stain was prepared by combining approximately 1.25 g of Commassie Brilliant Blue R dye with approximately 45 mL of acetic acid and approximately 455 mL of 50% methanol in distilled water. The composition of the decolorizing solution was 45% methanol and 10% acetic acid in distilled water. The amount of protein remaining on the glass and plastic cups after decolorization was visually graded on a scale of 1-5. A rating of 1 indicates that no protein is present after depigmentation. Grade 2 indicates random areas (barely perceptible) covered with protein after destaining. A grade of 3 means that approximately one quarter of the surface is covered with protein after depigmentation. A rating of 4 means that approximately half of the glass/plastic surface is covered with protein after decolorization. A rating of 5 indicates that the entire surface is coated with protein after depigmentation.
将用于蛋白质除去率测试的玻璃杯子的等级平均来确定从玻璃表面的平均蛋白质除去等级，和将用于蛋白质除去率测试的塑料杯子的等级平均来确定从塑料表面的平均蛋白质除去等级。类似地，将用于再沉积测试的玻璃杯子的等级平均来确定用于玻璃表面的平均蛋白质再沉积等级，和将用于蛋白质再沉积测试的塑料杯子的等级平均来确定对于塑料表面的平均蛋白质再沉积等级。The ratings of the glass cups used in the protein removal rate test were averaged to determine the average protein removal rating from the glass surface and the ratings of the plastic cups used in the protein removal rate test were averaged to determine the average protein removal rating from the plastic surface. Similarly, the ratings of the glass cups used in the redeposition test were averaged to determine the average protein redeposition rating for the glass surface, and the ratings of the plastic cups used for the protein redeposition test were averaged to determine the average protein redeposition rating for the plastic surface redeposition level.
玻璃是相对于黑色背景在玻璃观察区域中目视分级的。将每组玻璃分级为一组，即，对于全部测试产品的全部再沉积玻璃。可以对每组确定整体平均值。所用的等级刻度显示在表12中。Glasses are graded visually in the glass viewing area against a black background. Each set of glasses was graded into one group, ie, all redeposited glasses for all products tested. An overall mean can be determined for each group. The grade scale used is shown in Table 12.
表12Table 12
7周期测试的结果提供在表13-14中，其显示了玻璃和塑料杯的平均污点，膜和蛋白质玷污等级(标准偏差)：The results of the 7-cycle test are provided in Tables 13-14, which show the average stain, film and protein stain ratings (standard deviation) for glass and plastic cups:
表13Table 13
表14Table 14
实施例5-8Example 5-8
此处提供了实施例5-8所用的材料：The materials used in Examples 5-8 are provided here:
25R2：一种EO/PO共聚物，获自BASF。 25R2: an EO/PO copolymer available from BASF.
II 1012GB-21：一种醇烷氧基化物，获自Sasol。 II 1012GB-21 : An alcohol alkoxylate ex Sasol.
448：一种聚丙烯酸共聚物，获自Dow Chemical Company。 448: A polyacrylic acid copolymer available from Dow Chemical Company.
另外的材料市售自多个来源，包括：碳酸钠，灰单水合物，三聚磷酸钠(无水)，氯化锌，HEDP和KOH。Additional materials are commercially available from a variety of sources including: sodium carbonate, ash monohydrate, sodium tripolyphosphate (anhydrous), zinc chloride, HEDP and KOH.
制备了示例性二合一去垢剂，其包含聚合物，并且是表15所示的。在整个实施例中，配料被称作实验配料2(Exp.2)。Exemplary 2-in-1 detergents comprising polymers were prepared and are shown in Table 15. Throughout the examples, the formulation is referred to as Experimental Formulation 2 (Exp.2).
表15Table 15
现有的去垢剂，漂洗助剂和实验配料2是用蒸馏水来测试的。去垢剂对照物1和去垢剂对照物2是市售的去垢剂(磷酸盐基去垢剂)。漂洗助剂对照物1和漂洗助剂对照物是两种市售的漂洗助剂(使用更高量的至少两种离子类(例如非离子和阳离子)的活性成分表面活性剂)。下述全部实验的使用浓度提供在表16中：Existing detergents, rinse aids and test ingredient 2 were tested with distilled water. Detergent Control 1 and Detergent Control 2 are commercially available detergents (phosphate based detergents). Rinse Aid Control 1 and Rinse Aid Control are two commercially available rinse aids (with higher levels of active ingredient surfactants of at least two ionic classes (eg non-ionic and cationic)). The concentrations used for all of the experiments below are provided in Table 16:
表16Table 16
全部器皿清洗测试是用10盎司Libbey玻璃在Hobart AM-15洗碗机中进行的。Hobart AM-15洗碗机的规格如下：All warewash tests were performed in a Hobart AM-15 dishwasher using 10 oz Libbey glass. The specifications of the Hobart AM-15 Dishwasher are as follows:
Hobart AM-15洗碗机规格Hobart AM-15 Dishwasher Specifications
实施例5Example 5
动态表面张力dynamic surface tension
SITA科学线t60测量了高至半静态范围的液体的动态表面张力。从具有已知半径的毛细管产生了空气气泡。该气泡压力是作为气泡寿命的函数来测量的，其可以根据Young-Laplace等式与表面张力相关。动态表面张力提供了对于表面活性剂和其他表面活性化合物在动态条件下的动态行为的观察，即，表面活性剂多快可以到达表面。该动态表面张力是表面活性剂的浓度，温度和类型的函数。该表面活性剂的动态表面张力行为在这样的应用中是特别重要的，这里需要表面活性剂的快速响应，例如在自动洗碗中的短漂洗周期中。The SITA Scientific Line t60 measures the dynamic surface tension of liquids up to the semi-static range. Air bubbles are generated from capillaries with known radii. The bubble pressure is measured as a function of bubble lifetime, which can be related to surface tension according to the Young-Laplace equation. Dynamic surface tension provides insight into the dynamic behavior of surfactants and other surface active compounds under dynamic conditions, ie, how quickly a surfactant can reach a surface. This dynamic surface tension is a function of the concentration, temperature and type of surfactant. The dynamic surface tension behavior of the surfactant is particularly important in applications where a fast response of the surfactant is required, for example in short rinse cycles in automatic dishwashing.
设备和材料：Equipment and materials:
1.SITA T60(Sita Messtechnik，德国)1. SITA T60 (Sita Messtechnik, Germany)
2.具有搅拌棒的油浴2. Oil bath with stir bar
3.加热和搅拌盘3. Heating and stirring plate
4.玻璃烧杯4. Glass beaker
5.玻璃小瓶(20mL)5. Glass vial (20mL)
该SITA科学线t60是用去离子水校正的。在校正后清洁水样品的表面张力应当是72.0±1.0mN/m(取决于水品质和温度)。在校正后，该SITA程序化来在期望的时间间隔(即，0.3，1.6，3.0和9.1秒)采集读数。对于每个待测试的组合物(描述为A-C)(例如Exp.2的三个样品，去垢剂对照物1的三个样品)，准备了在期望的ppm的三种分别的溶液。将10-15mL转移到20mL小瓶中，并且浸入到热油浴至72℃(160°F)±2℃。该样品平衡化10-15分钟。将该样品从油浴中单个移除，并且在SITA中测试。在每个样品测试后，运行SITA清洁程序，然后检查去离子水的表面张力来确保该SITA充分清洁。如果去离子水测量不是在72.0±1.0mN/m内，则再次运行清洁程序。下表17A-17F提供了在160°F的表面张力(mN/m)vs气泡寿命实验数据，其中τ是气泡寿命(秒)；γ是表面张力(mN/m)。The SITA Scientific Line t60 is calibrated with deionized water. The surface tension of the clean water sample after calibration should be 72.0 ± 1.0 mN/m (depending on water quality and temperature). After calibration, the SITA was programmed to take readings at desired time intervals (ie, 0.3, 1.6, 3.0 and 9.1 seconds). For each composition (depicted as A-C) to be tested (eg three samples of Exp. 2, three samples of detergent control 1), three separate solutions at the desired ppm were prepared. Transfer 10-15 mL to a 20 mL vial and immerse in a hot oil bath to 72°C (160°F) ± 2°C. The sample was equilibrated for 10-15 minutes. The samples were individually removed from the oil bath and tested in SITA. After each sample test, run the SITA cleaning program, then check the surface tension of the deionized water to ensure that the SITA is sufficiently clean. If the deionized water measurement is not within 72.0 ± 1.0 mN/m, run the cleaning program again. Tables 17A-17F below provide experimental data for surface tension (mN/m) vs. bubble life at 160°F, where τ is bubble life (seconds); γ is surface tension (mN/m).
表17-ATable 17-A
表17-BTable 17-B
表17-CTable 17-C
表17-DTable 17-D
表17-ETable 17-E
表17-FTable 17-F
对于平均气泡寿命0.3，1.6，3.0，和9.1秒，测试了在160°F的平均表面张力。结果提供在表18中。The average surface tension at 160°F was tested for average bubble lifetimes of 0.3, 1.6, 3.0, and 9.1 seconds. Results are provided in Table 18.
表18Table 18
该数据证实了实验配料2的表面张力随着气泡寿命9.1秒时的表面张力的明显下降而快速降低。这类似于公知的漂洗助剂，例如漂洗助剂对照物2。这些结果显示在图2中。This data demonstrates that the surface tension of Experimental Formulation 2 decreases rapidly with a significant drop in surface tension at a bubble lifetime of 9.1 seconds. This is similar to known rinse aids such as Rinse Aid Control 2. These results are shown in Figure 2.
实施例6Example 6
用于公用器皿清洗去垢剂的100周期膜评价100-Cycle Membrane Evaluation for Utility Dishwashing Detergents
为了测定不同的去垢剂组合物除去器皿上的污点和膜的能力，通过除去玻璃表面上的全部膜和外来材料，来准备了6个Libby 10盎司玻璃杯。然后向Hobart AM-15洗碗机中填充适量的水，并且测试该水的硬度。在记录了硬度值之后，打开槽加热器。在实验日，水硬度是17格令。启动该洗碗机，并且在该机器中运行清洗/漂洗周期，直到达到清洗温度大约150°F-大约160°F和漂洗温度大约175°F-大约190°F。然后设定控制器来将适量去垢剂分配到清洗槽中。分配该去垢剂，以使得当去垢剂在所述周期过程中与水混合来形成使用溶液时，使用溶液中的去垢剂浓度是750份/百万份(ppm)。滴定该清洗槽中的溶液来检验去垢剂浓度。该洗碗机的清洗浴体积是58升，漂洗体积2.8升，清洗时间50秒和漂洗时间9秒。To determine the ability of different detergent compositions to remove stains and film from ware, six Libby 10 oz glasses were prepared by removing all film and foreign material from the glass surface. The Hobart AM-15 dishwasher was then filled with the appropriate amount of water and tested for hardness. After the hardness value is recorded, the bath heater is turned on. On the test day, the water hardness was 17 grains. Start the dishwasher and run a wash/rinse cycle in the machine until a wash temperature of about 150°F to about 160°F and a rinse temperature of about 175°F to about 190°F is reached. The controller is then programmed to dispense the proper amount of detergent into the wash tank. The detergent was dispensed such that when the detergent was mixed with water during the cycle to form the use solution, the detergent concentration in the use solution was 750 parts per million (ppm). Titrate the solution in the wash tank to check the detergent concentration. The dishwasher has a wash bath volume of 58 liters, a rinse volume of 2.8 liters, a wash time of 50 seconds and a rinse time of 9 seconds.
将6个洁净的玻璃杯对角线置于Raburn架子上，并且将4个Newport 10盎司塑料杯远离对角线置于该Raburn架子上(见下图的排列)，并且将该架子置于洗碗机内。(P＝塑料杯；G＝玻璃杯)。Place 6 clean glasses diagonally on the Raburn rack and place 4 Newport 10 oz plastic cups away from the diagonal on the Raburn rack (see arrangement below) and place the rack in the wash Inside the bowl machine. (P=plastic cup; G=glass cup).
然后开始该100周期测试。在每个清洗周期开始时，将适量去垢剂自动分配到洗碗机中来保持初始去垢剂浓度。该去垢剂浓度是通过电导率来控制的。The 100 cycle test is then started. At the start of each wash cycle, an appropriate amount of detergent is automatically dispensed into the dishwasher to maintain the initial detergent concentration. The detergent concentration is controlled by conductivity.
一旦完成100个周期，将所述架子从洗碗机中移除，并且使得该玻璃和塑料杯子干燥。然后将该玻璃和塑料杯子使用膜等级和使用分析光盒评估对污点和膜聚集进行分级。膜等级尺度提供在表19中。Once 100 cycles were completed, the rack was removed from the dishwasher and the glass and plastic cups were allowed to dry. The glass and plastic cups were then graded for staining and film accumulation using a film grade and assessed using an analytical light box. The film grade scale is provided in Table 19.
表19Table 19
该光盒测试使用了数码相机，光盒，光源，光度计和对照物计算机，其使用了“SpotAdvance”和“Image Pro Plus”商业软件。将待评估的玻璃置于光盒上它的侧面上，并且使用光度计来将光源强度调节到预定值。对该玻璃进行照相图像，并且存储到计算机。然后使用所述软件来分析该玻璃的上半部分，并且该计算机显示了柱状图，并且该图下的面积是与膜厚成比例的。The light box test uses a digital camera, light box, light source, photometer and control computer using "SpotAdvance" and "Image Pro Plus" commercial software. The glass to be evaluated is placed on its side on the light box, and a photometer is used to adjust the light source intensity to a predetermined value. A photographic image is taken of the glass and stored to a computer. The software was then used to analyze the top half of the glass and the computer displayed a histogram and the area under the graph was proportional to the film thickness.
通常，较低的光盒分数指示了更多的光能够通过所述杯子。因此，光盒分数越低，该组合物在防止杯子表面上的结垢方面越有效。洁净的，未用的玻璃杯的光盒分数是大约12000，其对于6个玻璃杯子来说对应于72000的分数，和洁净的，未用的塑料杯子的光盒分数是大约25500，其对于4个塑料杯子来说对应于大约102000的光盒分数。最小可获得的光盒分数(即，6个洁净的玻璃杯子和4个洁净的塑料杯子的总和)是大约174000。通常，如果6个玻璃杯子和4个塑料杯子的光盒分数之和是大约360000或者更低，则去垢剂组合物被认为在控制硬水结垢方面是有效的。In general, a lower light box score indicates that more light was able to pass through the cup. Thus, the lower the light box score, the more effective the composition is at preventing fouling on the surface of the cup. The light box score for a clean, unused glass cup is approximately 12000, which corresponds to a score of 72000 for 6 glass cups, and for a clean, unused plastic cup is approximately 25500, which corresponds to a score of 72000 for a clean, unused plastic cup. This corresponds to a light box score of about 102,000 for a plastic cup. The minimum achievable light box score (ie, the sum of 6 clean glass cups and 4 clean plastic cups) is about 174000. In general, a detergent composition is considered effective in controlling hard water scaling if the sum of the light box scores for the 6 glass cups and 4 plastic cups is about 360,000 or less.
100个循环测试的结果提供在表20和21中。The results of the 100 cycle tests are provided in Tables 20 and 21.
表20Table 20
表21Table 21
实施例7Example 7
用于公用器皿清洗去垢剂的50周期再沉积实验50-Cycle Redeposition Test of Detergent Used in Public Utensil Cleaning
对于公用器皿清洗去垢剂，使用50周期再沉积实验进一步评价了本发明组合物和对照物的清洁效率。为了测试组合物清洁玻璃和塑料的能力，使用了6个10盎司Libby耐热玻璃杯和1个塑料杯。该玻璃杯在使用前清洁。对每个实验使用新的塑料杯。For utility dishwashing detergents, the cleaning efficiency of the inventive compositions and controls was further evaluated using a 50 cycle redeposition test. To test the ability of the compositions to clean glass and plastic, six 10 oz Libby Pyrex cups and one plastic cup were used. The glass is cleaned before use. Use new plastic cups for each experiment.
使用50/50组合的炖牛肉和热点污垢，并且使用2000ppm污垢制备了食品污垢溶液。该污垢包括两罐Dinty Moore Beef Stew(1360g)，1大罐番茄酱(822g)，15.5根BlueBonnet Margarine(1746g)和奶粉(436.4g)。将热点污垢加入所述机器中来保持总浓度大约2000ppm。A 50/50 combination of goulash and hot spot soils was used and a food soil solution was prepared using 2000 ppm soil. The dirt included two tins of Dinty Moore Beef Stew (1360g), 1 large tin of tomato sauce (822g), 15.5 sticks of BlueBonnet Margarine (1746g) and milk powder (436.4g). Hot spot soil was added to the machine to maintain a total concentration of approximately 2000 ppm.
在用17格令水填充洗碗机之后，打开加热器。将清洗温度调节到大约150-160°F。将最终的漂洗温度调节到大约175-190°F。将控制器设定来显示清洗槽中的去垢剂的量。将玻璃和塑料杯子置于Raburn架子上(见下图的排列；P＝塑料杯；G＝玻璃杯)，并且将该架子置于洗碗机内。After filling the dishwasher with 17 grains of water, turn on the heater. Adjust the wash temperature to approximately 150-160°F. Adjust the final rinse temperature to approximately 175-190°F. Set the controller to display the amount of detergent in the wash tank. Place the glass and plastic cups on a Raburn rack (see arrangement below; P = plastic cups; G = glass cups) and place the rack in the dishwasher.
该洗碗机然后启动和运行自动的周期。在每个周期开始时，将适量的热点溶胶加入来保持总浓度2000ppm。该去垢剂浓度是通过电导率来控制的。The dishwasher then starts and runs an automatic cycle. At the beginning of each cycle, an appropriate amount of hot spot sol was added to maintain a total concentration of 2000 ppm. The detergent concentration is controlled by conductivity.
当50个周期结束时，使得所述玻璃干燥一整夜。其后将它们进行污点和膜聚集(目视)分级。When the 50 cycles were complete, the glass was allowed to dry overnight. Thereafter they were graded for stain and film aggregation (visual).
该玻璃和塑料杯子然后使用Commassie Brilliant Blue R污点，随后用乙酸/甲醇水溶液脱色，来进行蛋白质聚集分级。该Commassie Brilliant Blue R污点是通过将1.25g的Commassie Brilliant Blue R染料与45mL的乙酸和455mL的50％甲醇蒸馏水溶液合并来制备的。脱色溶液的组成为45％甲醇和10％乙酸的蒸馏水溶液。The glass and plastic cups were then stained using Commassie Brilliant Blue R followed by destaining with aqueous acetic acid/methanol for protein aggregation fractionation. The Commassie Brilliant Blue R stain was prepared by combining 1.25 g of Commassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water. The composition of the decolorizing solution was 45% methanol and 10% acetic acid in distilled water.
在脱色后保持在玻璃和塑料杯上的蛋白质的量以刻度1-5来目视分级的。等级1表示脱色后没有蛋白质存在–无污点/无膜。等级2表示随机区域(几乎不能察觉)在脱色后覆盖有蛋白质–随机污点(或者大约20％表面覆盖有膜)。等级3表示大约四分之一到一半的表面在脱色后覆盖有蛋白质(或者大约40％表面覆盖有膜)。等级4表示大约一半的玻璃/塑料表面在脱色后覆盖有蛋白质(或者大约60％表面覆盖有膜)。等级5表示整个表面在脱色后覆盖有蛋白质(或者至少大约80％表面覆盖有膜)。The amount of protein remaining on the glass and plastic cups after decolorization was visually graded on a scale of 1-5. Rating 1 means no protein present after destaining – no stain/no membrane. Grade 2 indicates random areas (barely perceptible) covered with protein-random stains after destaining (or approximately 20% surface covered with membrane). A rating of 3 indicates that approximately one quarter to one half of the surface is covered with protein after depigmentation (or approximately 40% of the surface is covered with a membrane). A rating of 4 means that about half of the glass/plastic surface is covered with protein after decolorization (or about 60% of the surface is covered with a film). A rating of 5 indicates that the entire surface is covered with protein after depigmentation (or at least about 80% of the surface is covered with a film).
将用于污垢除去率测试的玻璃杯子的等级平均来确定从玻璃表面的平均污垢除去等级，和将用于污垢除去率测试的塑料杯子的等级平均来确定从塑料表面的平均污垢除去等级。类似地，将用于再沉积测试的玻璃杯子的等级平均来确定对于玻璃表面的平均再沉积等级，和将用于再沉积测试的塑料杯子的等级平均来确定对于塑料表面的平均再沉积等级。The ratings of the glass cups used in the soil removal rate test were averaged to determine the average soil removal rating from the glass surface, and the ratings of the plastic cups used in the soil removal rate test were averaged to determine the average soil removal rating from the plastic surface. Similarly, the ratings of the glass cups used in the redeposition test were averaged to determine the average redeposition rating for the glass surface, and the ratings of the plastic cups used for the redeposition test were averaged to determine the average redeposition rating for the plastic surface.
结果显示在下表中，其证实了与市售产品相比，本发明的去垢剂组合物提供至少基本上类似的清洁效率和在不同的实施方案中提供更优的效率。等级刻度显示在表22中。The results, shown in the table below, demonstrate that the detergent compositions of the present invention provide at least substantially similar cleaning efficiencies and in various embodiments superior efficiencies compared to commercially available products. The rating scale is shown in Table 22.
表22Table 22
50周期测试的结果提供在表23和24中。The results of the 50 cycle test are provided in Tables 23 and 24.
表23.Table 23.
表24.Table 24.
实施例8Example 8
公用器皿清洗去垢剂或者漂洗助剂的7个周期污点、膜和污垢除去评估7-Cycle Stain, Film and Soil Removal Evaluation of Utility Dishwashing Detergents or Rinse Aids
为了测试组合物清洁玻璃和塑料的能力，使用了12个10盎司Libby耐热玻璃杯和4个Newport塑料杯。该玻璃杯在使用前清洁。To test the ability of the compositions to clean glass and plastic, 12 10 oz Libby Pyrex cups and 4 Newport plastic cups were used. The glass is cleaned before use.
使用50/50组合的炖牛肉和热点污垢制备了食品污垢溶液。该溶液的浓度是大约2000ppm。该污垢包括两罐Dinty Moore Beef Stew(1360g)，1大罐番茄酱(822g)，15.5根Blue Bonnet Margarine(1746g)和奶粉(436.4g)。A food soil solution was prepared using a 50/50 combination of beef stew and hot spot soil. The concentration of this solution is about 2000 ppm. The dirt included two tins of Dinty Moore Beef Stew (1360g), 1 large tin of tomato sauce (822g), 15.5 sticks of Blue Bonnet Margarine (1746g) and milk powder (436.4g).
然后用适量水填充洗碗机。在用水填充洗碗机之后，打开加热器。将最终的漂洗温度调节到大约180°F。将该玻璃和塑料杯如下来污染：将该玻璃在1：1(体积)的Campbell的鸡汤奶：Kemp的全脂奶混合物中滚动3次。该玻璃然后置于大约160°F烘箱中大约8分钟。在该玻璃干燥的同时，将洗碗机用大约120g的食品污垢溶液涂底，其对应于泵中大约2000ppm的食品污垢。Then fill the dishwasher with an appropriate amount of water. After filling the dishwasher with water, turn on the heater. Adjust the final rinse temperature to approximately 180°F. The glass and plastic cup were soiled by rolling the glass 3 times in a 1 : 1 (volume) mixture of Campbell's Chicken Stock Milk: Kemp's Whole Milk. The glass was then placed in an oven at about 160°F for about 8 minutes. While the glass was drying, the dishwasher was primed with approximately 120 g of food soil solution, which corresponds to approximately 2000 ppm food soil in the pump.
将该污染的玻璃和塑料杯子置于Raburn架子(见下图的排列；P＝塑料杯；G＝玻璃杯)，并且将该架子置于洗碗机内。前面两列杯子测试污垢除去，而接下来的两列杯子测试再沉积。The soiled glass and plastic cups were placed in a Raburn rack (see arrangement below; P = plastic cup; G = glass cup) and the rack was placed in the dishwasher. The first two columns of cups were tested for soil removal, while the next two columns were tested for redeposition.
然后启动洗碗机和运行自动周期。当该周期结束时，用干毛巾擦拭玻璃和塑料杯顶部。移除用于测试污垢除去的玻璃和塑料杯子，并且重复鸡汤/牛奶污垢程序。不移除再沉积玻璃和塑料杯子。Then start the dishwasher and run the automatic cycle. When the cycle is complete, wipe down glass and plastic cup tops with a dry towel. The glass and plastic cups used to test soil removal were removed and the chicken broth/milk soil procedure was repeated. Does not remove redeposited glass and plastic cups.
在每个周期开始时，将适量的去垢剂和食品污垢加入清洗槽中来补偿漂洗稀释。该污染和清洗步骤重复7个周期。At the beginning of each cycle, the appropriate amount of detergent and food soil is added to the wash tank to compensate for rinse dilution. This contamination and cleaning step was repeated for 7 cycles.
该玻璃和塑料杯子然后使用Commassie Brilliant Blue R污点，随后用乙酸/甲醇水溶液脱色，来进行蛋白质聚集分级。该Commassie Brilliant Blue R污点是通过将大约1.25g的Commassie Brilliant Blue R染料与大约45mL的乙酸和大约455mL的50％甲醇蒸馏水溶液合并来制备的。脱色溶液的组成为45％甲醇和10％乙酸的蒸馏水溶液。在脱色后保持在玻璃和塑料杯上的蛋白质的量以刻度1-5来目视分级的。等级1表示脱色后没有蛋白质存在。等级2表示随机区域(几乎不能察觉)在脱色后覆盖有蛋白质。等级3表示大约四分之一的表面在脱色后覆盖有蛋白质。等级4表示大约一半的玻璃/塑料表面在脱色后覆盖有蛋白质。等级5表示整个表面在脱色后覆盖有蛋白质。The glass and plastic cups were then stained using Commassie Brilliant Blue R followed by destaining with aqueous acetic acid/methanol for protein aggregation fractionation. The Commassie Brilliant Blue R stain was prepared by combining approximately 1.25 g of Commassie Brilliant Blue R dye with approximately 45 mL of acetic acid and approximately 455 mL of 50% methanol in distilled water. The composition of the decolorizing solution was 45% methanol and 10% acetic acid in distilled water. The amount of protein remaining on the glass and plastic cups after decolorization was visually graded on a scale of 1-5. A rating of 1 indicates that no protein is present after depigmentation. Grade 2 indicates random areas (barely perceptible) covered with protein after destaining. A grade of 3 means that approximately one quarter of the surface is covered with protein after depigmentation. A rating of 4 means that approximately half of the glass/plastic surface is covered with protein after decolorization. A rating of 5 indicates that the entire surface is covered with protein after destaining.
将用于蛋白质除去率测试的玻璃杯子的等级平均来确定从玻璃表面的平均蛋白质除去等级，和将用于蛋白质除去率测试的塑料杯子的等级平均来确定从塑料表面的平均蛋白质除去等级。类似地，将用于再沉积测试的玻璃杯子的等级平均来确定对于玻璃表面的平均蛋白质再沉积等级，和将用于蛋白质再沉积测试的塑料杯子的等级平均来确定对于塑料表面的平均蛋白质再沉积等级。The ratings of the glass cups used in the protein removal rate test were averaged to determine the average protein removal rating from the glass surface and the ratings of the plastic cups used in the protein removal rate test were averaged to determine the average protein removal rating from the plastic surface. Similarly, the ratings of the glass cups used for the redeposition test were averaged to determine the average protein redeposition rating for the glass surface, and the ratings for the plastic cups used for the protein redeposition test were averaged to determine the average protein redeposition rating for the plastic surface. deposition level.
评价结果：Evaluation results:
玻璃是相对于黑色背景在玻璃观察区域中来目视分级的。将每组玻璃分级为一组，即，对于全部测试产品的全部再沉积玻璃。可以对每组确定整体平均值。所用的等级刻度显示在表25中。The glass is visually graded in the glass viewing area against a black background. Each set of glasses was graded into one group, ie, all redeposited glasses for all products tested. An overall mean can be determined for each group. The grade scale used is shown in Table 25.
表25Table 25
7周期测试的结果提供在表26和27中，其显示了玻璃和塑料杯的平均污点、膜和蛋白质玷污等级(标准偏差)：The results of the 7-cycle test are provided in Tables 26 and 27, which show the average stain, film and protein stain ratings (standard deviations) for glass and plastic cups:
表26.Table 26.
表27.Table 27.
这些实施例证实了在传统洗碗程序中在大部分种类的清洁和抗再沉积中，与现有的去垢剂和现有的去垢剂和漂洗助剂相比，本发明的组合物提供了类似的，基本上类似的或者更好的性能。These examples demonstrate that in conventional dishwashing programs the compositions of the present invention provide similar, substantially similar, or better performance.
因此描述了本发明，很显然其可以以许多方式改变。这样的改变不被认为是脱离了本发明的主旨和范围，并且全部这样的改变目的是包括在下面的权利要求的范围内。上面的说明书提供了对于所公开的组合物和方法的制造和使用的说明。因为许多实施方案可以进行而不脱离本发明的主旨和范围，因此本发明存在于权利要求中。The invention thus being described, it will be obvious that it may be varied in many ways. Such changes are not to be regarded as a departure from the spirit and scope of the invention, and all such changes are intended to be included within the scope of the following claims. The above specification provides instructions for making and using the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the invention, the invention resides in the claims.
| Application Number | Priority Date | Filing Date | Title |
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| CN202111110572.1ACN113736588A (en) | 2014-03-07 | 2015-03-02 | Detergent composition exhibiting both cleaning and rinsing functions |
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| CN202111110572.1ADivisionCN113736588A (en) | 2014-03-07 | 2015-03-02 | Detergent composition exhibiting both cleaning and rinsing functions |
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| CN202111110572.1APendingCN113736588A (en) | 2014-03-07 | 2015-03-02 | Detergent composition exhibiting both cleaning and rinsing functions |
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| CN202111110572.1APendingCN113736588A (en) | 2014-03-07 | 2015-03-02 | Detergent composition exhibiting both cleaning and rinsing functions |
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| EP (2) | EP4227391A1 (en) |
| JP (3) | JP2017507236A (en) |
| KR (2) | KR20160119862A (en) |
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