阅读说明：本技术 多用途的酶洗涤剂和稳定使用溶液的方法 (Multipurpose enzymatic detergents and methods for stabilizing use solutions ) 是由 W·陈 J·斯托克斯 L·珍森 C·M·斯沃内尔 T·P·埃佛逊 G·勒加特 N·R·奥 于 2014-11-10 设计创作，主要内容包括：公开了采用用于清洁组合物的酶,低磷的碱金属碳酸盐洗涤剂的稳定的使用溶液。特别地,本发明涉及使用稳定的酶清洁组合物(即,它的使用溶液)用于除去污物、防止蛋白质污物再沉积并降低发泡的组合物以及方法。(Stable use solutions of low phosphorous alkali metal carbonate detergents employing enzymes for cleaning compositions are disclosed. In particular, the present invention relates to compositions and methods for removing soils, preventing redeposition of protein soils and reducing foaming using stable enzymatic cleaning compositions (i.e., its use solutions).)

1. A multi-purpose solid detergent composition comprising:

a source of alkali metal carbonate alkalinity;

a protease;

nitrogen-containing or soluble starch or polysaccharide stabilizers; and

water;

wherein the detergent has an alkaline pH of at least about 9; and

wherein the detergent use solution of the composition maintains cleaning performance within the use solution for at least about 20 minutes at a temperature of at least about 65 ℃.

2. The composition of claim 1, wherein the stabilizer is an amine, amide, polyamide, and/or polyamine.

3. The composition of claim 1, wherein the stabilizer is a casein or gelatin stabilizer, a combination of casein and gelatin or derivatives thereof (e.g., Amino 1000).

4. The composition of claim 1, wherein the stabilizing agent is a polysaccharide selected from the group consisting of: amylose, amylopectin, pectin, inulin, modified inulin, potato starch, modified potato starch, corn starch, modified corn starch, wheat starch, modified wheat starch, rice starch, modified rice starch, cellulose, modified cellulose, dextrin, dextran, maltodextrin, cyclodextrin, glycogen, fructo-oligosaccharide and other soluble, partially soluble starches or modified derivatives thereof.

5. The composition of claim 1, wherein the stabilizer is a starch comprising amylose and/or amylopectin.

6. The composition of claim 1, wherein the detergent composition comprises from about 50 wt% to about 85 wt% of an alkali metal carbonate, from about 5 wt% to about 30 wt% of water, from about 0.01 wt% to about 5 wt% of a protease, and from about 0.01 wt% to about 30 wt% of a stabilizer.

7. The composition of claim 1, further comprising at least one component selected from the group consisting of: a surfactant or surfactant system, a chelating agent, and an additional enzyme stabilizer.

8. The composition of claim 1, wherein the detergent is substantially free of phosphorous and/or NTA.

9. A stable all purpose detergent use solution composition produced by a process comprising the steps of:

providing a detergent use composition comprising: an alkali metal carbonate alkalinity source, a protease, or an amine, amide, polyamide and/or polyamine stabilizer or polysaccharide stabilizer, and water, wherein the detergent use composition is provided in one or more solid and/or liquid compositions to produce the use composition;

contacting the solid detergent composition with a diluent to produce an aqueous use solution;

wherein the use solution has a basic pH of at least about 9;

wherein the protease maintains enzyme activity in the use solution at a temperature of about 65-80 ℃ for at least 20 minutes.

10. The composition of claim 9, wherein the stabilizing agent results in at least about 40% protease activity remaining for the period of time.

11. The composition of claim 10, wherein the stabilizer is a casein or gelatin stabilizer or a combination thereof (e.g., Amino 1000).

12. The composition of claim 10, wherein the stabilizer is an amylose and/or amylopectin containing starch.

13. The composition of claim 9, wherein the use solution composition comprises from about 50 wt% to about 85 wt% of an alkali metal carbonate active, from about 5 wt% to about 30 wt% of water, from about 0.01 wt% to about 5 wt% of a protease enzyme, and from about 0.0001 wt% to about 30 wt% of a stabilizer active.

14. The composition of claim 9, wherein the use solution has at least about 60% protease activity for the period of time, and wherein the use solution comprises about 10ppm to 2000ppm active stabilizer and about 0.1ppm to 100ppm protease.

15. The composition of claim 9, wherein the detergent use solution comprises at least one additional functional ingredient selected from the group consisting of: defoamers, anti-redeposition agents, bleaching agents, surfactants, solubility modifiers, dispersants, rinse aids, polymers, metal protection agents, additional stabilizers, corrosion inhibitors, sequestrants and/or chelating agents, fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes or coupling agents, buffers, solvents, and combinations thereof.

16. A cleaning method using a stable multipurpose detergent composition, the method comprising:

forming a use solution of a detergent composition comprising: an alkali metal carbonate alkalinity source, a protease, or a nitrogen-containing stabilizer or a soluble starch or polysaccharide stabilizer, and water, wherein the detergent composition is provided in one or more solid and/or liquid compositions;

contacting a surface with the use solution; and

cleaning the surface with the use solution, wherein the use solution has an alkaline pH of at least about 9, and wherein the protease enzyme remains enzymatically active within the use solution for at least 20 minutes at a temperature of about 65-80 ℃.

17. The method of claim 16, wherein at least about 60% of the enzymatic activity is maintained for the period of time.

18. The method of claim 16, wherein at least about 30% of the enzyme activity is maintained for at least about 60 minutes at a pH of at least about 9 and a temperature of about 65-80 ℃.

19. The method of claim 16, wherein the enzyme is present in the use solution at about 0.1ppm to about 100ppm, wherein the stabilizer is present in the use solution at about 0.1ppm to about 10,000ppm active.

20. The method of claim 16, wherein the enzyme is present in the use solution at about 0.1ppm to about 100ppm, and wherein the stabilizer is present in the use solution at about 10ppm to about 1,000ppm active.

21. The method of claim 16, wherein the surface is a vessel.

22. The method of claim 16, wherein the detergent is a multi-purpose solid detergent composition.

23. The method of claim 16, wherein the use solution is introduced into the wash step of the wash cycle and enhances soil removal and/or prevents soil redeposition and maintains low foaming of the wash water source.

Technical Field

The present invention relates generally to the field of cleaning compositions. In particular, the present invention is a multi-purpose composition and method for removing/preventing redeposition of soils using a stable cleaning composition (i.e., its use solution), wherein the cleaning composition beneficially includes an enzyme. The use solutions of the present invention are preferably generated from solid compositions comprising an enzyme and an enzyme stabilizer, thereby advantageously providing shelf stability of the enzyme-containing solid compositions as opposed to the limited shelf stability of liquid formulations using enzymes.

Background

Detergency is defined as the ability to wet, emulsify, suspend, penetrate and disperse soils. Conventional detergents used in the warewashing and laundry industries include alkaline detergents. Alkaline detergent formulations using alkali metal carbonates and/or alkali metal hydroxides intended for both institutional and consumer use are known to provide effective detergency, especially when used with phosphorus-containing compounds.

Phosphates are a commonly used multifunctional component in detergents to reduce water hardness and increase detergency, antiredeposition and crystal modification. In particular, polyphosphates, such as sodium tripolyphosphate and its salts, are used in detergents because of their ability to prevent calcium carbonate precipitation and their ability to disperse and suspend soils. If the calcium carbonate is allowed to precipitate, the crystals may adhere to the surface being cleaned and cause undesirable effects. For example, calcium carbonate precipitation on the surface of ware can negatively impact the aesthetic appearance of the ware and produce an unclean appearance to the ware. In the laundry field, if calcium carbonate precipitates and adheres to the surface of the fabric, the crystals may leave the fabric with a hard and rough feel to the touch. In addition to preventing calcium carbonate precipitation, the ability of sodium tripolyphosphate to disperse and suspend soils promotes the detergency of the solution by preventing the soils from redepositing into the wash solution or wash water.

However, the use of phosphorus raw materials in detergents has become undesirable for various reasons, including environmental reasons. Due to recent regulations, recent work has been directed to replacing phosphorus in detergents. There is therefore a need in the art for environmentally friendly multifunctional components that can replace the properties of phosphorus-containing compounds such as phosphates, phosphonates, phosphites and acrylic hypophosphite polymers.

Enzymes have been used in cleaning compositions since the early twentieth century. Until the mid-sixties of the twentieth century, enzymes were not commercially available and had both pH stability and soil reactivity for detergent applications. Enzymes are known as effective chemicals for use with detergents and other cleaning agents to break down soils. Enzymes break down soils, making them more soluble and enabling surfactants to remove soils from surfaces to provide enhanced cleaning of substrates.

The enzyme may provide the desired activity to remove, for example, protein-based, carbohydrate-based, or triglyceride-based soils from the substrate. As a result, enzymes are used in various cleaning applications to digest or degrade soils such as grease, oils (e.g., vegetable oils or animal fats), proteins, carbohydrates, or the like. For example, enzymes may be added as components in compositions for laundry, textiles, ware washing, clean-in-place, drain, floor, carpet, medical or dental instruments, meat cutting tools, hard surfaces, personal care, or the like. Although enzyme products have evolved from simple powders containing alkaline proteases to more complex granular compositions containing multiple enzymes and still further liquid compositions containing enzymes, there is still a need for alternative cleaning applications using stable enzymes. Many mechanisms have been utilized to improve enzyme stability for storage in liquid compositions (i.e., liquid detergent compositions), such as disclosed in U.S. patent No.8,227,397, which is incorporated by reference in its entirety. However, there remains a need for improvements such that liquid use compositions maintain detergency and cleaning performance when exposed to elevated temperatures, pH and/or extended periods of time under use conditions.

It is therefore an object of the present invention to develop a solid stable detergent composition with a protease and a stabilizer such that the storage and/or transport of the composition is not restricted. Moreover, such solid compositions are then suitable for the production of stable use solutions which maintain suitable enzyme stability at elevated temperatures and pH of use.

It is a further object of the present invention to develop a detergent composition and a multipurpose stable use solution of enzymes to increase the stability of enzymes under high temperature and pH conditions, thereby providing improved detergency.

The object of the present invention is to develop a method for using stabilized enzymes and/or stabilized use solutions containing enzymes for improved detergency.

It is a further object of the present invention to develop methods of using stabilized enzymes and/or stabilized use solutions to maintain enzyme and use solution stability for at least about 20 minutes or more at temperatures of about 65-80 ℃ or more and under alkaline conditions at a pH of about 9 to about 11.5. Advantageously, these objects overcome the significant limitations of enzyme stability in detergent compositions of the prior art, i.e. wherein the unstable enzyme activity decreases significantly over time, including over a short period of time of as little as 5-20 minutes.

In one aspect of the invention, enzyme activity is maintained by stabilizing a detergent composition and/or detergent use solution comprising the enzyme under conditions of elevated temperature and pH.

It is a further object of the present invention to develop a multi-purpose composition and method of using it to improve the protein removal and anti-redeposition performance of low-phosphorous detergents and especially sodium carbonate based detergents.

These and other objects, advantages and features of the present invention will become apparent from the following description taken in conjunction with the claims set forth herein.

Brief description of the invention

According to the present invention, methods are provided for stabilizing use solutions for detergent warewashing and stabilizing enzymes in detergents and multi-purpose compositions, especially high temperature detergent applications, to prolong enzyme stability and cleaning performance. An advantage of the present invention is the extended stability of the enzyme (i.e., protease) for various detergent applications, and the extended stability of the use solution of the cleaning composition at elevated temperatures, as compared to compositions and use solutions of the compositions that do not contain the stabilizers disclosed herein.

In one embodiment, the present invention includes a detergent use solution for removing soils (including protein soils therein) from a substrate surface and preventing redeposition of protein soils on the substrate surface. The detergent use solution beneficially reduces and/or prevents foaming in cleaning applications, thereby providing further use benefits. The use solution according to embodiments of the invention comprises a source of alkali metal carbonate alkalinity, a protease, and a stabilizer, for example an amine, such as casein or gelatin (nitrogen-containing stabilizer) or a polysaccharide (starch-based stabilizer).

In further embodiments, the present invention includes a method of stabilizing a multipurpose detergent use solution and using it to remove soils (including protein soils) from a substrate surface and prevent redeposition of protein soils on the substrate surface. The method comprises generating and introducing a stable enzyme-containing detergent use solution during the wash step of a wash cycle, washing the surface of the substrate with the use solution during the wash cycle, and subsequently rinsing the surface of the substrate (with or without a rinse aid). The use solutions and wash cycles to produce the invention for cleaning substrates are suitable for use at elevated temperatures and pH for extended periods of time, including, for example, periods of at least 20 minutes or at least 30 minutes or still more preferably at least 40 minutes at temperatures in excess of about 65 ℃ at pH in excess of about 9.

The enzyme-containing multipurpose detergent use solution according to embodiments of the present invention may be obtained by contacting the enzyme-containing detergent composition with water and/or adding a source of the enzyme to the detergent use solution. For example, according to embodiments of the present invention, an aqueous use solution may be obtained by contacting the detergent composition and enzyme composition with a water source, by contacting the detergent/enzyme composition combination with a water source, and/or by providing the enzyme source directly into the use solution of the detergent composition. Thus, detergent compositions and enzyme compositions (or enzyme sources) may be formulated in the process of the invention, either in combination or independently, depending on the application. The actual level of aqueous use solution is adjusted to the desired level by controlling variables such as the amount of active enzyme in the detergent and enzyme composition, the length of time the water is contacted with the detergent and enzyme composition, the temperature, and the like.

For use in accordance with embodiments of the present invention, the particular enzyme or combination of enzymes may vary depending on various factors including, for example, the application in which the stable use solution is used, the physical product form, the use pH, the use temperature, and the type of soil to be cleaned. In accordance with the present invention, the enzyme is selected to provide optimal activity and stability for a given set of use conditions, as will be appreciated by those skilled in the art based on the disclosure of the claimed invention. In a preferred aspect, the protease is particularly suitable for use in high temperature detergent applications.

While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.

Brief Description of Drawings

Figures 1-2 show protein removal scores measured after 40 minute pool incubations using the enzyme detergent according to embodiments of the invention for glass substrates (figure 1) and plastic substrates (figure 2).

Figures 3A-3C illustrate the anti-foaming benefits of using the enzyme Esperase, according to embodiments of the present invention.

Figures 4A-4D show the anti-foaming benefits of using the enzyme Stainzyme according to embodiments of the present invention.

Various embodiments of the present invention are described in detail with reference to the drawings, wherein like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the invention. The drawings presented herein are not to be taken as limiting the various embodiments of the invention and are presented for purposes of illustrating the invention.

Detailed description of the preferred embodiments

Embodiments of the present invention are not limited to particular methods of stabilizing multi-purpose detergent use solutions and compositions using enzymes in detergent use applications, which may vary and are understood by those skilled in the art. It is further to be understood that all terms used herein are merely descriptive of particular embodiments and are not intended to be limiting in any way or scope. For example, as used in this specification and the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the content clearly dictates otherwise. Further, all units, prefixes, and symbols may be represented in their SI accepted form. Recitation of ranges of values in the specification are inclusive of the values recited and include each integer within the defined range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which 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 present 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 definitions set out below.

The term "about" as used herein refers to variations in the numerical quantities that may occur, for example, in the real world through typical measurement and liquid handling procedures used to prepare concentrates or use solutions, through inadvertent error within such procedures, and through differences in the preparation or source or purity of the ingredients used to prepare the compositions or to practice the methods. The term "about" also encompasses the differential amounts resulting from different equilibrium conditions of the composition resulting from a particular starting mixture. Whether or not modified by the term "about," the claims include equivalents to the amounts used, meaning changes in the numerical amounts may occur.

The term "cleaning" as used herein refers to a method used to aid or assist in any soil removal, bleaching, microbial community reduction, and any combination thereof. The term "microorganism" as used herein refers to any non-cellular or single-cell (including colony) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, tunicates, fungi, protozoa, virions (virinos), viroids, viruses, bacteriophages and certain algae. The term "microorganism" as used herein is synonymous with microorganism (microbe).

The phrase "food product" as used herein includes any food substance that may require treatment with an antimicrobial agent or composition and that is edible with or without further preparation. Food products include meat (e.g., red meat and pork), seafood, poultry, produce (e.g., fruits and vegetables), eggs, raw eggs, egg products, ready-to-eat food, wheat, seeds, roots, tubers, leaves, stems, corn, flowers, sprouts, spices, or combinations thereof. The term "agricultural products" refers to food products such as fruits and vegetables and plants or plant-derived materials that are typically sold uncooked and often unpackaged, and sometimes eaten raw.

The term "ware" as used herein refers to items such as eating and cooking utensils, dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors. The term "warewashing" as used herein refers to washing, cleaning or rinsing ware. Vessel also refers to an item made of plastic. The types of plastics that can be cleaned with the compositions of the present invention include, but are not limited to, those including polycarbonate Polymers (PC), acrylonitrile-butadiene-styrene polymers (ABS), and polysulfone Polymers (PS). Another exemplary plastic that can be cleaned using the compounds and compositions of the present invention includes polyethylene terephthalate (PET).

As used herein, the terms "water" and "water source" and similar terms refer to a source of water used in warewashing and other detergent use applications in accordance with the present invention. According to embodiments of the invention, water is used to create a detergent use solution and to recycle or re-circulate aqueous detergents or other cleaning agents (including enzymes) used in cleaning applications to treat various surfaces.

According to certain regulated cleaning applications, it is required that the water source be periodically discarded and replaced with clean water for use in the cleaning application. For example, certain regulations require water to be replaced at least every four hours to adequately maintain a clean water source for cleaning applications. According to the invention, the water is not limited by the source of the water. Exemplary water sources suitable for use include, but are not limited to, water from municipal water sources or private water systems, such as public water sources or water wells, or any water source, including those containing hardness ions. As used herein, "wt%", "weight percent," or "weight percent," and variations thereof, refer to the concentration of a substance when the weight of that substance is divided by the total weight of the composition and multiplied by 100. It is to be understood that as used herein, "percent," "percent," and similar terms are intended to be synonymous with "weight percent," "wt%", and the like.

The terms "active" or "% active" or "wt% active" or "active concentration" are used interchangeably herein and refer to the concentration of those ingredients involved in cleansing, expressed as a percentage minus inert ingredients (e.g., water or salt). The concentrations and wt% of the enzymes mentioned in the present application are not expressed as "actives (e.g. active enzyme proteins)" but refer to the concentration and weight percentage of the raw material.

According to one embodiment of the invention, an enzyme is included in the detergent use solution according to the method of the invention to effectively remove soils and prevent redeposition of the soils onto the cleaning substrate using low phosphorous detergent compositions.

Detergent composition

Exemplary ranges of solid detergent compositions according to the invention are shown in table 1 as weight percent of the detergent composition.

TABLE 1

According to embodiments of the present invention, the detergent use composition advantageously provides a stable enzyme for improved detergency, i.e. provides stability of the enzyme for use under warewashing conditions including elevated temperatures for a period of at least 20 minutes. Various enzymes (preferably proteases) are used in combination with stabilizers to control the stability and cleaning efficacy of the cleaning composition under cleaning conditions (i.e., under elevated temperature and pH conditions). In one aspect, the stable use composition maintains the efficacy of the enzyme at conditions of at least about 60 ℃ and pH at least about 9, at conditions of at least about 65 ℃ and pH at least about 9, and preferably at least about 65-80 ℃ and pH from about 9 to about 11.5. Using enzyme analysis, the stability of the enzyme was confirmed to demonstrate that at least significantly similar washability was maintained using the solution under such elevated temperature and pH conditions for at least about 20 minutes or longer. In some aspects, the stability of the enzyme under elevated temperature and pH conditions is at least about 40 minutes, at least about 60 minutes, at least about 90 minutes, at least about 2 hours or more.

The multi-purpose detergent use compositions employing the enzyme stabilizer result in at least about 30% enzyme activity retention, at least about 35% enzyme retention, at least about 40% enzyme retention, at least about 45% enzyme retention, at least about 50% enzyme retention, at least about 55% enzyme retention, at least about 60% enzyme retention, at least about 65% enzyme retention, at least about 70% enzyme retention, or at least about 75% enzyme retention or greater under conditions of high alkalinity and high temperature over an extended period of time as set forth herein. This retention of enzyme activity in the use solution has not been achieved before under conditions of high alkalinity and high temperature according to the present invention, demonstrating the significant benefits of the present invention.

The compositions of the present invention are preferably provided in the form of multi-purpose or multi-dose solid concentrates to be diluted to form a use composition or aqueous use solution. Concentrate refers to a composition intended to be diluted with water to provide a use solution that contacts an object to provide a desired cleaning, rinsing or similar effect. The detergent composition that contacts the article to be washed may be referred to as a concentrate or use composition (or use solution), depending on the formulation used in the method of the invention. It will be appreciated that the concentration of alkali metal carbonate, enzyme stabilizer and other optional functional ingredients within the detergent composition will vary depending on whether the detergent composition is provided as a concentrate or as a use solution. As further set forth herein, not all components need be prepared in concentrate form, e.g., the detergent composition can be provided in combination with the individual components (e.g., enzymes and/or stabilizers) in the form of a use solution.

In an alternative embodiment, the multi-purpose cleaning composition may be provided as a ready-to-use (RTU) composition. If the cleaning composition is provided as a RTU composition, a more significant amount of water is added to the cleaning composition as a diluent. When the concentrate is provided in solid form, the aqueous solution is first obtained and may then be further diluted to provide it in flowable form so that it may be pumped or pumped. It has been found that it is often difficult to accurately pump small amounts of liquid. Large volumes of liquid are typically pumped more efficiently. Thus, while it is desirable to provide a concentrate with as little water as possible to reduce shipping costs, it is also desirable to provide a concentrate that can be dispensed accurately.

In one aspect of the present invention, a use solution is generated from the solid multipurpose detergent composition of table 1 having a dilution ratio range of about 1:10 to 1:10,000. In one aspect of the invention, a use solution of the stabilized detergent composition has from about 1ppm to about 2500ppm alkali metal carbonate, from about 1ppm to about 1000ppm active stabilizer, and from 1ppm to about 200ppm enzyme. Furthermore, all ranges recited include the numerical values defining the range and include each integer within the defined range without limiting the invention.

In some embodiments of the present invention, the solid multi-purpose composition and/or use solution described above may be substantially free of phosphorus or free of phosphorus. In additional aspects, the solid compositions and/or use solutions described above may be substantially free of NTA or free of NTA. In additional aspects, the solid compositions and/or use solutions described above contain less than 0.5 wt% phosphorus and/or NTA.

The solid multipurpose detergent composition is preferably a solid block to provide shelf stability to the protease containing composition. Such as disclosed in U.S. Pat. Nos.32,762 and 32,818, for example to SOLIDBranding technology, listing hardening technology and use of solid block detergents for institutional and industrial operations, and includes sodium carbonate hydrate cast solid products disclosed in U.S. patent nos.4,595,520 and 4,680,134 to Heile et al. Each of these references is incorporated herein by reference in its entirety. According to the mechanism of action, without limitation, the hardening mechanism is hydration of the ash or the interaction of sodium carbonate with water. According to the present invention, the solid detergent composition comprises any compressed, extruded or cast solid composition and a loose powder form. In a preferred aspect, the solid detergent composition is pressed and/or extruded.

Detergent composition

The process of the invention uses an aqueous use solution comprising, consisting of and/or consisting essentially of an alkaline detergent composition, preferably an alkali metal carbonate detergent, an enzyme and a stabilizer. The stable use solutions of the detergent composition and the enzyme advantageously result in a stabilization of the enzyme and/or the use solution itself. In other aspects, the enzyme and/or stabilizer may be formulated in a separate composition and/or provided at the point of use to produce a use solution comprising, consisting of and/or consisting essentially of an alkaline detergent composition (preferably an alkali metal carbonate detergent), the enzyme and the stabilizer.

Unlike most cleaning compositions currently known in the art, the cleaning compositions do not have to include phosphate to be effective. Thus, the cleaning compositions of the present invention provide a green alternative to conventional cleaning compositions. The detergent composition may be phosphorus free and/or nitrilotriacetic acid (NTA) free to make the cleaning composition more environmentally beneficial. By "phosphorus-free" is meant that the composition has less than about 0.5%, more specifically less than about 0.1%, and even more specifically less than about 0.01% by weight phosphorus, based on the total weight of the composition. This includes phosphates, phosphonates, phosphites or mixtures thereof. By "NTA-free" is meant that the composition has less than about 0.5 wt%, less than about 0.1 wt%, and especially less than about 0.01 wt% NTA, based on the total weight of the composition. In some aspects, when the composition is NTA-free, it may also be compatible with chlorine, which acts as an anti-redeposition and soil removal agent. However, in some aspects of the invention, the composition does not include chlorine because it is not compatible with enzymes.

Alkalinity source

The detergent composition comprises an effective amount of one or more alkalinity sources. An effective amount of one or more alkalinity sources should be considered an amount that controls the pH of the resulting use solution when water is added to the detergent composition to form the use solution. The pH of the use solution must be maintained in the alkaline range to provide adequate wash performance. In one embodiment, the pH of the use solution is from about 9 to about 13. If the pH of the use solution is too low, for example below about 9, the use solution may not provide sufficient wash performance. If the pH of the use solution is too high, for example above about 13, the use solution may be too basic and attack or damage the surface to be cleaned.

According to a preferred embodiment, the alkalinity source provides a composition having a pH of from about 7 to about 12. In particular embodiments, the cleaning composition has a pH of from about 8 to about 12. In particular embodiments, the pH of the cleaning composition is from about 9 to about 11.5. The pH of the use solution during the wash cycle is from about 8 to about 11.5, preferably from about 9 to about 11.5. Since the use solution of the present invention includes an enzyme composition, the pH can be further adjusted to provide an optimal pH range for the effectiveness of the enzyme composition. In particular embodiments of the present invention wherein the stabilized enzyme composition is incorporated into a cleaning composition, the optimum pH is from about 9.0 to about 11.5. In another particular embodiment of the invention, the pH of the use solution with an active concentration of about 0.01-0.5 wt% is from about 9 to about 13, or preferably the pH of the use solution with an active concentration of about 0.01-0.25 wt% is from about 9 to about 11.5.

Examples of suitable alkalinity sources in the cleaning composition include, but are not limited to, carbonate-based alkalinity sources including, for example, carbonates, such as alkali metal carbonates; caustic-based alkalinity sources including, for example, alkali metal hydroxides; other suitable alkalinity sources may include metal silicates, metal borates, and organic alkalinity sources.

The detergent composition of the present invention is preferably an alkali metal carbonate detergent. Illustrative alkali metal carbonates that may be used include, but are not limited to, sodium or potassium carbonate, sodium or potassium bicarbonate, sodium or potassium sesquicarbonate, and mixtures thereof.

In an alternative embodiment, the detergent composition may further comprise an alkali metal silicate. Examples of alkali metal silicates include, but are not limited to, sodium or potassium silicate or polysilicate, sodium or potassium metasilicate, and hydrated sodium or potassium metasilicate, or combinations thereof. In a preferred aspect, the detergent composition does not comprise an alkali metal silicate.

In additional embodiments, the detergent composition may comprise further alkalinity sources, such as caustic-based alkalinity sources, including, for example, alkali metal hydroxides. Exemplary alkali metal hydroxides that can be used include, but are not limited to, sodium hydroxide, lithium hydroxide, or potassium hydroxide. In a preferred aspect, the detergent composition comprises an alkali metal hydroxide.

In still further alternative embodiments, the detergent composition may further comprise a source of organic alkalinity, including, for example, strong nitrogen bases, including, for example, ammonia, amines, alkanolamines, and aminoalcohols. Typical examples of amines include primary, secondary or tertiary amines and diamines carrying at least one nitrogen-bonded hydrocarbon group representing a saturated or unsaturated, linear or branched alkyl group having at least 10 carbon atoms and preferably 16 to 24 carbon atoms, or an aryl, aralkyl or alkaryl group containing up to 24 carbon atoms, and wherein the optional other nitrogen-bonded groups are formed by optionally substituted alkyl, aryl or aralkyl groups or polyalkoxy groups. Typical examples of alkanolamines include monoethanol amine, monopropanol amine, diethanol amine, dipropanol amine, triethanol amine, tripropanol amine, and the like. Typical examples of aminoalcohols include 2-amino-2-methyl-l-propanol, 2-amino-l-butanol, 2-amino-2-methyl-l, 3-propanediol, 2-amino-2-ethyl-l, 3-propanediol, hydroxymethylaminomethane, and the like. In a preferred aspect, the detergent composition does not comprise an organic alkalinity source.

Alkaline detergent compositions, preferably alkali metal carbonates in the composition, may also act as hydratable salts to form solid detergents, i.e. cast solids. The hydratable salt can be referred to as substantially anhydrous. By "substantially anhydrous" it is meant that the component contains less than about 2 wt% water, based on the weight of the hydratable component. The amount of water may be less than about 1 wt%, and may be less than about 0.5 wt%. It is not required that the hydratable component be completely anhydrous.

According to the present invention, the detergent composition may be a liquid or a solid, including for example a moulding composition, as will be appreciated by those skilled in the art. Pastes and gels can be considered as liquid types. Powders, aggregates, pellets, tablets and blocks can be considered as solid types. For example, the detergent composition may be provided in the form of a block, pellet, powder (i.e., a mixture of particulate dry materials), aggregate, and/or liquid at room temperature and atmospheric pressure. Powder detergents are often prepared by mixing dry materials or by mixing a slurry and drying the slurry. Pellets and blocks are typically provided with a size determined by the shape or configuration of the die or extruder through which the detergent composition is compressed. The pellets are generally characterized by an average diameter of from about 0.5cm to about 2 cm. The blocks are generally characterized by an average diameter greater than about 2cm, preferably from about 2cm to about 2ft, and may have an average diameter of from about 2cm to about 1 ft. According to a preferred embodiment, the solid block is at least 50 g.

Additional descriptions of detergent compositions suitable for use in the present invention and methods of forming the same are disclosed, for example, in U.S. Pat. Nos.7,674,763,7,153,820,7,094,746, 7,037,886,6,924,257, and 6,730,653, the contents of which are incorporated by reference in their entirety.

Enzyme composition

The enzyme compositions used in the compositions and methods of the invention provide enzymes for enhanced soil removal, prevention of redeposition and additionally reduction of suds in the use solution of the cleaning compositions. The purpose of the enzyme composition is to break down adherent soils, such as starch or proteinaceous material, which are typically found in contaminated surfaces and are removed into the wash water source by the detergent composition. The enzyme composition removes soil from the substrate and prevents redeposition of soil onto the substrate surface. Enzymes provide additional cleaning and washing benefits, such as anti-foaming. Without being limited to a particular mechanism of action, the detergency of the use solutions according to the invention, the enzymes in the detergent use solutions beneficially enhance the removal of soils, especially protein removal in the case of the use of proteases, prevent soil redeposition, and reduce foaming, including for example the height of foam in the use solutions of the detergent and enzyme compositions. The combined benefits of the low foaming, cleaning enzyme use solution allow for both extended life of the effluent used in warewashing applications and improved cleaning of ware (and other articles).

Exemplary types of enzymes that can be incorporated into the detergent composition or detergent use solution include amylases, proteases, lipases, cellulases, cutinases, glucanases, peroxidases and/or mixtures thereof. The enzyme compositions of the invention may use more than one enzyme from any suitable source (e.g., plant, animal, bacterial, fungal or yeast source). However, according to a preferred embodiment of the invention, the enzyme is a protease. The term "protease" or "protease" as used herein refers to an enzyme that catalyzes the hydrolysis of peptide bonds.

One skilled in the art would recognize that enzymes are designed to work with specific types of soils. For example, according to one embodiment of the present invention, a warewashing application can use a protease because it is effective at the high temperatures of a warewasher and effective at reducing protein-based soils. Protease is particularly useful for cleaning protein-containing soils such as blood, skin scales, mucous, grass, food (e.g., egg, milk, spinach, meat residue, tomato paste) or the like. Proteases are capable of cleaving macromolecular protein bonds in amino acid residues and converting substrates into small segments that are readily dissolved or dispersed into aqueous use solutions. Proteases are often referred to as cleaning enzymes because they break down soils by a chemical reaction called hydrolysis. Proteases may for example be obtained from Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus. Proteases are also commercially available as serine endoproteases.

Examples of commercially available proteases are available under the following trade names: esperase, Purafect, Purafect L, Purafect Ox, Everlase, Liquanase, Savinase, Prime L, Prosperase and Blap.

According to the present invention, the enzyme composition may vary based on the particular cleaning application and the type of soil that needs to be cleaned. For example, the temperature of a particular cleaning application will affect the enzyme selected for the enzyme composition of the present invention. Enzymes such as proteases are desirable for warewashing applications, e.g., cleaning substrates at temperatures in excess of about 60 ℃, or at temperatures in excess of 70 ℃ or about 65 ℃ to 80 ℃, because of their ability to retain enzymatic activity at such high temperatures.

The enzyme compositions of the invention may be separate entities and/or may be formulated in conjunction with detergent compositions. According to one embodiment of the invention, the enzyme composition may be formulated as a detergent composition in the form of a liquid or solid formulation. In addition, the enzyme composition may be formulated into various delayed or controlled release formulations. For example, solid molded detergent compositions can be prepared without heating. Those skilled in the art will appreciate that enzymes tend to denature by the application of heat, and thus the use of enzymes in detergent compositions requires a process of forming the detergent composition that does not rely on heating as a step (e.g. hardening) within the forming process.

Commercially, the enzyme composition may further be available in solid (i.e., disk, powder, etc.) or liquid formulation form. Commercially available enzymes are usually combined with stabilizers, buffers, cofactors and inert carriers. The actual active enzyme content depends on the preparation method, which is well known to the person skilled in the art and which is not critical to the present invention.

Alternatively, the enzyme composition may be provided separately from the detergent composition, e.g., may be added directly to the wash liquor or wash water of a particular use application (e.g., of a warewashing machine).

Additional descriptions of enzyme compositions suitable for use in the present invention are disclosed, for example, in U.S. patent nos.7,670,549,7,723,281,7,670,549, 7,553,806,7,491,362,6,638,902,6,624,132, and 6,197,739, and U.S. patent publication nos.2012/0046211 and 2004/0072714, each of which is incorporated herein by reference in its entirety. In addition, the references Kirk-Othmer Encyclopedia of Chemical Technology, 3 rd edition (edited Grayson, M. and EcKroth, D.), volume 9, page 173-.

In a preferred aspect, the enzyme composition is provided in the solid composition in an amount of from about 0.01% to about 40%, from about 0.01% to about 30%, from about 0.01% to about 10%, from about 0.1% to about 5%, and preferably from about 0.5% to about 1%.

Stabilizer

The enzyme compositions used in the methods of the invention further comprise a stabilizing agent (referred to herein as a stabilizing agent) which can be manually or automatically dispensed into the detergent composition and/or use solution of the enzyme composition to stabilize the enzyme against loss of activity (i.e., to maintain proteolytic activity or enzyme retention under alkaline and high temperature conditions). In a preferred embodiment, the stabilizer and enzyme are formulated directly into the alkali metal carbonate detergents of the present invention. The formulation of the detergent composition and/or enzyme composition may vary based on the particular enzyme and/or stabilizer used. Starch-based and/or protein-based stabilizers are preferred stabilizers. In one aspect, the stabilizer is a starch, polysaccharide, amine, amide, polyamide, or polyamine. In still a further aspect, the stabilizer can be a combination of any of the foregoing stabilizers.

Protein stabilizing agent

In one embodiment, the stabilizing agent may include a nitrogen-containing group, including a quaternary nitrogen group, to increase the stability of the enzyme. In a preferred aspect, the stabilizing agent is a proteinaceous material. The protein or proteinaceous material may comprise casein, gelatin, collagen or the like. In one embodiment, the protein stabilizing agent is present in the use solution at a concentration of about 100-. In one embodiment, the ratio of stabilizer to enzyme is from about 10:1 to about 200:1, or from about 10:1 to about 100: 1.

In one aspect, the average molecular weight of the protein stabilizing agent is about 10,000 to 500,000, about 30,000 to 250,000, or about 50,000 to 200,000 (e.g., for casein). Exemplary proteins suitable for use in the present invention include, for example, casein and gelatin. Combinations of such exemplary proteins may also be used according to the present invention. A commercially available example is Amino 1000(GNC), which provides a combination of caseinate and gelatin proteins, as well as other ingredients such as vitamin E and soy lecithin. In some aspects, the protein stabilizing agent does not include small amino acids having a molecular weight below the defined ranges set forth herein.

In one aspect, the protein stabilizing agent is soluble or dispersible in water. In a further aspect, the protein stabilizing agent can include denatured or untangled proteins. Various commercially available proteins (e.g., casein) are sold in powder form and exist in long chemical chain form. Commercially as a powder, the protein chains fold on themselves and form hydrogen bonds, thereby maintaining the protein in a globular form. In one aspect, the untangled or denatured proteins form a more random structure and can be achieved by methods known in the art (e.g., boiling in water). In one aspect, for enzyme stability, denatured proteins are used.

In one aspect, the protein stabilizing agent may also include a protein hydrolysate, a polypeptide, or a natural or synthetic analog of a protein hydrolysate or a polypeptide. The term "hydrolysate" refers to any material produced by hydrolysis, without limitation to the specific material produced by any particular hydrolysis process. The term is intended to include "hydrolysates" produced by enzymatic as well as non-enzymatic reactions. "protein hydrolysate" refers to a hydrolysate produced by hydrolyzing any type or group of proteins, which may also be produced by enzymatic or non-enzymatic methods. Exemplary protein hydrolysates may include protein hydrolysates from wheat protein, soy protein acid hydrolysates, casein acid hydrolysates from cow milk and the like.

In one aspect, the protein stabilizing agent is not an antimicrobial agent, such as an amine. Amine refers to primary, secondary or tertiary amines. In one aspect, the protein stabilizing agent is not an antimicrobial amine and/or quaternary ammonium compound.

Starch-based stabilizers

In one embodiment, the stabilizer may comprise a starch-based stabilizer and optionally an additional food soil component (e.g., fat and/or protein to modify the starch-based stabilizer). In one aspect, the stabilizer is a starch, a polysaccharide (polysaccharide), or a polysaccharide (poly sugar). In one embodiment, the starch stabilizer is present in the use solution at a concentration of about 10-2000ppm active, preferably about 100-2000ppm active, or more preferably about 100-1000ppm active. In one embodiment, the ratio of stabilizer to enzyme is from about 10:1 to about 200:1, or from about 10:1 to about 100: 1.

Starch is a suitable stabilizer according to the invention. Starch refers to food stock material from plants and/or animals. Starch contains two major polysaccharide components, amylose, an amylose, and amylopectin, a highly branched material.

Polysaccharides are suitable stabilizers according to the invention. Polysaccharides as referred to herein are high molecular weight carbohydrates including, for example, condensation polymers of monosaccharide residues (most commonly greater than or equal to five monosaccharide residues). Polysaccharides may be substituted or unsubstituted and/or branched or straight chain and have alpha and/or beta linkages or linkages between sugar monomers (e.g., glucose, arabinose, mannose, etc.).

In one aspect, the polysaccharide has terminal groups with alpha-1, 4 linked substituted or unsubstituted glucose monomers, glucoside monomers, terminal glucoside monomers, or combinations thereof. As used herein, "end group" refers to a monomer or monomer group present at the end or terminal portion of a polysaccharide. All polysaccharides described herein have at least two terminal moieties, wherein the unsubstituted linear polysaccharide has two terminal moieties, the substituted linear polysaccharide has at least two terminal moieties, and the substituted or unsubstituted branched polysaccharide has at least three terminal moieties.

In another aspect, the polysaccharide has an end group with at least three alpha-1, 4 linked substituted or unsubstituted glucose monomers, glucoside monomers, end group glucoside monomers, or combinations thereof.

In one embodiment, the polysaccharide enzyme stabilizer is a homopolysaccharide or heteropolypolysaccharide, such as a polysaccharide containing only alpha-linkages or linkages between saccharide monomers. "alpha-linkage between sugar monomers" is to be understood as having its conventional meaning, that is to say that the linkage between the sugar monomers is a linkage of the anomeric isomer, for example the disaccharide (+) maltose or 4-O- (. alpha. -D-glucopyranosyl) -D-glucopyranose, the disaccharide (+) -cellobiose or 4-O- (. beta. -D-glucopyranosyl) -D-glucopyranose.

In another aspect, the polysaccharide enzyme stabilizer is a homopolysaccharide or heteropolysaccharide, and may comprise only glucose monomers, or a polysaccharide containing only glucose monomers, wherein a majority of the glucose monomers are bonded by α -1,4 linkages. Glucose is an aldohexose or a glucose monomer containing six carbon atoms. It is also a reducing sugar (e.g., glucose, arabinose, mannose, etc., most disaccharides, i.e., maltose, cellobiose, and lactose).

In another embodiment, the polysaccharase stabilizer is a substituted or unsubstituted glucose monomer having any ratio of α -1,4 linked monomers to α -1,6 linked monomers. Thus, the glucose monomers can be attached to the polysaccharide chain via any suitable position (e.g., 1,4, or 6 positions). By examining any particular enzyme stabilizer¹H NMR Spectroscopy (proton)NMR), the number of α -1,4, α -1,6, α -1,3, α -2,6 linkages is determined.

Polysaccharides are suitable stabilizers according to the invention. Advantageously, polysaccharides are biodegradable and are often classified as Generally Regarded As Safe (GRAS).

Exemplary stabilizers include, but are not limited to, amylose, amylopectin, pectin, inulin, modified inulin, potato starch (e.g., potato sprouts/flakes), modified potato starch, corn starch, modified corn starch, wheat starch, modified wheat starch, rice starch, modified rice starch, cellulose, modified cellulose, dextrin, dextran, maltodextrin, cyclodextrin, glycogen, fructo-oligosaccharides and other soluble or partially soluble starches. Particularly suitable stabilizers include, but are not limited to, inulin, carboxymethyl inulin, potato starch, sodium carboxymethyl cellulose, linear sulfonated alpha- (l,4) -linked D-glucose polymers, cyclodextrins, and the like. Combinations of stabilizers may also be used according to embodiments of the present invention. Modified stabilizers may also be used, wherein additional food soil components are combined with the stabilizer (e.g., fat and/or protein).

In one embodiment, the starch-based stabilizing agent is an amylopectin-and/or amylose-containing starch. In a further embodiment, the stabilizer is potato starch. In still further embodiments, the starch-based stabilizing agent is an amylopectin-and/or inulin-containing starch, such as potato starch modified (e.g., combined) with protein.

Stabilizer formulations

The stabilizers of the present invention may be formulated independently for the entity and/or in combination with the detergent composition and/or the enzyme composition. According to one embodiment of the present invention, the stabilizer may be formulated into the multipurpose detergent composition (with or without enzymes) in the form of a liquid or solid formulation. In addition, the stabilizer composition may be formulated into various delayed or controlled release formulations. For example, solid molded detergent compositions can be prepared without the addition of heat. Alternatively, the stabilizing agent may be provided separately from the detergent and/or enzyme composition, for example, added directly to the wash liquor or wash water of a particular use application (e.g., a warewashing machine).

In a preferred aspect, the stabilizer is formulated as a concentrated solid detergent with the enzyme.

In a preferred aspect, the stabilizer provides the only stability required by the enzyme within the detergent formulation. In this preferred aspect, no other stabilizers are used, such as any one or more of the following: boron compounds (e.g., borax, boron oxide, alkali metal borates, boric acid esters, alkali metal salts of boric acid, and the like) and calcium compounds. In preferred embodiments, the stabilizer and detergent composition are free of boric acid or borate.

Water (W)

Embodiments of the present invention can include water in the detergent composition and/or use solution. One skilled in the art can select the desired water grade to have the desired water hardness and grain level.

Additional Components

The compositions and methods of the present invention using aqueous detergent use solutions may further comprise additional components used in conjunction with the enzymes, stabilizers, and detergent compositions. Additional components that may be incorporated into the enzyme composition, detergent composition, combined enzyme and detergent composition and/or added separately to the water source include, for example, solvents, polymers, dyes, fragrances, anti-redeposition agents, solubility modifiers, dispersants, rinse aids, corrosion inhibitors, buffering agents, antifoam agents, antimicrobial agents, preservatives, chelating agents, bleaching agents, additional stabilizing agents, and combinations thereof.

Additional functional ingredients provide desirable properties and functionality to the compositions of the present invention. For the purposes of this application, the term "functional ingredient" includes materials that provide beneficial properties in a particular application when dispersed or dissolved in a use and/or concentrated solution, such as an aqueous solution. Some specific examples of functional materials are discussed in more detail below, but the specific materials discussed are given as examples only, and a wide variety of other functional compositions may 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 used in other applications.

Polymer system

The present invention includes a polymer system comprised of at least one polycarboxylic acid polymer, copolymer and/or terpolymer. In a preferred embodiment, the polymer system comprises at least two polycarboxylic acid polymers, copolymers and/or terpolymers. In a most preferred embodiment, the polymer system comprises at least three polycarboxylic acid polymers, copolymers and/or terpolymers. Polycarboxylic acid polymers particularly suitable in the present invention include, but are not limited to, polymaleic acid homopolymers, polyacrylic acid copolymers, and maleic anhydride/olefin copolymers. Polymaleic acid (C)₄H₂O₃)_xOr a hydrolyzed polymaleic anhydride or cis-2-butenedioic acid homopolymer having the following structural formula:

wherein n and m are any integer. Particularly preferred polymaleic acid homo-, co-and/or terpolymers (and salts thereof) useful in the present invention are those having a molecular weight of from about 0 to about 5000, more preferably from about 200 to about 2000. Commercially available polymaleic acid homopolymers include those available from BWA^TMWater Additives,979 Lakeside Parkway, Suite 925 Tucker, GA 30084, USA, the maleic acid homopolymer Belclene 200 series and Aquetreat AR-801 from Akzo Nobel. The polymaleic acid homopolymer, copolymer, and/or terpolymer may be present in the polymer system at an active concentration of about 25 wt% to about 55 wt%, about 30 wt% to about 50 wt%, or about 35 wt% to about 47 wt%.

The multipurpose detergent compositions of the present invention may use polyacrylic acid polymers, copolymers and/or terpolymers. Polyacrylic acid has the following structural formula:

where n is any integer. Examples of suitable polyacrylic acid polymers, copolymers, and/or terpolymers include, but are not limited to, polyacrylic acid (C)₃H₄O₂)_nOr 2-acrylic acid, polyacrylic acid, polymers, copolymers and/or terpolymers of acrylic acid.

In one embodiment of the present invention, particularly suitable acrylic polymers, copolymers and/or terpolymers have a molecular weight of from about 100 to about 10,000, in preferred embodiments from about 500 to about 7000, in even more preferred embodiments from about 1000 to about 5000, and in most preferred embodiments, from about 1500 to about 3500. Examples of polyacrylic acid polymers, copolymers and/or terpolymers (or salts thereof) useful in The present invention include, but are not limited to, Acusol 448 and Acusol 425 available from The Dow Chemical Company, Wilmington Delaware, USA. In particular embodiments, polyacrylic acid polymers (and salts thereof) having a molecular weight greater than about 10,000 may be desired. Examples include, but are not limited to, Acusol 929(10,000MW) and Acumer 1510(60,000MW), both available from Dow Chemical; AQUATREAT AR-6(100,000MW) available from Akzo Nobel Strawinskylan 25551077 ZZ Amsterdam Postbus 757301070 AS Amsterdam. Polyacrylic acid polymers, copolymers and/or terpolymers may be present in the polymer system at an active concentration of about 25 wt% to about 55 wt%, about 30 wt% to about 50 wt%, or about 35 wt% to about 47 wt%.

Maleic anhydride/olefin copolymers are copolymers of polymaleic anhydride and olefins. Maleic anhydride (C2H2(CO)2O has the following structure:

part of the maleic anhydride may be substituted by maleimide, N-alkyl (C)_1-4) Maleimide, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl (C) groups of the aforementioned acids_1-18) Esters, cycloalkyl radicals (C) of the foregoing acids_3-8) Esters, sulfated castor oil, or the like.

At least 95 weight percent of the maleic anhydride polymer, copolymer or terpolymer has a number average molecular weight in the range of from about 700 to about 20,000, preferably from about 1000 to about 100,000.

For the purposes of the present invention, a wide variety of linear and branched alpha-olefins may be used. Particularly useful alpha-olefins are diolefins having 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene and 2-methyl-1, 5-hexadiene; containing 4 to 8 carbon atoms and preferably C_4-10Such as isobutylene, 1-butene, 1-hexene, 1-octene and the like.

In one embodiment of the present invention, particularly suitable maleic anhydride/olefin copolymers have a molecular weight of from about 1000 to about 50,000, in a preferred embodiment from about 5000 to about 20,000, and in a most preferred embodiment from about 7500 to about 12,500. Examples of maleic anhydride/olefin copolymers useful in The present invention include, but are not limited to, Acusol 460N available from The Dow Chemical Company, Wilmington Delaware, USA. The maleic anhydride/olefin copolymer can be present in the polymer system at an actives concentration of about 5 wt% to about 35 wt%, about 7 wt% to about 30 wt%, or about 10 wt% to about 25 wt%.

Generally, it is contemplated that the composition will include a polymer system having an active concentration of about 0 wt% to about 20 wt%, about 0.01 wt% to about 15 wt%, and about 1 wt% to about 10 wt%. The polymer system of the present invention may comprise at least one polymaleic acid homopolymer, copolymer and/or terpolymer; at least one polyacrylic acid polymer, copolymer and/or terpolymer; and at least one maleic anhydride/olefin copolymer consisting essentially of, or consisting of, the foregoing. In one embodiment of the present invention, the polymer system comprises at least one polymaleic acid homopolymer, copolymer and/or terpolymer in a ratio of about 1:1:1 to about 2:2:1, or about 2:2:1 to about 3:3: 1; at least one polyacrylic acid polymer, copolymer and/or terpolymer; and at least one maleic anhydride/olefin copolymer. Further, without limiting the invention, a recited range of ratios includes the values defining the range and includes each integer within the defined range of ratios.

In additional aspects, the polycarboxylic acid polymer may also comprise a polymethacrylic acid homopolymer. An exemplary polymer is available from Akzonobel under the trade name Alcosperse 125 (30%).

The polymer system may be used in an amount sufficient to provide the desired level of scale control and soil dispersion when used in a use solution. The polymer system should be present in sufficient quantity to provide the desired scale control inhibition effect. It is expected that the upper limit of the polymer system will be determined by solubility. In a preferred embodiment, the polymer system is present in the use solution at about 1ppm to 500ppm, more preferably about 10ppm to 100ppm and most preferably about 20ppm to about 50 ppm.

Surface active agent

In some embodiments, the compositions of the present invention comprise a surfactant. The surfactant component serves primarily as a defoamer and as a wetting agent for the use solutions of the present invention. Surfactants suitable for use with the compositions of the present invention include, but are not limited to, nonionic surfactants, anionic surfactants, amphoteric surfactants, and zwitterionic surfactants. In some embodiments, the compositions of the present invention comprise a surfactant active concentration of about 0 wt% to about 50 wt%. In other embodiments, the compositions of the present invention comprise a surfactant active concentration of from about 0.1 wt% to about 30 wt%. In some embodiments, the compositions of the present invention comprise a surfactant active concentration of about 100ppm to about 10,000 ppm.

Nonionic surfactant

Useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically produced by condensing an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilic basic oxide moiety, which in common practice is ethylene oxide or its polyhydration product polyethylene glycol. In practice, any hydrophobic compound having a hydroxyl, carboxyl, amino or amide group with a reactive hydrogen atom may be condensed with ethylene oxide or its polyhydrated adduct or its mixture with an alkyleneoxy group (e.g., propylene oxide) to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be readily adjusted to provide a desired degree of water-dispersible or water-soluble compound having a desired balance of hydrophilic and hydrophobic properties. Useful nonionic surfactants include:

1. block polyoxypropylene-polyoxyethylene polymers based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator-reactive hydrogen compounds. Examples of polymers prepared from sequential propoxylated and ethoxylated initiators are under the trade name prepared by BASF CorpAndand (4) carrying out commercial purchase.The compounds are bifunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. The molecular weight of this hydrophobic moiety is from about 1,000 to about 4,000. Ethylene oxide is then added, sandwiching this hydrophobe between hydrophilic groups, the ethylene oxide being controlled by length to constitute from about 10 to about 80 weight percent of the final molecule.The compounds are tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylene diamine. The propylene oxide hydrotrope has a molecular weight ranging from about 500 to about 7,000; and adding the hydrophile ethylene oxide to comprise from about 10 wt% to about 80 wt% of the molecule.

Condensation products of 2.1mol of alkylphenols with about 3 to about 50mol of ethylene oxide, where the linear chain in the alkylphenolsOr a branched configuration or a single or dibasic alkyl component having an alkyl chain of from about 8 to about 18 carbon atoms. The alkyl group may be represented, for example, by the following: diisobutylene, di-pentyl, polymeric propylene, isooctyl, nonyl and dinonyl. These surfactants may be polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols. An example of a commercial compound of this chemistry is marketed under the trade name prepared by RhodiaAnd trade names made by Dow Chemical CompanyAnd (4) obtaining.

Condensation products of 3.1mol of saturated or unsaturated, linear or branched alcohols having from about 6 to about 24 carbon atoms with from about 3 to about 50mol of ethylene oxide. The alcohol moiety may consist of a mixture of alcohols within the carbon range described above, or it may consist of an alcohol having a specific number of carbon atoms within this range. An example of a similar commercial surfactant is under the trade name manufactured by Shell Chemical CoAnd trade name made by Sasol North America IncAnd (4) obtaining.

Condensation products of 4.1mol of saturated or unsaturated, linear or branched carboxylic acids having from about 8 to about 18 carbon atoms with from about 6 to about 50mol of ethylene oxide. The acid moiety may consist of a mixture of acids within the carbon atom range defined above, or it may consist of an acid having a specific number of carbon atoms within this range. An example of a commercial compound of this chemistry is marketed under the trade name Lipopeg, manufactured by Lipo Chemicals, Inc^TMAnd (4) obtaining.

In addition to ethoxylated carboxylic acids (often referred to as polyethylene glycol esters), other alkanoic acid esters formed by reaction with glycerides, glycerin, and polyols (sugars or sorbitan/sorbitol) are useful in the present invention for particular embodiments, especially indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecule that can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these materials. When adding these fatty esters or acylated carbohydrates to the compositions of the present invention containing amylase and/or lipase care must be taken because of potential incompatibility.

Examples of nonionic low-foaming surfactants include:

5. by addition of ethylene oxide to ethylene glycol to provide a hydrophile of a specified molecular weight; propylene oxide is then added to obtain hydrophobic blocks on the outside (ends) of the molecule to modify (substantially reverse) the compounds of group (1). The molecular weight of the hydrophobic portion is from about 1,000 to about 3,100, and the central hydrophile comprises from 10 wt% to about 80 wt% of the final molecule. Under the trade name of BASF CorporationR surfactants preparation of these reverseAlso, by sequentially adding ethylene oxide and propylene oxide to ethylenediamine, manufactured by BASF CorporationAnd (3) an R surfactant. The hydrophobic portion has a molecular weight of from about 2,100 to about 6,700 and the central hydrophile comprises from 10 wt% to 80 wt% of the final molecule.

6. Compounds of groups (1), (2), (3) and (4) modified by "capping" or "endcapping" (polyfunctional moieties) one or more terminal hydroxyl groups to reduce foaming by reaction with small hydrophobic molecules (e.g. propylene oxide, butylene oxide, benzyl chloride) and short chain fatty acids containing 1 to about 5 carbon atoms, alcohols or alkyl halides and mixtures thereof. Also included are reactants such as thionyl chloride which convert the terminal hydroxyl groups to chloride groups. This modification of the terminal hydroxyl groups can result in all-block, block-hetero, hetero-block, or all-hetero nonionic surfactants.

Additional examples of effective low foaming nonionic surfactants include:

alkylphenoxypolyethoxyalkanols of the formula, in U.S. Pat. No.2,903,486 to Brown et al, 8.9. 7.1959:

wherein R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.

U.S. Pat. No.3,048,548 issued to Martin et al on 8/7/1962 has a polyalkylene glycol condensate having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains wherein the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units and the weight of the attached hydrophilic units each comprise about 1/3 of the condensate.

A defoaming nonionic surfactant disclosed in U.S. Pat. No.3,382,178 issued to Lissant et al on 5/7/1968 and having the general formula Z [ (OR)_nOH]_zWherein Z is an oxyalkylatable material, R is a group derived from a basic oxide, which may be ethylene and propylene, and n is an integer of, for example, 10 to 2,000 or more and Z is an integer determined by the number of reactive oxyalkylatable groups.

Conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700 to Jackson et al, 5/4/1954, which correspond to the general formula Y (C)₃H₆O)_n(C₂H₄O)_mH, wherein Y is the residue of an organic compound having from about 1 to 6 carbon atoms and 1 reactive hydrogen atom, n is an average value of at least about 6.4 as determined by the number of hydroxyl groups, and m has a value such that the oxyethylene moiety comprises from about 10 to about 90 weight percent of the molecule.

Awarded to Lundste 4 month and 6 days 1954d et al, U.S. Pat. No.2,674,619, having the general formula Y [ (C)₃H₆O_n(C₂H₄O)_mH]_xWherein Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein x is a number of at least about 2, n is a number such that the molecular weight of the polyoxypropylene hydrophobe is at least about 900 and m is a number such that the oxyethylene content of the molecule is from about 10% to about 90% by weight. Compounds falling within the definition of Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylenediamine and the like. The oxypropylene chains optionally but advantageously contain a small amount of ethylene oxide, and the oxyethylene chains also optionally but advantageously contain a small amount of propylene oxide.

The additional conjugated polyoxyalkylene surface active agents advantageously used in the compositions of the present invention correspond to the general formula: p [ (C)₃H₆O)_n(C₂H₄O)_mH]_xWherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene moiety is at least about 44 and m has a value such that the oxypropylene content of the molecule is from about 10% to about 90% by weight. In either case, the oxypropylene chains may optionally but advantageously contain small amounts of ethylene oxide, and the oxyethylene chains may also optionally but advantageously contain small amounts of propylene oxide.

8. Polyhydroxy fatty acid amide surfactants suitable for use in the compositions of the present invention include those having the formula R²CONR¹Those of Z wherein R¹Is H, C₁-C₄A hydrocarbyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, an ethoxy group, a propoxy group, or a mixture thereof; r²Is C₅-C₃₁A hydrocarbon group, which may be linear; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and having at least three hydroxyl groups directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived from reducing sugars in reductive amination, for exampleSuch as glycidyl (glycidyl) moieties.

9. Alkyl ethoxylate condensation products of aliphatic alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the compositions of the present invention. The alkyl chain of the aliphatic alcohol may be linear or branched primary or secondary and typically contains from 6 to 22 carbon atoms.

10. Ethoxylated C₆-C₁₈Fatty alcohols and C₆-C₁₈Mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the compositions of the present invention, especially those that are water soluble. Suitable ethoxylated fatty alcohols include C with a degree of ethoxylation of from 3 to 50₆-C₁₈Ethoxylated fatty alcohols.

11. Suitable nonionic alkyl polysaccharide surfactants particularly suitable for use in the compositions of the present invention include those disclosed in U.S. Pat. No.4,565,647 to Llenado on 21.1.1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide (e.g., polyglycoside) hydrophilic group containing from about 1.3 to about 10 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example glucose, galactose, and galactosyl moieties can be substituted for glucosyl moieties. (optionally, the hydrophobic group is attached at the 2-,3-,4-, etc. position, thereby yielding glucose or galactose, as opposed to glucoside or galactoside.) the intersugar linkage may be, for example, between one position of the additional sugar unit and the 2-,3-, 4-and/or 6-position of the preceding sugar unit.

12. Fatty acid amide surfactants suitable for use in the compositions of the present invention include those having the general formula R⁶CON(R⁷)₂Wherein R is⁶Is an alkyl group having 7 to 21 carbon atoms, and each R⁷Independently of one another is hydrogen, C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl or- - (C)₂H₄O)_XH, wherein x ranges from 1 to 3.

13. One class of useful nonionic surfactants includes those defined as alkoxylated amines or most particularly alcohol alkoxylated/aminated/alkoxylated surfactants. These nonionic surfactantsThe sex agent may be at least partially represented by the following general formula: r²⁰-(PO)_sN-(EO)_tH， R²⁰-(PO)_sN-(EO)_tH(EO)_tH, and R²⁰--N(EO)_tH; wherein R is²⁰Is alkyl, alkenyl or other aliphatic group, or alkyl-aryl of 8 to 20 and preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5, and u is 1 to 10, preferably 2 to 5. Other variations within the scope of these compounds may be represented by the following alternative general formulae:

R²⁰-(PO)_v-N[(EO)_wH][(EO)_zH]wherein R is²⁰As defined above, v is 1 to 20 (e.g., 1,2,3 or 4, preferably 2), and w and z are independently 1 to 10, preferably 2 to 5. These compounds are commercially represented by a series of products sold by Huntsman Chemicals as nonionic surfactants. Preferred chemicals of this type includePEA 25 Amine Alkoxylate. Preferred nonionic surfactants for use in the compositions of the present invention include alcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates, and the like.

The therapeutic nonionics Surfactants, edited by Schick, m.j., volume 1, Marcel Dekker, inc., New York,1983 is a good reference for a wide variety of Nonionic compounds commonly used in The practice of The present invention. A typical list of the classes and species of the nonionic surfactants is given in U.S. Pat. No.3,929,678 to Laughlin and Heurin at 12.30.1975. Further examples are given in Surface Active Agents and Detergents, volumes I and II, Schwartz, Perry and Berch.

Semi-polar nonionic surfactants

Semi-polar types of nonionic surfactants are another class of nonionic surfactants useful in the compositions of the present invention. In general, semi-polar nonionic surfactants are high foaming agents and foam stabilizers, which can limit their use in CIP systems. However, within the embodiments of the compositions of the present invention designed for high foam cleaning methods, semi-polar nonionic surfactants have immediate efficacy. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.

14. Amine oxides are tertiary amine oxides corresponding to the general formula:

wherein the arrow is a conventional representation of a semi-polar bond, and R¹，R²And R³May be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. In general, for amine oxides for detergent purposes, R¹Is an alkyl group of from about 8 to about 24 carbon atoms; r²And R³Is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or mixtures thereof; r²And R³May be attached to each other, for example through an oxygen or nitrogen atom, to form a ring structure; r⁴Is a basic group or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to about 20.

Useful water-soluble amine oxide surfactants are selected from coconut or tallow alkyl di- (lower alkyl) amine oxides, specific examples of which are dodecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, octadecyl dimethylamine oxide, dodecyl dipropylamine oxide, tetradecyl dipropylamine oxide, hexadecyl dipropylamine oxide, tetradecyl dibutylamine oxide, octadecyl dibutylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, 3,6, 9-trioctadecyl dimethylamine oxide and 3-dodecyloxy-2-hydroxypropyl bis- (2-hydroxyethyl) amine oxide.

Useful semi-polar nonionic surfactants also include water-soluble phosphine oxides having the structure:

wherein the arrow is a conventional representation of a semi-polar bond; and R¹Is an alkyl, alkenyl or hydroxyalkyl moiety having a chain length ranging from 10 to about 24 carbon atoms; and R is²And R³Each is an alkyl moiety independently selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis (2-hydroxyethyl) dodecylphosphine oxide and bis (hydroxymethyl) tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include water-soluble sulfoxide compounds having the structure:

wherein the arrow is a conventional representation of a semi-polar bond; and R¹An alkyl or hydroxyalkyl moiety of from about 8 to about 28 carbon atoms, from 0 to about 5 ether linkages, and from 0 to about 2 hydroxyl substituents; and R is²Is an alkyl moiety consisting of an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group.

Useful examples of such sulfoxides include dodecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide and 3-hydroxy-4-dodecyloxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants useful in the compositions of the present invention include dimethylamine oxides, such as lauryl dimethylamine oxide, myristyl dimethylamine oxide, cetyl dimethylamine oxide, combinations thereof and the like. Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coco or tallow alkyl di- (lower alkyl) amine oxides, specific examples of which are octyl dimethylamine oxide, nonyl dimethylamine oxide, decyl dimethylamine oxide, undecyl dimethylamine oxide, dodecyl dimethylamine oxide, isododecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, octadecyl dimethylamine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl-2- (hydroxydodecyl) amine oxide, 3,6, 9-trioctadecyl dimethylamine oxide and 3-dodecyloxy-2-hydroxypropyl bis- (2-hydroxyethyl) amine oxide.

Suitable nonionic surfactants suitable for use with the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO/PO copolymers, capped EO/PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof or the like. Suitable alkoxylated surfactants for use as solvents include EO/PO block copolymers, for exampleAnd in the reverse directionA surfactant; alcohol alkoxylates, e.g.LS-54(R-(EO)₅(PO)₄) AndLS-36 (R-(EO)₃(PO)₆) (ii) a And blocked alcohol alkoxylates, e.g.LF221 andan ECU; mixtures thereof or the like.

Anionic surfactants

Also useful in the present invention are surface active materials that are classified as anionic surfactants because the charge on the hydrophobe is negative; or where the hydrophobic part of the molecule does not carry a charge unless the pH is raised to neutral or above (e.g. carboxylic acids). Carboxylates, sulfonates, sulfates and phosphates are polar (hydrophilic) solubilizing groups present in anionic surfactants. Among the cations (counter ions) bound to these polar groups, sodium, lithium and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; calcium, barium and magnesium promote oil solubility. It will be appreciated by those skilled in the art that anionic surfactants are excellent cleaning surfactants and are therefore routinely advantageously added to heavy duty detergent compositions.

Anionic sulfate surfactants suitable for use in the compositions of the present invention include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil alkenyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C₅-C₁₇acyl-N- (C)₁-C₄Alkyl) and-N- (C)₁-C₂Hydroxyalkyl) glucosamine sulfate and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides and the like. Also included are alkyl sulfates, alkyl poly (ethyleneoxy) ether sulfates and aromatic poly (ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 oxyethylene groups per molecule).

Anionic sulfonate surfactants suitable for use in the compositions of the present invention also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

Anionic carboxylate surfactants suitable for use in the compositions of the present invention include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleic acid, and the like. Such carboxylates include alkyl ethoxy carboxylates, alkylaryl ethoxy carboxylates, alkylpolyethoxypolycarboxylate surfactants, and soaps (e.g., alkylcarboxylates). Secondary carboxylates useful in the compositions of the present invention include those containing a carboxyl unit attached to a secondary carbon. The secondary carbon may be within the ring structure, for example in p-octylbenzoic acid, or in an alkyl-substituted cyclohexyl carboxylate. Secondary carboxylate surfactants typically contain no ether linkages, no ester linkages, and no hydroxyl groups. Further, they typically lack a nitrogen atom in the head group (the amphiphilic moiety). Suitable secondary soap surfactants typically contain 11-13 total carbon atoms, but more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acylamino acids (and salts), such as acylglutamates, acyl peptides, sarcosinates (e.g., N-acyl sarcosinates), taurates (e.g., N-acyl taurates and fatty acid amides of methyl tauric acid), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula:

R-O-(CH₂CH₂O)_n(CH₂)_m-CO₂X (3)

wherein R is C₈-C₂₂Alkyl orWherein R is¹Is C₄-C₁₆An alkyl group; n is an integer from 1 to 20; m is

Is an integer from 1 to 3; and X is a counterion, for example hydrogen, sodium, potassium, lithium, ammonium or an amine salt, for example monoethanolamine, diethanolamine orTriethanolamine. In some embodiments, n is an integer from 4 to 10, and m is 1. In some embodiments, R is C₈-C₁₆An alkyl group. In some embodiments, R is C₁₂-C₁₄Alkyl, n is 4, and m is 1.

In other embodiments, R isAnd R is¹Is C₆-C₁₂An alkyl group. In still other embodiments, R¹Is C₉Alkyl, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are typically available in the acid form, which can be readily converted to the anionic or salt form. Commercially available carboxylates include Neodox 23-4, a C_12-13Alkyl Polyethoxy (4) carboxylic acid (Shell Chemical), and Emcol CNP-110, a C₉Alkylaryl polyethoxy (10) carboxylic acid (Akzo Nobel). Carboxylic acid salts are also obtained from Clariant, e.g. productsDTC, a C₁₃Alkyl polyethoxy (7) carboxylic acids.

Cationic surfactant

If the charge on the hydrotrope portion of the molecule is positive, the surfactant is classified as a cationic surfactant. Surfactants in which the hydrotrope is uncharged unless the pH is lowered to near neutral or below, but which are cationic in the medium (e.g., alkylamines), are also included in this group. In theory, cationic surfactants can be synthesized from any combination of elements containing the "onium" structure RnX + Y- -, and it can also include compounds other than nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, the field of cationic surfactants is dominated by nitrogen-containing compounds, probably because the synthetic route of nitrogen-containing cationic surfactants is simple and straightforward and gives high yields of products, which can make them less expensive.

Cationic surfactants preferably include and more preferably refer to compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen. The long carbon chain groups may be directly attached to the nitrogen atom by simple substitution or more preferably indirectly attached to the nitrogen atom through one or more bridging functional groups in so-called interrupted alkylamine and amidoamine groups. These functional groups can make the molecule more hydrophilic and/or more water dispersible, more easily solubilized by water and/or made water soluble by the co-surfactant mixture. For increased water solubility, additional primary, secondary or tertiary amino groups may be introduced, or the amino nitrogen may be quaternized with a low molecular weight alkyl group. Further, the nitrogen may be part of a linear or branched moiety of variable unsaturation, or part of a saturated or unsaturated heterocyclic ring. Additionally, the cationic surfactant may contain a complex bond having more than one cationic nitrogen atom.

Surfactant compounds classified as amine oxides, amphoteric surfactants, and zwitterions are typically cationic in nature in solutions of near neutral to acidic pH, and may overlap the classification of surfactants. Polyoxyethoxylated cationic surfactants generally behave like nonionic surfactants in alkaline solutions and cationic surfactants in acidic solutions.

The simplest cationic amines, amine salts and quaternary ammonium compounds can thus be illustrated:

wherein R represents a long alkyl chain, R ', R "and R'" can be alkyl chains or aryl groups or hydrogen, and X represents an anion. For the practical application of the present invention, amine salts and quaternary ammonium compounds are preferred because of their high degree of water solubility.

Most of the large number of commercial cationic surfactants can be subdivided into four major classes and additional subgroups known to those skilled in the art and are described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Vol.104 (2), pp.86-96 (1989). The first class includes alkylamines and salts thereof. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourth class includes quaternary ammonium salts such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkylammonium salts, and the like. Cationic surfactants are known to have various properties that may be beneficial in the compositions of the present invention. These desirable properties may include detergency in compositions at or below neutral pH, anti-microbial efficacy, thickening or gelling in combination with other agents, and the like.

Cationic surfactants useful in the compositions of the present invention include those having the general formula R¹ _mR² _xY_LZ, wherein each R¹Is an organic group containing a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxyl groups and optionally spaced apart by up to 4 of the following structures or isomers or mixtures of these structures and which contains from 8 to 22 carbon atoms:

R¹the radicals may additionally contain up to 12 ethoxy groups, m having a number from 1 to 3. Preferably, when m is 2, not more than 1R is present in the molecule¹The group has greater than or equal to 16 carbon atoms, or greater than 12 carbon atoms when m is 3. Each R²Is an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, or a benzyl radical, and has no more than 1R in the molecule²Is benzyl, and x has a value of from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom position on the Y group is filled with hydrogen. Y may be a group including, but not limited to:

p-is about 1 to 12

p-is about 1 to 12

Or mixtures thereof. Preferably, L is 1 or 2, and when L is 2, the Y group is selected from R having 1 to about 22 carbon atoms and two free carbon single bonds¹And R²Preferably alkylene or alkenylene. Z is a water-soluble anion, for example a halide, sulfate, methylsulfate, hydroxide or nitrate anion, particularly preferably a chloride, bromide, iodide, sulfate or methylsulfate anion, in an amount such that the cationic component is rendered electrically neutral.

Amphoteric surfactant

Amphoteric surfactants contain both basic and acidic hydrophilic groups as well as organic hydrophobic groups. These ionic entities may 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 some surfactants, the sulfonate, sulfate, phosphonate, or phosphate provides a negative charge.

Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, phospho, or phosphono. 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), pp.69-71 (1989), which is incorporated herein by reference in its entirety. The first class includes acyl/dialkyl ethylenediamine derivatives (e.g., 2-alkyl hydroxyethyl imidazoline derivatives) and their salts. The second class includes N-alkyl amino acids and their salts. It is envisioned that some amphoteric surfactants are classified into both classes.

Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethylimidazolines are synthesized by condensing and ring-closing long-chain carboxylic acids (or derivatives) and dialkylethylenediamine. Commercial amphoteric surfactants are derived by subsequent hydrolysis and ring opening of the imidazoline ring, for example, by alkylation with chloroacetic acid or ethyl acetate. During alkylation, one or both carboxy-alkyl groups are reacted with a different alkylating agent to form a tertiary amine and an ether bond, thereby producing a different tertiary amine.

The long chain imidazole derivatives having application in the present invention generally have the following general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18 carbon atoms, and M is a cation to neutralize the charge of an anion (typically sodium). Commercially outstanding imidazoline derived amphoteric surfactants that can be used in the compositions of the present invention include, for example: cocoamphopropionate (Cocoamphopropionate), cocoamphocarboxy-propionate, cocoamphoglycinate, cocoamphocarboxy-glycinate, cocoamphopropyl-sulfonate and cocoamphocarboxy-propionic acid. Amphoteric carboxylic acids can be produced from fatty imidazolines, wherein the functional groups of the dicarboxylic acids in the amphoteric dicarboxylic acids are diacetic acid and/or dipropionic acid.

The carboxy-methylated compounds (glycinates) described several times herein above are referred to as betaines. Betaines are a particular class of amphoteric Surfactants discussed herein below in the section entitled Zwitterion Surfactants.

By making RNH₂Fatty amines are readily reacted with halogenated carboxylic acids to prepare long chain N-alkyl amino acids, where R ═ C₈-C₁₈Straight or branched chain alkyl. Alkylation of primary amino groups in amino acids leads to secondary and tertiaryAn amine. The alkyl substituent may have an additional amino group that provides more than one reactive nitrogen center. Most commercial N-alkyl amino acids are alkyl derivatives of beta-alanine or beta-N (2-carboxyethyl) alanine. Examples of commercial N-alkyl amino acid amphiphiles useful in the present invention include alkyl beta-amino dipropionate, RN (C)₂H₄COOM)₂And RNHC₂H₄And (4) COOM. In one embodiment, R may be an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.

Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut derived surfactants include ethylene diamine moieties, alkanolamide moieties, amino acid moieties (e.g., glycine), or combinations thereof as part of their structure and aliphatic substituents of about 8 to 18 (e.g., 12) carbon atoms. The surfactant may also be considered to be an alkyl amphoteric dicarboxylic acid. These amphoteric surfactants may include chemical structures represented by the formula: c₁₂-alkyl-C (O) -NH-CH₂-CH₂-N⁺(CH₂-CH₂-CO₂Na)₂-CH₂-CH₂-OH or C₁₂alkyl-C (O) -N (H) -CH₂-CH₂-N⁺(CH₂-CO₂Na)₂-CH_2-CH₂-OH. Disodium cocoamphodipropionate is a suitable amphoteric surfactant and is available under the trade nameFBS is commercially available from Rhodia inc. Another suitable coconut derived amphoteric surfactant having the chemical name disodium coconut amphodiacetate is sold under the trade nameJCHA is also sold by Rhodia inc, Cranbury, n.j.

A typical list of the amphoteric class and species of these surfactants is given in U.S. Pat. No.3,929,678 to Laughlin and Heurin at 12/30 of 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol.I and II, Schwartz, Perry and Berch). Each of these references is incorporated herein by reference in its entirety.

Zwitterionic surfactants

Zwitterionic surfactants can be considered a subset of amphoteric surfactants and can include an anionic charge. 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 carboxy groups, and alkyl groups. Zwitterionic surfactants usually contain cationic and anionic groups that ionize to nearly equal degrees in the isoelectric region of the molecule and can produce strong "endo-salt" attraction between positive-negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain and wherein one of the aliphatic substituents contains 8-18 carbon atoms and one of the aliphatic substituents contains an anionic water-solubilizing group, e.g., a carboxy group, a sulfonate group, a sulfate group, a phosphate group, or a phosphonate group.

Betaine and sulfobetaine surfactants are exemplary zwitterionic surfactants for use herein. These compounds have the general formula:

wherein R is^lAn alkyl, alkenyl or hydroxyalkyl group containing from 8 to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; y is selected from nitrogen, phosphorus and sulfur atoms; r²Is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom, x is 2 when Y is a nitrogen or phosphorus atom, R³Is alkylene or hydroxyalkylene of 1 to 4 carbon atoms and Z is selected from the group consisting ofAcid, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structure listed above include: 4- [ N, N-bis (2-hydroxyethyl) -N-octadecylammonium (ammonio) ] -butane-1-carboxylate; 5- [ S-3-hydroxypropyl-S-hexadecylsulfonium (sulfonio) ] -3-hydroxypentane-l-sulfate; 3- [ P, P-diethyl-P-3, 6, 9-trioxabitetracos-sphonium (phosphonio) ] -2-hydroxypropane-1-phosphate; 3- [ N, N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonio ] -propane-l-phosphonate; 3- (N, N-dimethyl-N-hexadecylammonium) -propane-l-sulfonate; 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-l-sulfonate; 4- [ N, N-bis (2 (2-hydroxyethyl) -N (2-hydroxydodecyl) ammonio ] -butane-1-carboxylate; 3- [ S-ethyl-S- (3-dodecyloxy-2-hydroxypropyl) sulfo ] -propane-1-phosphate; 3- [ P, P-dimethyl-P-dodecylphosphonium ] -propane-l-phosphonate; and S [ N, N-bis (3-hydroxypropyl) -N-hexadecylammonium ] -2-hydroxy-pentane-l-sulfate the alkyl groups contained in the detergent surfactant may be linear or branched and saturated or unsaturated.

Zwitterionic surfactants suitable for use in the compositions of the present invention include betaines of the general structure:

these surfactant betaines typically do not exhibit strong cationic or anionic character at pH extremes nor do they exhibit reduced water solubility in their isoelectric domain. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic surfactants. Examples of suitable betaines include cocoacylamidopropyl dimethyl betaine, cetyl dimethyl betaine, C_12-14Acylamidopropyl betaine, C_8-14Acylamidohexyl diethylbetaine, 4-C_14-16Acylmethylamido-diethylammonium-1-carboxybutane, C_16-18Acylamidodimethyl betaine, C_12-16Acylamidopentane diethylsweetCauliflower base and C_12-16Acyl methyl amido dimethyl betaine.

Sultaines (sultaines) useful in the present invention include those having the general formula (R)^l)₂N⁺R²SO^3-Wherein R is C₆-C₁₈A hydrocarbon radical, each R¹Typically independently C₁-C₃Alkyl, e.g. methyl, and R²Is C₁-C₆Hydrocarbyl radicals, e.g. C₁-C₃Alkylene or hydroxyalkylene.

A typical list of zwitterionic classes and species of these surfactants is given in U.S. Pat. No.3,929,678 to Laughlin and Heuring, 12/30 in 1975. Further examples are given in Surface Active Agents and Detergents (Vol.I and II, Schwartz, Perry and Berch), each of which is incorporated herein by reference in its entirety.

Additional enzyme stabilizers

Those skilled in the art will recognize suitable enzyme stabilizers and/or stabilizing systems for enzyme compositions suitable for use in the present invention, such as those described in U.S. Pat. Nos.7,569,532 and 6,638,902, which are incorporated herein by reference in their entirety. According to one embodiment of the invention, the enzyme stabilizing system may comprise a mixture of carbonate and bicarbonate, and may also include other ingredients to stabilize certain enzymes or to enhance or maintain the effectiveness of the mixture of carbonate and bicarbonate. The enzyme stabilizer may further comprise a boron compound or a calcium salt. For example, the enzyme stabilizer may be a boron compound selected from the group consisting of a boronic acid, a boric acid, a borate, a polyborate, and combinations thereof.

The enzyme stabilizer may also include a chlorine bleach scavenger that is added to prevent chlorine bleach species present from attacking and deactivating the enzyme, particularly under alkaline conditions. Thus, suitable chlorine scavenger anions may be added as enzyme stabilizers to prevent inactivation of the enzyme compositions of the present invention. Exemplary chlorine scavenger anions include salts of ammonium-containing cations with sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like. Antioxidants such as carbamates, ascorbates, and the like, organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof may also be used.

Rinse aid

The cleaning composition may optionally include a rinse aid composition, such as a rinse aid formulation containing a wetting agent or a stripping agent (sheeting agent) in combination with other optional ingredients in the solid composition. The rinse aid component can reduce the surface tension of the rinse water, promote stripping action and/or prevent spotting or streaking caused by water that beads after rinsing is complete, for example, in a warewashing process. Examples of release agents include, but are not limited to, polyether compounds in the form of homopolymer or block or hetero copolymer structures prepared from ethylene oxide, propylene oxide, or mixtures. Such polyether compounds are called polyalkylene oxide polymers, polyoxyalkylene polymers or polyalkylene glycol polymers. Such strippers require a relatively hydrophobic region and a relatively hydrophilic region to provide surfactant properties to the molecule. When a rinse aid composition is used, it may be present from about 1 to about 5 ml/cycle, with one cycle including about 6.5 liters of water.

Thickening agent

Thickeners useful herein include those compatible with alkaline systems. The viscosity of the cleaning composition increases with the amount of thickener used, and for applications in which the cleaning composition adheres to a surface, a viscous composition is useful. Suitable thickeners may include those that do not leave a contaminating residue on the surface to be treated. In general, thickeners that may be used in the present invention include natural gums, such as xanthan gum, guar gum, modified guar gum, or other gums from plant mucilage; polysaccharide-based thickeners, such as alginates, starches, and cellulosic polymers (e.g., carboxymethyl cellulose, hydroxyethyl cellulose, and the like); a polyacrylate thickener; and hydrocolloid thickeners such as pectin. Generally, the concentration of thickener used in the present compositions or methods will be determined by the desired viscosity in the final composition. However, as a general rule, the viscosity of the thickener, if present, in the compositions of the present invention ranges from about 0.1 wt% to about 3 wt%, from about 0.1 wt% to about 2 wt%, or from about 0.1 wt% to about 0.5 wt%.

Dyes and fragrances

Various dyes, odorants including perfumes, and other aesthetic enhancers may also be included in the cleaning compositions. Dyes may be included to modify the appearance of the composition, such as any of a variety of FD & C dyes, D & C dyes, and the like. Additional suitable dyes include Direct Blue 86(Miles), Fastussol Blue (Mobay Chemical Corp.), Acid Orange 7(American cyanamide), Basic Violet 10(Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17(Sigma Chemical), Sap Green (Keystone emulsion and Chemical), Metalne Yellow (Keystone emulsion and Chemical), Acid Blue 9(Hilton Davis), Sandolan Blue/Acid Blue 182(Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorsein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), Pylakor Red (Pylam), and the like. Fragrances or perfumes that may be included in the composition include, for example, terpenoids (e.g., citronellol), aldehydes (e.g., amyl cinnamaldehyde), jasmine (e.g., CIS-jasmine), or benzyl acetate, vanillin, and the like.

Bleaching agent

The cleaning compositions may optionally include a bleaching agent for lightening or whitening the substrate, and may include a material capable of releasing an active halogen, such as Cl, under conditions typically encountered during the cleaning process₂、Br₂-OCl-and/or-OBr-, etc. Examples of suitable bleaching agents include, but are not limited to, chlorine-containing compounds, such as chlorine, hypochlorite or chloramine; however, in some aspects of the invention, compatibility with the enzyme results in the use of no chlorine-containing compounds. Examples of suitable halogen-releasing compounds include, but are not limited to, alkali metal dichloroisocyanurates, alkali metal hypochlorates, monochloramine, and dichloramine. Encapsulated chlorine sources can also be used to improve the stability of the chlorine source within the composition (see, e.g., U.S. Pat. Nos. 4618914 and 4830773, the disclosures of which are incorporated herein by referenceIn). The bleaching agent may also include an agent that contains or acts as a source of active oxygen. The active oxygen compound functions to provide a source of active oxygen and may release active oxygen in an aqueous solution. The active oxygen compound may be inorganic or organic or a mixture thereof. Examples of suitable active oxygen compounds include, but are not limited to, peroxy compounds, peroxy compound adducts, hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrate, potassium permonosulfate, and sodium perborate monohydrate and tetrahydrate, with and without activators such as tetraacetylethylenediamine.

Disinfectant/antimicrobial agent

The cleaning composition may optionally include a disinfectant (or antimicrobial). Disinfectants (also referred to as antimicrobial agents) are chemical compositions that can be used to prevent microbial contamination and deterioration of material systems, surfaces, and the like. Generally, these materials fall into a specific group that includes phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, anilides, organo-sulfur and sulfur-nitrogen compounds, and a variety of compounds.

Depending on the chemical composition and concentration, a given antimicrobial agent may simply limit further propagation of microbial numbers, or may destroy all or a portion of the microbial community. The term "microorganism" typically refers primarily to bacteria, viruses, yeasts, spores and fungal microorganisms. In use, the antimicrobial agent is typically formed as a solid functional material that, when optionally diluted and dispensed, e.g., using an aqueous stream, forms an aqueous disinfectant or sanitizer composition that can be contacted with various surfaces, resulting in the prevention of the growth of or killing of a portion of a microbial community. Resulting in a 3 log reduction in microbial populations within the disinfectant composition. Antimicrobial agents may be encapsulated, for example, to improve their stability.

Examples of suitable antimicrobial agents include, but are not limited to, phenolic antimicrobial agents, such as pentachlorophenol, p-phenylphenol, chloro-p-benzylphenol, p-chloro-m-xylenol, quaternary ammonium compounds, such as alkyldimethylbenzylammonium chloride, alkyldimethylethylbenzylammonium chloride, octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride, and didodecyldimethylammonium chloride. Examples of suitable halogen-containing antimicrobial agents include, but are not limited to, sodium trichloroisocyanurates, sodium dichloroisocyanate (anhydrous or dihydrate), iodine-poly (vinylpyrrolidone) complexes, brominated compounds, such as 2-bromo-2-nitropropane-1, 3-diol, and quaternary antimicrobial agents, such as benzalkonium chloride, didecyldimethylammonium chloride, diiodocholine chloride, and tetramethylphosphonium tribromide. Other antimicrobial components, such as hexahydro-l, 3, 5-tris (2-hydroxyethyl) -s-triazine, dithiocarbamates, such as sodium dimethyldiiodocarbamate, and various other materials are known in the art for their antimicrobial properties.

It should also be understood that active oxygen compounds (such as those discussed in the bleach section above) may also act as antimicrobial agents, and may even provide disinfecting activity. In fact, in some embodiments, the ability of the active oxygen compound to act as an antimicrobial agent reduces the need for additional antimicrobial agents within the composition. For example, the percarbonate component has been shown to provide excellent antimicrobial action.

Activating agent

In some embodiments, the antimicrobial activity or bleaching activity of the cleaning composition may be enhanced by the addition of materials that react with active oxygen to form an activated component when the cleaning composition is placed in use. For example, in some embodiments, a peracid or a peracid salt is formed. For example, in some embodiments, tetraacetylethylenediamine may be included in the detergent composition to react with active oxygen and form a peracid or peracid salt that acts as an antimicrobial agent. Other examples of active oxygen activators include transition metals and compounds thereof, compounds containing carboxylic acid, nitrile or ester moieties, or other such compounds known in the art. In one embodiment, the activator comprises tetraacetylethylenediamine, a transition metal, a compound containing a carboxylic acid, nitrile, amine or ester moiety, or mixtures thereof. In some embodiments, the activator for the active oxygen compound combines with the active oxygen to form the antimicrobial agent.

In some embodiments, the cleaning composition is in the form of a solid block and an activator material for active oxygen is combined with the solid block. The activator can be incorporated onto the solid block by any of a variety of methods of incorporating one solid detergent composition onto another. For example, the activator may be in solid form bonded, fixed, glued, or otherwise adhered to the solid block. Alternatively, a solid activator may be formed around the block and encased therein. As a further example, the solid activator may be combined with the solid block by a container or package for the detergent composition, for example by a plastic or shrink wrap or film.

Builders or fillers

The cleaning composition may optionally include a minor but effective amount of one or more fillers that do not necessarily function as a cleaning agent by themselves, but may be complexed with a cleaning agent to enhance the overall cleaning ability of the composition. Examples of suitable fillers include, but are not limited to, sodium sulfate, sodium chloride, starch, sugars, C1-C10 alkylene glycols such as propylene glycol.

Defoaming agent

The cleaning composition may optionally include a minor but effective amount of a defoamer to reduce the stability of the foam. Examples of suitable antifoaming agents include, but are not limited to, silicone 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, and alkyl phosphate esters, such as monostearyl phosphate. A discussion of defoamers can be found, for example, in U.S. Pat. No.3,048,548 to Martin et al, U.S. Pat. No.3,334,147 to Brunelle et al, and U.S. Pat. No.3,442,242 to Rue et al, the disclosures of which are incorporated herein by reference.

Anti-redeposition agent

The cleaning composition may optionally include an anti-redeposition agent that can promote the continued suspension of soils in the cleaning solution and prevent the removed soils from redepositing onto the substrate being cleaned. Examples of suitable anti-redeposition agents include, but are not limited to, fatty acid amides, fluorocarbon surfactants, complex phosphate esters, polyacrylates, styrene maleic anhydride copolymers, and cellulose derivatives, such as hydroxyethyl cellulose, hydroxypropyl cellulose.

Additional stabilizers

The cleaning composition may also include further stabilizers. Examples of suitable stabilizers include, but are not limited to, borates, calcium/magnesium ions, propylene glycol, and mixtures thereof.

Dispersing agent

The cleaning composition may also include a dispersant. Examples of suitable dispersants that may be used in the solid detergent composition include, but are not limited to, maleic acid/olefin copolymers, polyacrylic acid, and mixtures thereof.

Hardening agent/solubility modifier

The cleaning composition may include a small but effective amount of a hardening agent. Examples of suitable hardeners include, but are not limited to, amides such as stearyl monoethanolamide or lauryl diethanolamide, alkylamides, solid polyethylene glycols, solid EO/PO block copolymers, starches that have been rendered water soluble by acid or base treatment processes, and various inorganic substances that impart hardening properties to the heated composition upon cooling. Such compounds may also alter the solubility of the composition in aqueous media during use, allowing detergents and/or other active ingredients to be dispensed from the solid composition over an extended period of time.

Auxiliary agent

The compositions of the present invention may also include any number of adjuvants. In particular, the cleaning composition may include stabilizers, wetting agents, foaming agents, corrosion inhibitors, biocides, and hydrogen peroxide, among any number of other ingredients that may be added to the composition. Such an adjuvant may be pre-formulated with the composition of the invention or may be added to the system simultaneously or even after the addition of the composition of the invention. The cleaning composition may also contain any number of other ingredients as required by the application, which are known and may contribute to the activity of the compositions of the present invention.

Application method

The cleaning compositions can be used in a variety of industries including, but not limited to, warewashing (institutional and consumer), food and beverage, health and fabric care for cleaning substrates and providing a number of beneficial results including enhanced detergency of carbonate alkaline detergent compositions (and/or stable use solutions) containing stabilized enzymes, wherein the detergent compositions are more effective in removing soils, preventing soil redeposition, and maintaining low sudsing of wash water. In particular, the cleaning compositions can be safely used to clean a variety of surfaces, including, for example, surfaces on ceramics, tiles, grout, granite, concrete, mirrors, enameled surfaces, metals (including aluminum), brass, stainless steel, glass, plastics, and the like. The compositions of the present invention can also be used to clean soiled linen such as towels, bed sheets and nonwoven webs. As such, the compositions of the present invention are useful in formulating hard surface cleaners, laundry detergents, oven cleaners, hand soaps, automotive detergents and warewashing detergents, whether automatic or manual. In preferred aspects of the invention, the cleaning compositions and methods of use are particularly suited for warewashing applications.

The compositions of the present invention may be provided as solids, liquids or gels or combinations thereof. As set forth in the composition description, the cleaning composition may be provided in one or more parts, such as in the formulation of a detergent composition, to include alkali metal carbonate, enzyme and stabilizer. Alternatively, the cleaning composition may be provided in two or more parts such that upon combining the two or more compositions, the total cleaning composition is formed within a stable use solution. Each of these embodiments is included in the following description of the process of the invention.

In one embodiment, the cleaning composition may be provided in the form of a concentrate, such that the cleaning composition is substantially free of any added water, or the concentrate may contain a nominal amount of water. The concentrate can be formulated without any water or can be provided using relatively small amounts of water to reduce the cost of shipping the concentrate. For example, the composition concentrates may be provided in a variety of solid compositions including, for example, capsules or granules as compressed powders, compressed, extruded and/or cast solids, or loose powders, either contained or absent by water-soluble materials. Where the capsules or granules of the composition are provided within a material, the capsules or granules may be introduced into a volume of water, and if present, the water soluble material may solubilize, degrade or disperse to allow contact of the composition concentrate with the water. For purposes of the present disclosure, the terms "capsule" and "pellet" are used for exemplary purposes and are not intended to limit the delivery mode of the present invention to a particular shape. When provided as a liquid concentrate composition, the concentrate can be diluted by dispensing equipment using pipettes, peristaltic pumps, gear pumps, mass flow meters, and the like. This liquid concentrate embodiment can also be delivered in bottles, cans, dose bottles, bottles with dose caps, and the like. The liquid concentrate composition may be filled into a multi-chamber cartridge insert, which is then placed into a squirt bottle or other delivery device that is filled with a pre-measured amount of water.

In yet another embodiment, the concentrate composition may be provided in a solid form that resists collapse or other degradation until placed in a container. Such a container may be filled with water either before the composition concentrate is placed in the container or after the composition concentrate is placed in the container, it may be filled with water. In either case, the solid concentrate composition dissolves, solubilizes, or otherwise disintegrates upon contact with water. In particular embodiments, the solid concentrate composition dissolves rapidly, thereby allowing the concentrate composition to become a use composition, and further allowing the end user to apply the use composition to a surface in need of cleaning.

In another embodiment, the solid concentrate composition can be diluted by a dispensing apparatus in which water is sprayed at the solid composition (e.g., compressed solids) to form a use solution. The water flow is delivered at a relatively constant rate using mechanical, electrical or hydraulic controls, etc. The solid concentrate composition may also be diluted by a dispensing device in which water flows around the solids, thereby creating a use solution when the solid concentrate is dissolved. Solid concentrate compositions may also be diluted by pellet, tablet, powder and paste dispensers and the like.

Conventional detergent dispensing equipment may be used in accordance with the present invention. For example, commercially available detergent dispensing equipment that can be used according to the present invention is known by the name Solid System^TMObtained from Ecolab, Inc. Use of such dispensing means results in the detergent composition being eroded by the water source to form the aqueous use solution of the present invention.

The water used to dilute the concentrate (dilution water) may be available at the site or location of dilution. The dilute water may contain varying levels of hardness depending on the location. Municipal water (service water) available from various municipalities has varying levels of hardness. It is desirable to provide a concentrate that can address the hardness levels present in municipal water of various municipalities. The dilution water used to dilute the concentrate can be characterized as hard water when it comprises at least 1 grain hardness. It is contemplated that the dilute water may comprise at least 5 grain hardness, at least 10 grain hardness, or at least 20 grain hardness.

The use solution can be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides the use solution with the desired stain removal properties. The water used to dilute the concentrate to form the use composition may be referred to as dilution water or diluent and may vary from location to location. Typical dilution factors are from about 1 to about 10,000, but depend on factors including water hardness, the amount of soil to be removed, and the like. In one embodiment, the concentrate is diluted at a concentrate to water ratio of about 1:1 to about 1:10,000. In particular, the concentrate is diluted at a concentrate to water ratio of about 1:1 to about 1:1,000. If it is desired to use the solution to remove tough or heavy duty soils, it is contemplated that the concentrate may be diluted with dilution water at a weight ratio of at least 1:1 and at most 1: 8. If a light load of cleaning use solution is desired, it is contemplated that the concentrate may be diluted at a weight ratio of concentrate to dilution water of up to about 1: 256.

In some aspects of the invention, from about 1ppm to about 10,000ppm, preferably from about 10ppm to about 5000ppm, more preferably from about 10ppm to about 2000ppm, and in most preferred embodiments from about 10ppm to about 5000ppm of the detergent composition is present in the use solution.

The method of the present invention relates to cleaning substrates, such as ware in ware washing applications, with a number of beneficial results, including enhanced detergency of an optionally low phosphorus carbonate alkaline detergent composition (and/or a stable use solution) containing a stable enzyme, wherein the detergent composition is more effective in soil removal, preventing soil redeposition, and maintaining low foaming of the wash water.

In use, a cleaning composition comprising a stabilized enzyme is applied to a surface to be washed during a wash step of a wash cycle. The wash cycle may comprise at least one wash step and one rinse step, and may optionally further comprise a pre-rinse step. The wash cycle involves dissolving a cleaning composition that may include the components of the present invention, such as alkali metal carbonate alkalinity sources, proteases and stabilizers, and optionally other functional ingredients such as builders, surfactants, corrosion inhibitors, and the like. During the rinsing step, water, which is usually warm or hot, flows over the surface to be washed. The rinse water may include components such as surfactants or rinse aids. The cleaning composition is intended to be used only during the wash step of the wash cycle and not during the rinse step.

According to a further embodiment of the invention, the amount of enzyme required to clean and remove soils for a particular use application varies with the type of cleaning application and the soils encountered in such application. According to various embodiments of the invention, the amount of enzyme in the aqueous use solution is effectively equal to or less than about 0.1ppm,0.5ppm,1ppm,10ppm,100ppm, or 200 ppm. According to one embodiment, the enzyme may be used at levels as high as 200 ppm.

The actual amount of enzyme in the aqueous use solution according to the invention may vary depending on the precise requirements of the cleaning application. For example, the amount of enzyme formulated into the enzyme composition can vary. Alternatively, one skilled in the art will appreciate that the activity level of the aqueous use solution can be adjusted to a desired level by controlling the wash time, the water temperature at which the water source contacts the enzyme composition or enzyme and detergent composition to form the aqueous use solution, the selection and concentration of the detergent. According to a preferred embodiment, the stabilized aqueous use solution comprises from about 0.1ppm to 100ppm enzyme, preferably from about 0.5ppm to about 50ppm and more preferably from about 1ppm to 20ppm enzyme.

During the washing step, the cleaning composition contacts the surface and acts to clean protein and other debris and/or soils from the surface, such as ware. In addition, the stable use solution of the cleaning composition assists in preventing soil from being deposited onto the surface. Although stabilizers and enzymes (e.g., proteases) are generally discussed as part of the cleaning composition, the stabilizers and/or enzymes may optionally be added as separate components to the wash step of the wash cycle. Thus, in one embodiment, the stabilizer and/or enzyme is introduced into the wash step of the wash cycle separately from the detergent composition. In one aspect, when provided as separate components, the stabilizer and/or enzyme may be provided in liquid or solid form at relatively high stabilizer and/or enzyme levels (up to about 100%), and may be introduced manually or automatically.

Advantageously, according to the method of the invention, the stable use solution allows the enzyme to be formulated for use at elevated temperatures for a period of at least 20 minutes. In another aspect, the stable use solution allows the enzyme to be formulated for use at elevated temperatures for a period of time of at least 20 minutes to greater than or equal to about 2 hours. In one aspect, the composition is suitable for use at temperatures of at least about 150 ° F, at least about 160 ° F, at least about 170 ° F, and at least about 180 ° F for at least 20 minutes or longer. In a preferred aspect, the composition is suitable for use at a temperature of from about 65 ℃ to at least about 80 ℃ for at least about 20 minutes. The stability of the enzyme can be determined by maintaining the activity and cleaning performance of the enzyme under high temperature conditions for a period of time.

As a further benefit, the method of the present invention may be further used in any cleaning application where water persistence is desired. According to embodiments of the present invention, the use of a stable enzymatic detergent composition further provides the benefit of removing soils from water and increases the time frame in which water changes are required, such that less water is used, which results from a reduced need to change wash water (or pool water in dishwashing applications). This extended use reduces the volume of cleaning water used in cleaning applications, which reduces the energy used to heat the wash water source for various cleaning applications.

The ability of the cleaning composition to reduce residual water levels can be enhanced by contacting the ware with a rinse aid composition during the rinse step of the wash cycle. The rinse aid composition significantly reduces the amount of residual water resident on the ware cleaned with the cleaning composition. There is about 1 to about 5 mL/rinse cycle of the rinse aid composition during the rinse step (this can vary with the total volume of the rinse cycle, which varies with machine size and type).

All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein 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.

Examples

Embodiments of the present 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, can make various changes and modifications of the embodiments of the invention to adapt it to various usages and conditions. 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 modifications are intended to fall within the scope of the appended claims.

Example 1

Multi-cycle stain, film and soil removal tests. Experiments were conducted to evaluate the stability of protease-containing detergent use solutions to test the ability of the compositions to clean glass and plastic. The cleaning formulations shown in table 2 were used as control detergents. This detergent is then modified to further include an enzyme and a latent stabilizer according to embodiments of the present invention.

TABLE 2

Using the control formulation, the exemplary enzyme-containing detergent was tested for its ability to clean and/or prevent food soil redeposition onto glass and plastic ware using the solution. 6 Libbey heat resistant 10oz glasses and two plastic cups were used. Before use, glass cups are cleaned in an institutional dishwasher. A new plastic cup was used for each multi-cycle soil removal experiment.

A food soil solution was prepared using a combination of 1:1 (by volume) Campbell's cream chicken soup and Kemp's whole milk. Glass and plastic cups were soiled by rolling the glass 3 times in a 1:1 mixture of Campbell's cream chicken soup Kemp's full fat milk soil. The glass was then placed in an oven at about 160 ° F for about 8 minutes.

After filling the dishwasher with 15-17 grains of water, the heater is turned on. The wash water temperature is adjusted to about 155F-160F. The final rinse temperature is adjusted to be about 180 ° F to 185 ° F. The rinse pressure is adjusted to about 20-25 psi. The dish washing machine was filled with the use solutions of detergent composition, enzyme and potential enzyme stabilizer listed in table 3. Potential enzyme stabilizers tested included glycerol, hydrolyzed protein source (GNC Pro Performance, Amino 1000), and mashed potato chips/sprouts (Clear Value) as the soluble starch source.

TABLE 3

The contaminated glass and plastic cups were placed in a Raburn rack (see the arrangement of the following figures: P ═ plastic cups; G ═ glasses) and the rack was placed inside the dish washing machine.

		G6
								G5
	P2	G4
							P1	G3
		G2
								G1

The dishwasher is started and the automatic cycle is run. When the cycle was terminated, the top of the glass and plastic cups were wiped with a dry towel. The glass and plastic cups were removed and the soup/milk contamination procedure was repeated. At the beginning of each cycle, an appropriate amount of detergent is added to the wash tank to replenish the rinse dilution. Note that when enzymes or additives are used, the initial dose is introduced into the cell only at the beginning of the multi-cycle test. The contamination and washing steps were repeated for a total of 7 cycles.

Then, for the accumulation of proteins, staining was performed using Commassie Brilliant Blue R, followed by destaining with acetic acid/methanol aqueous solution, and fractionating the glass and plastic cups. A Commassie Brilliant Blue R dye was prepared by combining 0.05 wt% Commassie Brilliant Blue R dye with 40 wt% methanol, 10 wt% acetic acid, and about 50 wt% deionized water. The solution was mixed until all the dye was dissolved. The decolorized solution was composed of 40 wt% methanol, 10 wt% acetic acid, and 50 wt% deionized water. The quality of protein retained on glass and plastic cups after destaining was assessed visually on a scale of 1-5.

Grade 1 indicates no protein detected after destaining. Grade 2 indicates that 20% of the surface was covered with protein after destaining. Grade 3 indicates that 40% of the surface was covered with protein after destaining. Grade 4 indicates that 60% of the surface was covered with protein after destaining. Grade 5 indicates that at least 80% of the surface was coated with protein after destaining. The grades of glass and plastic cups tested for soil removal were averaged to determine an average soil removal grade. The results are shown below in tables 4-5 and FIGS. 1-2. Photographs of unstained and stained scored glass and plastic cups were analyzed to determine the score of the grading. The cell residence time refers to the amount of time the various formulations are held in the cell under heated temperature and pH conditions prior to the start of the multi-cycle test to assess the stability of the enzyme and/or use solution containing the enzyme.

TABLE 4 average grade fractions (glass)

TABLE 5 average grade fractions (Plastic cups)

Not all dwell times provide post-stain data points, as for the cell, T-40 time is the smallest data point that is functional according to embodiments of the present invention. In aspects where cleaning compositions according to the present invention are used, it is reasonable to require cleaning performance based on a residence time of up to about 2 hours.

This test illustrates the effect of the sump residence time (or incubation time) on the stability and wash efficacy of the protease used in the institutional warewashing machine, as determined by performance testing. Compare the efficacy of various additives in the wells with enzymes. Reference herein to "dwell time" refers to an incubation period of idling prior to initiating a machine test according to embodiments described herein. The residence times listed are thus additionally the total test time required for the various test cycles (e.g., about 1.5 hours for a multi-cycle test).

In particular, the results of multi-cycle cleaning using the detergent use solutions of the present invention demonstrate that the addition of enzymes enhances protein removal when formulated with sodium carbonate based formulations and there is no residence time (shown as T ═ 0 in formulation 2) between the addition of detergent to the tank and the start of the multi-cycle experiment. Protein removal by enzymes, sodium carbonate based detergents, declined rapidly if a 40 minute delay (see formulation 2, T40) occurred between detergent addition to the tank and the start of the multi-cycle test. Formulation 5 containing high molecular weight potato starch performed the same with and without a 40 minute residence time, thereby illustrating the efficacy of the enzyme stabilizer of the present invention. In contrast, the formulation containing the specific protein (formula 4) or the formulation of the low molecular weight saccharide (glycerol, formula 3) failed to maintain the performance over a period of 40 minutes. The results show that the performance of the enzyme, sodium carbonate based detergent can be maintained under institutional dishwashing conditions with the addition of high molecular weight polysaccharides such as potato starch.

Example 2

The sodium (or alkali metal) carbonate detergents containing the enzyme were further analyzed for anti-redeposition benefits to demonstrate the need to stabilize efficacy for prolonged efficacy of the enzyme.

Hot spot/beef stew soil was prepared by melting 15.5 Blue Bonnet margarine sticks in a capped container to prevent water evaporation. Using a commercial blender, the following ingredients were mixed: melted margarine; 29oz. of one pot of Hunt tomato paste; 436.4g Nestle Carnation ready-to-eat non-fat dry milk; and 2 pots 24oz. of Dinty Moore stewed beef. The contents were blended for at least 3 minutes until all chunks and lumps were broken up. A Blue dye (Commassie Brilliant Blue R) for visual inspection of protein soil on glass was prepared by combining 0.05 wt% dye with 40 wt% methanol, 10 wt% acetic acid and about 50 wt% deionized water. The solution was mixed until all the dye was dissolved. The decolorizing solution consisted of 40 wt% methanol, 10 wt% acetic acid and 50 wt% deionized water.

50 cycle tests were performed using an institutional machine with 17gpg water, using food soil. Tests were carried out with 1000ppm of the formulation in Table 6.

TABLE 6

Description of the invention	Wt％
		Alkali source	75-95
Citric acid salt	2-10
		Surface active agent	1-8
Ash mono	1-30
		Water (W)	0.1-20
Candy	1-5
		Polymer and method of making same	0.1-10
Chelating agents	0.1-5

As shown in FIG. 3, as little as 1ppm of enzyme was effective in preventing redeposition in the presence of soil in the warewash tank. The efficacy of the enzyme in the presence of up to 4000ppm of Hot spot Soil (Hot Point Soil) (HPS) is shown in fig. 3. In contrast, the absence of enzyme in the warewash tank (see control detergent) resulted in the glass showing a positive Commassie blue, which is a reflection of redeposition of protein. In the presence of enzymes, protein soils are not prevented from redepositing on the ware. In addition, the inclusion of enzymes provides the benefits of membrane prevention.

Example 3

The antifoaming benefit of the sodium carbonate (or alkali metal carbonate) detergents containing enzymes was further analyzed to demonstrate the efficacy of another aspect of the requirement to stabilize the efficacy for the long term of the enzyme.

The test method of the Glewwe procedure using milk dirt includes the following. Glewwe was rinsed with water of the type used. Add 3L of water, turn on the pump for 1 minute, and drain. Add 3L of water to the cylinder. The lid was closed, the pump was turned on, and the steam valve was opened. The water was heated to l60 ° F. The steam valve is closed. The pump was turned off and ash and Esperase 8.0L were added to the food soil (powdered milk). The pump was turned on and the lid closed and run at 8psi for 1 minute. The pump was turned off and the foam height was recorded at 0,0.5,1,1.5,2,2.5,3,4, and 5 minutes.

For the delayed start test, once the desired temperature is reached, chemicals are added to the solution. The pump was operated for 3 seconds and the solution was mixed. The solution was allowed to stand for the required time. The pump was turned on and the lid closed and run at 8psi for 1 minute. The pump was turned off and the foam height was recorded at 0,0.5,1,1.5,2,2.5,3,4, and 5 minutes.

The formulations and results are shown in table 7 below. A polymer blend with an active agent amount of 30ppm polymer was used.

As shown in fig. 4A-C, the inclusion of enzymes within alkali metal carbonates shows an overall benefit to the warewashing process by reducing foaming. The reduced foaming allows the dishwasher pump to operate efficiently. For example, in high foaming applications, the pump cavitates and loses pressure, and the cleaning efficiency decreases. Advantageously, in one aspect of the invention, the antifoam benefit of the enzyme in the detergent use solution reduces the concentration of antifoam surfactant required in the detergent composition.

Example 4

The defoaming benefits of the enzyme-containing sodium carbonate (or alkali metal carbonate) detergents were further analyzed using the method of example 3. Rice soil (instead of the milk soil of example 3) and Stainzyme 12L as a protease were evaluated. A rice slurry was prepared by adding 1 cup of cooked rice (using 5gpg of water) to a blender along with 100g of cold 5gpg of water and blending into a slurry. The slurry was mixed for 10 seconds before starting the test.

The formulations tested and the results are shown in table 8 below. The polymer blend was used at an active dose of 30 ppm. The enzyme used was 50ppm of Stainzyme 12L.

As further shown in fig. 4A-D, the inclusion of enzymes in alkali metal carbonate detergents shows the overall benefits of the warewashing process by reducing foaming. The reduced foaming allows the dishwashing machine pump to operate efficiently. For example, in high foaming applications, the pump cavitates and loses pressure, and the cleaning efficacy decreases. Advantageously, in one aspect of the invention, the antifoam benefit of the enzymes in the detergent use solution reduces the concentration of antifoam surfactant required in the detergent composition.

Example 5

Analysis of enzyme activity in the formulations (% retention) was performed to simulate washing conditions in a beaker using the chemical, temperature and pH conditions associated with warewashing applications. Enzyme activity is an indicator of protease stability in detergents and in particular in aqueous use solutions inside the tank (which are under high pH, temperature and dilution conditions). Various enzyme stabilizers of the present invention were evaluated to determine which agents significantly improved the stability of the protease.

The analysis by protease analysis was performed as follows. For this analysis, solid detergent compositions containing various enzyme stabilizers were used to generate the aqueous use solutions evaluated herein.

Enzyme activity under warewashing conditions was quantitatively followed using standard protease assays. Samples were prepared under bench-top conditions, where the detergent formulation with the stabilizer was dissolved/suspended in water and maintained at the warewash bar temperature in a stirred water bath. The addition of the enzyme was performed with the aid of a pipette and the time course was started to evaluate the enzyme stability. Aliquots were taken at each time point and snap frozen. For each series, samples with time-0 were prepared by dissolving the detergent formulation, stabilizer and enzyme at room temperature, thoroughly mixing, and snap freezing. The samples were thawed and diluted in assay buffer as needed for use in the protease assay. This assay monitors the direct reaction of the protease on a small commercially available peptidyl substrate and releases the product, providing a correlation of the active enzyme content. The product was tested using a plate reader (plate reader) with a detectable dynamic range (upper absorbance limit of the instrument > 3.5). The average of the replicate experiments used to plot protease stability under the use conditions of the ware wash was used to assess the level of enzyme activity relative to the calibration curve. The enzyme retention at each time point was calculated as% enzyme activity of the sample relative to time-0.

TABLE 9

As shown in table 9, the enzyme stabilizers evaluated improved enzyme stability for use under high alkalinity and high temperature conditions. In many cases, the stabilizer results in at least about 30% enzyme retention, at least about 35% enzyme retention, at least about 40% enzyme retention, at least about 45% enzyme retention, at least about 50% enzyme retention, at least about 55% enzyme retention, at least about 60% enzyme retention, at least about 65% enzyme retention, at least about 70% enzyme retention, or at least about 75% enzyme retention for 20 minutes under conditions of high alkalinity and high temperature.

Also as shown in table 9, the Amino 1000 stabilizer was evaluated at the extended 4 hour point due to the additional benefits observed in this evaluation. However, the 2 hour result with efficacy (retained enzyme) as shown in the other amine and starch/sugar stabilizers provides sufficient warewashing application efficacy. According to the measurements of the present invention, at least 70% enzyme retention provides enzyme retention for warewashing application efficacy at a particular use condition (length of time under temperature and pH conditions).

The beneficial use stability of the detergent compositions of the present invention using enzymes and enzyme stabilizers provides sufficient stability of the composition to achieve detergency and other benefits of the present invention. Advantageously, the stable use compositions of the present invention provide dramatically enhanced enzyme stability, even at long residence times in the sump and in use in the machine during the wash cycle.

Example 6

Various enzyme stabilizers were further tested for soil removal using a multi-cycle spot, membrane and soil removal assay. The solid composition is used to form an aqueous use solution. To test the ability of the compositions to clean glass and plastic, 6 10oz. libbey heat resistant glasses and two Newport plastic cups were used. The glass is cleaned prior to use. For each multi-cycle experiment, a new plastic cup was used. A food soil solution was prepared according to the method set forth in example 1. The glass and plastic cups were stained 3 times by rolling the glass in a 1:1 mixture of Campbell's cream chicken soup Kemp's whole milk stain. The glass was then placed in an oven at about 160 ° F for about 8 minutes.

After filling the dishwasher with 5 grain water, the heater was turned on. The wash water temperature is adjusted to about 155F-160F. The final rinse temperature is adjusted to be about 180 ° F to 185 ° F. The rinse pressure is adjusted to about 20-25 psi. The dishwasher is filled with a detergent composition, an enzyme and/or a use solution of a potential enzyme stabilizer.

The contaminated glass and plastic cups were placed in a Raburn holder (as described in the method of example 1). The dishwasher is started and the automatic cycle is operated. When the cycle was terminated, the glass and plastic cup tops were wiped with a dry towel. The glass and plastic cups were removed and the soup/milk staining procedure was repeated. At the beginning of each cycle, an appropriate amount of detergent was added to the wash tank to replenish the rinse dilution. Note that when enzymes or additives are used, the initial dose is introduced into the cell only at the beginning of the multi-cycle test. The contamination and washing steps were repeated for a total of 7 cycles.

Then, for the accumulation of proteins, staining was performed using Commassie Brilliant Blue R, followed by destaining with acetic acid/methanol aqueous solution, and fractionating the glass and plastic cups. A Commassie Brilliant Blue R dye was prepared by combining 0.05 wt% dye with 40 wt% methanol, 10 wt% acetic acid, and about 50 wt% deionized water. The decolorizing solution consisted of 40 wt% methanol, 10 wt% acetic acid and 50 wt% deionized water. The amount of protein retained on the glass and plastic cups after destaining was assessed visually on a scale of 1-5.

Grade 1 indicates no protein detected after destaining. Grade 2 indicates that 20% of the surface was covered with protein after destaining. Grade 3 indicates that 40% of the surface was covered with protein after decolourisation. Grade 4 indicates that 60% of the surface was covered with protein after destaining. Grade 5 indicates that at least 80% of the surface was coated with protein after destaining.

The grades of the glass cups tested for soil removal were averaged to determine an average soil removal grade from the glass surface, and the grades of the plastic cups tested for soil removal were averaged to determine an average soil removal grade from the plastic surface. The results are shown in table 10, where the residual enzyme activity was determined based on a normalization of t ═ 0 (i.e., 100% enzyme activity).

Watch 10

Stabilizer	t-40 glass grade	t-40 plastic grade	Residual enzyme activity
				2000ppm Potato sprouts	2.0	1.9	82％
1000ppm Potato sprout	3.7	3.0	87％
				100ppm potato sprout	2.5	2.3	66％
500ppm gelatin	1.1	1.5	81％
				100ppm gelatin	2.1	1.9	78％
10ppm gelatin	n/a	n/a	48％
				500ppm Casein	1.5	1.8	91％
100ppm Casein	1.9	1.8	77％
				10ppm Casein	n/a	n/a	51％
2000ppm Amino 1000	1.6	1.5	91％
				500ppm Amino 1000	n/a	n/a	78％
100ppm Amino 1000	2.6	2.8	72％
				Is free of	5.0	5.0	15％

The results of the multi-cycle warewasher test with time delay in the presence of protein/starch based stabilizers correlated with the results of the beaker-simulation in terms of residual enzyme activity. There are limitations in associating the two methods. The warewashing results indicate the rating of glass and plastic after completion of the test with time delay (about 2 hours); while the results of the beaker-simulation show residual enzyme activity at 40 minutes (start of the multi-cycle test with time delay). The beaker-simulated results show activity at the liquid/liquid interface, while the warewasher results show enzyme activity at the solid/liquid interface (solids include insoluble soil and general ware). Despite these limitations, the same trend was observed in terms of residual enzyme activity with and without the presence of the stabilizer.

Warewasher tests revealed the extent of soil removal on the ware surface in systems that are not fully solubilized due to the presence of food soil particulates, and the systems inherently involve a solid-solution interface for the enzyme to interact with the soil on the ware surface. The results demonstrate the increased enzyme activity retention using the stabilized enzyme compositions of the invention, shown by high protein removal efficacy in the warewasher test and by enzyme analysis of residual enzyme activity of substantially more than 30% at 40 minutes.

The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims.