Detergent composition and method of cleaning surface

Abstract

The present disclosure relates to a detergent composition and a method of cleaning a surface, in particular to a detergent composition effective to remove dirt, in particular starch dirt. The compositions described herein are useful for removing dirt from surfaces including hard and soft surfaces, most preferably on vessels. Preferably, the detergent composition comprises a detergent, a bleaching agent, and an enzyme. Also described herein are methods of making and using detergent compositions for starch removal.

Description

[0001] This application is a divisional application of the invention patent application with application number 202180011141.1, application date January 29, 2021, and invention name "Synergistic effect of amylase and oxygen bleach in warewashing applications".

[0002] Cross-references

[0003] This application is related to and claims priority under 35 U.S.C. §119 to U.S. Provisional Application Serial No. 62 / 968,225, filed on January 31, 2020 and entitled “AMYLASE SYNERGY WITH OXYGEN BLEACH IN WAREWASH APPLICATION”; the entire contents of which are hereby expressly incorporated herein by reference. Technical Field

[0004] The present disclosure relates to detergent compositions that are effective in removing soils, particularly starchy soils. The detergent compositions comprise an amylase and an oxygen source. Also provided herein are methods of making and using the detergent compositions. Background Art

[0005] Effective cleaning is a critical component of many industries; if not done properly, it can have serious consequences. Cleaning involves removing dirt and residue from surfaces, leaving them visually clean. Disinfection, the removal of microorganisms, can be performed after cleaning. However, for disinfection to be effective, a thorough cleaning must have taken place first. Typically, cleaning regimens involve rinsing away debris, cleaning with a detergent, and rinsing again. The detergent used to remove dirt usually depends on the type of dirt present and the type of surface.

[0006] Typical surfaces that need to be soiled include food processing surfaces, hard surfaces including warewashing surfaces, and laundry / textile surfaces. The most common soils include proteins such as meat, eggs, milk, keratin, etc.; carbohydrates such as sugar, cellulose, and starch; oils such as animal fats, vegetable oils, sebum, mineral oils, and greases; other food soils; urea and minerals such as compounds containing calcium and magnesium, to name a few. Removing starch is particularly challenging. Starch-based soils accumulate on surfaces and become increasingly difficult to remove. For example, starchy soils may accumulate on utensils, including, for example, cutlery, plates, bowls, pots, pans, glassware, etc. Utensils can be made of ware glass, plastic, ceramic, and / or metal. Starchy soils may also accumulate on clothing surfaces, including, for example, napkins, tablecloths, uniforms, towels, sheets, etc. If starchy dirt is not successfully removed from the article during the first cleaning cycle, the starch will be more deeply embedded or firmly adhered to the surface of the article, thereby increasing the difficulty of removal. The adhered and embedded starchy dirt is also more likely to attract additional dirt, causing it to accumulate over time. This adhered and embedded accumulated dirt cannot usually be removed by conventional detergent compositions and methods. These dirts must then be removed by thorough hand washing and / or higher concentrations or amounts of cleaning compositions. Hand washing is time-consuming, and using a larger amount of detergent compositions over time can corrode the surface, which results in the need to replace the article more frequently. Both of these make costs higher and efficiency reduced.

[0007] Conventional detergents are typically phosphate-based, highly alkaline compositions containing chlorine bleach. However, high alkalinity and chlorine bleach have proven to be too aggressive and hazardous for ordinary use. As a result, there is a growing interest in replacing these compositions with detergents that can be used under less alkaline and milder (chlorine-free) bleaching conditions.

[0008] For example, U.S. Patent No. 8,092,613 attempts to remove starch-based soils using several compositions in several steps. U.S. Patent No. 8,092,613 involves treating with a first alkaline detergent composition, a second acidic composition, and additionally treating with an alkaline detergent composition. These compositions are applied separately and, in some cases, stored separately. Using multiple compositions increases costs and reduces efficiency.

[0009] U.S. Patent No. 9,969,958 teaches a detergent composition for removing soils by using a bleach catalyst and a mild alkaline detergent raw material such as sodium carbonate, rather than using harsher caustic raw materials. However, U.S. Patent No. 9,969,958 does not consider or fully appreciate the interaction between enzymes and bleach compositions.

[0010] U.S. Patent No. 2018 / 0044613 focuses on the removal of protein soils, which is different from the removal of starch soils. Therefore, U.S. Patent Publication No. 2018 / 0044613 relies on the interaction between MGDA, GLDA and alkali metal tripolyphosphate to improve soil removal. U.S. Patent No. 2018 / 0044613 does not fully appreciate the interaction between bleach components and enzymes to significantly enhance the removal of starch soils.

[0011] U.S. Patent Publication No. 2018 / 0216041 combines bleach catalysts with MGDA, GLDA and alkali metal tripolyphosphates for improved soil removal. However, like U.S. Patent No. 2018 / 0044613, U.S. Patent No. 2018 / 0216041 only provides a brief discussion of enzymes because they are optional. U.S. Patent No. 2018 / 0216041 also fails to teach insights into the interaction between bleach components and enzymes to significantly enhance starch soil removal.

[0012] In summary, existing compositions cannot successfully combine enzymes with detergent compositions containing active bleach components (such as oxygen sources and bleach activators). This is because many compositions using bleach components, whether chlorine bleach or milder percarbonate bleach, are incompatible with enzymes. Usually when enzymes are combined into detergent compositions containing bleach components, the enzymes are completely inactivated, resulting in no improvement in stain removal, or to some extent minimizing the improvement in stain removal. The improvement in stain removal efficacy is very small or no improvement and it is usually not reasonable to add enzymes to the composition because the cost of the enzyme itself and the cost of other stain removal components that still need to be used in large quantities (or high concentrations) exceed the benefits provided by the enzyme. In the past, enzyme stability issues further reduced the benefits of using enzymes: without an enzyme stabilization system (which would increase the overall cost of the composition), many enzymes would degrade over time, or could not be easily incorporated into a solid block composition that is stable in size.

[0013] Therefore, there is a need to develop detergent compositions that utilize mild alkaline detergent materials but are still effective in removing stubborn soils such as starch soils.

[0014] There is also a need to develop detergent compositions which combine bleaching agent components, such as oxygen sources and bleach activators, with enzymes without causing complete or partial inactivation of the enzymes.

[0015] There is also a need to develop detergent compositions combining bleach components and enzymes which are dimensionally stable so that the compositions can be manufactured and stored in the form of solid blocks.

[0016] There is also a need to develop a mild alkaline detergent composition that can remove stubborn soils in as little as one wash cycle.

[0017] There is also a need to develop detergent compositions that can remove stubborn soils in a more cost-effective manner.

[0018] Surprisingly, it has been found that a detergent composition comprising an alkali metal carbonate as alkalinity source, a peroxygen source, an iron or manganese peroxidation catalyst and an amylase is not only stable and cost effective but also provides synergistic soil removal on tough soils such as starchy soils. Summary of the invention

[0019] Preferred embodiments relate to detergent compositions comprising a source of alkalinity, one or more surfactants, an oxygen source, a bleach activator, an amylase and one or more chelating agents. In the most preferred embodiments, additional enzymes are also included.

[0020] A preferred embodiment is directed to a method of cleaning a surface comprising mixing a detergent composition comprising an alkalinity source, one or more surfactants, an oxygen source, a bleach activator, an amylase, and one or more chelating agents with water to form a use solution; and contacting the detergent composition with a surface, wherein the surface is soiled with starch-based soils; wherein the composition can remove starch-based soils. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Shown is a comparison of soil removal demonstrated by a base detergent composition, a detergent + bleach composition, a detergent + enzyme composition, and a detergent + bleach + enzyme composition.

[0022] Figure 2 Shown with Figure 1 The same comparison, i.e., comparing the soil removal demonstrated by the base detergent composition, the detergent + bleach composition, the detergent + enzyme composition, and the detergent + bleach + enzyme composition, except that Figure 2 Different amylase species were used.

[0023] Figure 3 Various detergent compositions were evaluated for compatibility with amylases as demonstrated by stain removal efficacy.

[0024] Various embodiments of the composition will be described in detail with reference to the accompanying drawings. The reference to various embodiments does not limit the scope of the invention. The drawings shown herein do not limit the various embodiments according to the invention, but are presented for exemplary illustration of the invention. DETAILED DESCRIPTION

[0025] The compositions described herein relate to detergent compositions using alkali metal carbonate as a source of alkalinity, a peroxygen source, an iron or manganese peroxidation catalyst, and an amylase. The detergent compositions have many advantages over conventional alkali metal carbonate and / or alkali metal hydroxide detergents and conventional detergents containing enzymes. For example, the detergent compositions described herein are stable and cost-effective while providing significantly improved stain removal efficacy.

[0026] Embodiments described herein are not limited to specific enzyme-containing alkaline detergent compositions, which can vary and be understood by those skilled in the art. It should be further understood that all terms used herein are only used for the purpose of describing specific embodiments, and are not intended to be limited in any way or scope. For example, as used in this specification and the appended claims, unless the content clearly indicates otherwise, the singular "a (a)", "an (an)" and "described" may include plural indicators. It should also be noted that, unless the content clearly indicates otherwise, the term "or" is generally used to include the meaning of "and / or". In addition, all units, prefixes and symbols can be expressed in the form accepted by its SI.

[0027] Numerical ranges listed in the specification include the numbers defining the ranges, and include each integer within the defined ranges. Throughout this disclosure, various aspects of the present invention are presented in range format. It should be understood that the description using range format is only for convenience and clarity, and should not be construed as a rigid limitation on the scope of the present invention. Therefore, the description of the range should be considered to have clearly disclosed all possible sub-ranges, fractions, and individual numerical values ​​within the range. For example, it should be considered that the description of a range such as 1 to 6 has clearly disclosed sub-ranges, such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and individual numbers within the range, for example, 1, 2, 3, 4, 5, and 6, as well as decimals and fractions, such as 1.2, 3.8, 11 / 2, and 43 / 4. This is applicable regardless of the width of the range.

[0028] For the sake of clarity, some terms are first defined. Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as generally understood in the art. Many methods and materials similar to, modified or equivalent to the methods and materials described herein can be used in the practice of the embodiments described herein without undue experimentation, and preferred materials and methods are described herein. When describing and claiming the embodiments described herein, the following terms will be used according to the definitions given below.

[0029] As used herein, the terms "weight percent", "wt. %", "percent by weight", "% by weight" and variations thereof refer to the concentration of the substance by the weight of the substance divided by the total weight of the composition and multiplied by 100. It should be understood that as used herein, "percent", "%", etc. are intended to be synonymous with "weight percent", "wt. %", etc.

[0030] As used herein, the term "about" refers to a variation in a value that may occur, for example, with respect to any quantifiable variable, including, but not limited to, concentration, mass, volume, time, temperature, pH, reflectivity, etc., by typical measurement techniques and equipment. In addition, given the solid and liquid handling procedures used in the real world, there are certain inadvertent errors and variations, which may be due to differences in the manufacture, source, or purity of the ingredients used to prepare the composition or implement the method, etc. The term "about" also encompasses amounts that differ due to different equilibrium conditions for the composition formed from a particular initial mixture. The term "about" also encompasses these variations. Whether or not modified by the term "about", the claims include equivalent values ​​of this quantity.

[0031] As used herein, the term "cleaning" means performing or assisting in any soil removal, bleaching, microbial population reduction, or combinations thereof.

[0032] The term "substantially similar cleaning performance" generally refers to being achieved by an alternative cleaning product or alternative cleaning system having substantially the same degree of cleaning (or at least not significantly less) or substantially the same air consumption (or at least not significantly less) or both.

[0033] As used herein, the phrase "food processing surfaces" refers to surfaces of tools, machines, equipment, structures, buildings, etc., used as part of food or beverage processing, preparation, or storage activities. Food processing surfaces are intended to cover all surfaces used in brewing (including beer brewing and preparation of white and hard liquor) and winemaking processes (e.g., bright beer tanks and production lines, fermentation vessels, mash tuns, bottling equipment, pipes, and storage vessels). Examples of food processing surfaces include food processing vessels (e.g., utensils, tableware, washing utensils, and bar cups), food processing or preparation equipment (e.g., boiling, fermenting, slicing, canning, or conveying equipment, including chutes), and surfaces of floors, walls, or fixtures of structures where food processing is performed. Food processing surfaces are found and used in food preservation air circulation systems, aseptic packaging sanitization, food refrigerator and cooler cleaners and sanitizers, warewashing sanitizers, blancher cleaning and sanitizing, food packaging materials, cutting board additives, third sink sanitizers, beverage coolers and warmers, meat cooling or scalding water, automatic dish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial clothing sprays, and non-aqueous to low-aqueous food preparation lubricants, oils and rinse additives.

[0034] As used herein, the phrase "food" includes any food that may need to be treated with an antimicrobial agent or composition and can be eaten with or without further preparation. Food includes meat (e.g., red meat and pork), seafood, poultry, agricultural products (e.g., fruits and vegetables), eggs, live eggs, egg products, ready-to-eat foods, wheat, seeds, roots, tubers, leaves, stems, corn, flowers, sprouts, seasonings, or combinations thereof. The term "agricultural products" refers to foods such as fruits and vegetables and plants or plant-derived materials that are usually sold in an uncooked and usually unpackaged manner and can sometimes be eaten raw.

[0035] As used herein, the phrase "health care surface" refers to a surface of an instrument, device, cart, cover, furniture, structure, building, etc., used as part of a health care activity. Examples of health care surfaces include medical or dental instruments, medical or dental devices, electronic devices used to monitor patient health, and surfaces of floors, walls, or structural fixtures in which health care is performed. Health care surfaces are found in hospitals, operating rooms, wards, delivery rooms, morgues, and clinical diagnostic rooms.

[0036] The term "hard surface" refers to any surface that is or has a hard and generally non-porous or microporous component, such as a wall, floor, counter, table, chair, bed tray, diagnostic instrument, tray, pan, holder, bracket, forceps, scissors, shears, saws (e.g., bone saws and their blades), hemostats, knives, chisels, rongeurs, files, pliers, drills, drill bits, rasps, burrs, spreaders, crushers, elevators, clamps, needle holders, shelves, clamps, hooks, chisels, curettes, retractors, levelers , punches, extractors, spoons, keratomes, scrapers, presses, trocars, dilators, covers, glassware, tubes, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthroscopes) and related equipment, utensils such as ovens, toasters, microwave ovens, shelves, food storage containers, drying racks, pans, pots, blenders, mixers, chef / food preparation knives, bowls, whisks, bakeware, cutlery (knife, fork, spoon, etc.), plates, tongs, glasses, mugs, mason jars, etc., or a combination thereof.

[0037] As used herein, the term "ware" refers to items such as eating and cooking utensils, dishes, such as ovens, toasters, microwave ovens, racks, food storage containers, drying racks, pans, pots, blenders, mixers, chef / food preparation knives, bowls, whisks, baking sheets, cutlery (knife, fork, spoon, etc.), plates, tongs, glasses, cups, glass bottles, and other hard surfaces, such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors, etc. As used herein, the term "warewashing" refers to washing, cleaning, or rinsing utensils. Utensils may include materials composed of metal, ceramics, porcelain, and glass; "ware" also refers to items made of plastic. The types of plastics that can be cleaned with the detergent compositions described herein include, but are not limited to, those comprising polycarbonate polymers (PC), acrylonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers (PS). Another exemplary plastic that can be cleaned with a detergent composition includes polyethylene terephthalate (PET).

[0038] The term "soft surface" refers to any surface that is not a hard surface, and generally includes fabric surfaces, which refers to any knitted, woven and non-woven surface (such as surgical gowns, drapes, sheets, bandages, etc.), or patient care equipment (such as ventilators, diagnostic equipment, shunts, body mirrors, wheelchairs, beds, etc.) or clothing surfaces.

[0039] As described herein, the term "clothing" refers to articles or products washed in a washing machine. In general, clothing refers to any article or product made of or including textile materials, woven fabrics, nonwoven fabrics and knitted fabrics. Textile materials can include natural or synthetic fibers, such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers (such as nylon), acrylic fibers, acetate fibers and blends thereof, including cotton and polyester blends. The fiber can be treated or untreated. Exemplary treated fibers include those fibers treated for flame retardancy. It should be understood that the term "flax" is generally used to describe certain types of clothing items including sheets, pillowcases, towels, linen tablecloths, tablecloths, bar mops and uniforms.

[0040] As used herein, the terms "free of", "not", "substantially free of" or "substantially free of" refer to compositions, mixtures or ingredients that do not contain a particular compound or have not yet added a particular compound or a compound containing a particular compound. In some embodiments, the reduction and / or elimination of hydrogen peroxide according to the embodiments provides a composition that does not contain hydrogen peroxide or is substantially free of hydrogen peroxide. If a particular compound is present by contamination and / or use of a minimal amount of a composition, mixture or ingredient, the amount of the compound should be less than about 3 wt-%. More preferably, the amount of the compound is less than 2 wt-%, less than 1 wt-%, and most preferably, the amount of the compound is less than 0.5 wt-%.

[0041] The methods and compositions described herein may include, consist essentially of, or consist of the components and ingredients listed in the exemplary embodiments, as well as other ingredients described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or ingredients, but only if the additional steps, components, or ingredients do not materially alter the basic and novel features of the claimed methods and compositions.

[0042] Composition

[0043] According to the embodiment, the composition preferably includes an alkalinity source, a peroxygen source, an iron or manganese peroxidation catalyst and an amylase, as well as additional chelating agents, water conditioners, surfactants, corrosion inhibitors and desired additional functional ingredients. In the most preferred embodiment, the composition includes additional enzymes.

[0044] Suitable formulations are further described in Tables 1 and 2:

[0045] Table 1

[0046]

[0047] Table 2

[0048]

[0049] Alkalinity Source

[0050] According to an embodiment, the detergent composition comprises one or more sources of alkalinity. Exemplary sources of alkalinity include alkali metal carbonates and / or alkali metal hydroxides. In a preferred embodiment, the composition includes dense ash or light ash. In a further preferred embodiment, the source of alkalinity includes sodium carbonate.

[0051] The alkali metal carbonates used in detergent formulations are generally referred to as ash-based detergents, and sodium carbonate is most often used. Additional alkali metal carbonates include, for example, sodium carbonate or potassium carbonate. On the one hand, alkali metal carbonates are further understood to include metasilicates, silicates, bicarbonates and sesquicarbonates. As described herein, any "ash-based" or "alkali metal carbonate" is also understood to include all alkali metal carbonates, metasilicates, silicates, bicarbonates and / or sesquicarbonates.

[0052] Alkali metal hydroxides used in detergent formulations are often referred to as caustic detergents. Examples of suitable alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Exemplary alkali metal salts include sodium carbonate, potassium carbonate, and mixtures thereof. The alkali metal hydroxide can be added to the composition in any form known in the art, including in the form of solid beads, dissolved in an aqueous solution, or a combination thereof. The alkali metal hydroxide is a solid in the form of granular solids or beads of a mixture having a particle size in the range of about 12-100 mesh (U.S.), or in the form of an aqueous solution, such as a 45% and 50% solution by weight.

[0053] In some embodiments, the composition includes between about 10 wt.% and about 80 wt.% of the first alkalinity source, preferably between about 20 wt.% and about 60 wt.%, more preferably between about 40 wt.% and about 60 wt.%, and even more preferably between about 40 wt.% and about 50 wt.% of the first alkalinity source.

[0054] Active oxygen bleach

[0055] According to an embodiment, the detergent composition comprises one or more active oxygen bleaching agents. As used herein, the term "active oxygen bleaching agent" refers to a composition comprising at least one oxygen source (also referred to as "bleaching agent") and / or at least one bleach activator. In an embodiment, the active oxygen bleaching agent comprises an oxygen source and a bleach activator.

[0056] Oxygen source / bleach

[0057] Bleaching agents suitable for use in the compositions and methods include, but are not limited to, oxygen-based bleaches. Suitable oxygen-based bleaches are peroxygen bleaches, such as sodium perborate (tetrahydrate or monohydrate), sodium percarbonate, hydrogen peroxide, and peracids, etc. Preferably, the bleaching agent does not include non-oxygen-based bleaches, including, for example, halogen bleaches. In this regard, the composition may be free of non-oxygen-based bleaches, including, in particular, halogen bleaches.

[0058] Suitable peracids may be single species or mixtures. Suitable peracids may be selected based on the desired end use in the composition and method and based on compatibility with other components. Preferred peracids include those having carbon chain lengths of C2 to C12. Suitable peracids may include those described in U.S. Pat. No. 8,846,107, entitled "In Situ Generation of Peroxycarboxylic Acids at Alkaline pH, and Methods of Use Thereof," which is expressly incorporated herein by reference in its entirety, including, but not limited to, the drawings and chemical structures contained therein. Suitable peracids may include alkyl ester peroxycarboxylic acids, ester peroxycarboxylic acids, sulfoperoxycarboxylic acids, and the like. Suitable alkyl ester peroxycarboxylic acids and ester peroxycarboxylic acids may include those described in U.S. Pat. No. 7,816,555, entitled "Peroxycarboxylic Acid Compositions with Reduced Odor," which is hereby expressly incorporated herein by reference in its entirety, including, but not limited to, all drawings and chemical structures contained therein. Suitable sulfoperoxycarboxylic acids may include those described in U.S. Pat. No. 8,809,392, entitled "Sulfoperoxycarboxylic Acids, Their Preparation and Methods of Use as Bleaching and Antimicrobial Agents," which is expressly incorporated herein by reference in its entirety, including, but not limited to, all drawings and chemical structures contained therein.

[0059] Peroxygen bleaching agents suitable for use in the composition include, but are not limited to, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, sodium peroxide, and mixtures thereof. Preferred peroxygen bleaching compounds are selected from perborates and percarbonates selected from the group consisting of: perborates and percarbonates, including sodium perborate monohydrate, sodium percarbonate, sodium perborate tetrahydrate, and mixtures thereof. In a preferred embodiment, the oxygen source includes sodium percarbonate.

[0060] In some embodiments, the composition includes between about 1 wt.% and about 40 wt.% of an oxygen source, preferably between about 5 wt.% and about 30 wt.%, more preferably between about 10 wt.% and about 20 wt.%, and even more preferably between about 12 wt.% and about 18 wt.% of an oxygen source.

[0061] Bleach Activator

[0062] According to an embodiment, the detergent composition comprises one or more bleach activators. Suitable bleach activators include, but are not limited to, peroxy catalysts, bleach activators such as tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzene sulfonate (SNOBS), glucose pentaacetate (GPA), tetraacetylmethyldiamine (TAMD), triacetylcyanurate, sulfonylethyl sodium carbonate ester, acetylhydroxybenzene sodium and single long chain acyl tetraacetyl glucose, and other activators such as choline sulfonylbenzene carbonate (CSPC) disclosed in U.S. Patent No. 4,751,015 and U.S. Patent No. 4,818,426 can also be used. Suitable peroxygen bleach precursors include, but are not limited to, sodium pbenzoyloxy-benzene sulfonate, N,N,N,N-tetraacetylethylenediamine (TEAD), sodium nonanoyloxybenzene sulfonate (SNOBS) and choline sulfonylbenzene sulfonate (CSPC).

[0063] In an embodiment, the composition includes a peroxidation catalyst which is a Mn or Fe catalyst. Mn and Fe peroxidation catalysts, wherein the metal in the form of a complex advantageously increases the activity and stability of the complex. In particular, in the case of Mn complexes, various ligands can help increase the solubility of the metal. Therefore, in a preferred embodiment, the composition includes a Mn or Fe catalyst having a ligand according to formula (I):

[0064] [(L p M q ) n X r ]Y s (I)

[0065] Wherein, each L is independently an organic ligand containing at least three nitrogen atoms and / or at least two carboxyl groups coordinated with the metal M; "M" is preferably a transition metal, most preferably Mn or Fe; each "X" is independently a coordinating or bridging group of one of the following: H2O, OH - SH - HO2 - , O 2- 、O2 2- , S 2- 、F - , Cl - Br - ,I - 、NO3 - 、NO2 - 、SO4 2- 、SO3 2- PO43- 、N3 - , CN - 、NR3、NCS - , RCN, RS - , RCO2 - ,RO - or wherein R is hydrogen or a C1 to C6 alkyl group; "p" is an integer from 1 to 4; "q" is an integer from 1 to 2; "r" is an integer from 0 to 6; "Y" is a counterion; and "s" is the number of counterions.

[0066] In a further preferred embodiment, the peroxidation catalyst is a binuclear complex according to formula (II):

[0067]

[0068] Wherein, L1 and L2 can each be a separate ligand, or L1 and L2 can be combined into a single molecule. Any suitable bridging group can be used in the binuclear complex of formula (II), although the coordinating group or bridging group, i.e., group O 2- 、O2 2- 、CH3O-、CH3CO 2- , or Cl- is particularly preferred.

[0069] In an embodiment, the ligand can be a triazacyclononane, a triazacyclononane derivative, a ligand containing a Schiff base, a polypyridylamine ligand, a pentadentate nitrogen-donor ligand, a bipyridine ligand, or a macrocyclic tetraamide ligand. Examples of these types of ligands are described in Ronald Hage and Achim Lienke, Applications of Transition-Metal Catalysts to Textile and Wood-Pulp Bleaching, Angew. Chem. Int. Ed., 45 (2) 206-222 (2006), the entire contents of which are incorporated herein by reference.

[0070] In another embodiment, the ligand comprises a dicarboxylate, for example, an oxalate. In yet another embodiment, the ligand may be a compound according to formula (II) to (IV):

[0071]

[0072]

[0073] Among them, each R 1 are independently hydrogen or a C1 to C6 alkyl group. Other suitable ligands are compounds according to formula (V) to (XVIII)

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] If the metal M is Mn, ligands (V) to (X) are particularly suitable. If the metal M is Fe, ligands (XII) to (XVIII) are particularly suitable. Ligand (XI) applies to Mn and Fe to the same extent.

[0080] The choice of counterion Y depends on the complex [(L p M q ) n X r ] The counterion number s is equal to the number of counterions required to achieve charge neutrality. Preferably, the counterion number s is from 1 to 3. The type of counterion Y used for charge neutrality is not important for the activity of the complex and can be selected from, for example, the group consisting of: Cl - Br - ,I - 、NO3 - 、ClO4 - 、NCS - ,BPh4 - 、BF4 - PF6 - , R 2 -SO3 - , R 2 -SO4 - and R 2 -CO2 - , where R 2 is hydrogen or a C1 to C4 alkyl group. A particularly preferred counterion is PF6 - and ClO4 - .

[0081] In an embodiment, the peroxidation catalyst is a complex according to formula (II), wherein M is manganese and X is selected from the group consisting of: 2- 、O2 2- 、CH3O-、CH3CO 2- , or Cl-, and the ligand L is a compound according to formula (II) and / or (IV).

[0082] In a preferred embodiment, M is manganese and L is oxalate.

[0083] Additional suitable peroxidation catalysts include, but are not limited to, compounds according to formula (XIX) and (XX), and are referred to as MnTACN and MnDTNE, respectively.

[0084]

[0085]

[0086] When the peroxidation catalyst is a compound containing M, the detergent may contain from about 0.0005% to about 0.12% by weight of a metal M in the form of a peroxidation catalyst complex, preferably from about 0.001% to about 0.05% by weight. In general, the bleach activator may contain from about 0.0001 wt.% to about 10 wt.% of the detergent composition, preferably between about 0.001 wt.% to about 5 wt.%, more preferably between 0.01 wt.% to about 0.5 wt.%, and most preferably between 0.02 wt.% to about 0.03 wt.% of the detergent composition.

[0087] Enzymes

[0088] In some embodiments, the composition may include one or more enzymes to provide synergistically improved removal of starch-based soils and other soils. Although not limiting the present invention, enzymes suitable for detergent compositions may act by degrading or altering one or more types of soil residues present on crockery, thereby removing the soil or making the soil more easily removable by surfactants or other components of the cleaning composition. In a preferred embodiment, the enzyme is an amylase.

[0089] Exemplary amylases can be derived from plants, animals or microorganisms. Amylases can be derived from microorganisms, such as yeast, mold or bacteria. Exemplary amylases include amylases derived from Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus. Amylases can be purified, or components of microbial extracts, and are wild-type or variant (chemical or recombinant).

[0090] Exemplary amylases include (Netherlands) those sold under the trade name Rapidase; those sold by Novozymes under the trade name Achieve or those sold by Genenco under the trade names Purastar STL or PurastarOXAM; those sold by Deerland under the trade names L340 or PAG 510 / 220; etc. A mixture of amylases may also be used. In a preferred embodiment, the amylase is or Achieve Choice

[0091] The composition may also include enzymes other than the one or more amylases. The additional enzymes may include proteases, lipases, glucanases, cellulases, peroxidases, catalases or mixtures thereof of any suitable origin, such as plant, animal, bacterial, fungal or yeast origin.

[0092] Examples of proteolytic enzymes that can be used in the detergent composition of the present invention include (including trade names) Proteases derived from Bacillus lentus types, such as and etc.; proteases derived from Bacillus licheniformis, such as or Deterzyme PAG 510 / 220, etc.; proteases derived from Bacillus amyloliquefaciens, such as and proteases derived from alkalophilic Bacillus, such as Deterzyme APY. Exemplary commercially available proteases include those manufactured by Novo Nordisk Industries A / S (Denmark) under the trade name (For example, Exceed, )or Those sold by Gist-Brocades (Netherlands) under the trade name or Those sold by Genencor International under the trade name Those sold under the trade names PurafectOX and Properase; by Solvay Enzymes under the trade names or Those sold by Deerland under the trade name Those sold as Deterzyme APY and Deterzyme PAG 510 / 220, among others.

[0093] Exemplary cellulases can be derived from plants, animals or microorganisms, such as fungi or bacteria. Fungal cellulases include those derived from the fungi Humicola insolens, Humicola strain DSM1800 or the fungus that produces cellulase 212 belonging to the genus Aeromonas, and those extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander. The cellulases can be purified, or components of extracts, and are wild-type or variant (chemical or recombinant). Examples of cellulases include those produced by Novo under the trade name or those sold by Genencor under the trade name Cellulase; those sold by Deerland under the trade name Deerland Cellulase 4000 or Deerland Cellulase TR; etc. Mixtures of cellulases may also be used.

[0094] Exemplary lipases can be derived from plants, animals or microorganisms, such as fungi or bacteria. Exemplary lipases include those derived from Pseudomonas or Humicola, Pseudomonas such as Pseudomonas stutzeri ATCC19.154, Humicola such as Humicola lanuginosa (usually produced in Aspergillus oryzae in a recombinant manner). The lipase can be purified, or a component of an extract, and is wild type or variant (chemical or recombinant). Exemplary lipases include those sold by Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano" or "Amano-P" or by Novo under the trade name and the like. Other commercially available lipases include Amano-CES, lipases derived from Chromobacter viscosum, such as Chromobacter viscosum variant lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., USA and Disoynth; and lipases derived from Pseudomonas gladioli or Humicola lanuginosa. Preferred lipases are sold by Novo Corp. under the trade name Mixtures of lipases may also be used.

[0095] Additional suitable enzymes include cutinases, peroxidases, glucosidases, and the like. Exemplary cutinases are described in WO 88 / 09367A, which is incorporated herein by reference in its entirety. Exemplary peroxidases include horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- or bromo-peroxidases, and the like. Exemplary peroxidases are also disclosed in WO 89 / 09813A, which is incorporated herein by reference in its entirety. These additional enzymes may be derived from plants, animals, or microorganisms. The enzyme may be purified, or a component of an extract, and may be wild-type or variant (chemical or recombinant). Mixtures of different additional enzymes may be used.

[0096] Regardless of the type of enzyme used, the form of the enzyme can vary depending on the availability or form of the composition. For example, the enzyme can be provided as a liquid, solid, granular, encapsulated liquid, encapsulated solid, and / or as part of an enzyme-catalyst complex or package. For example, a granular protease can be provided with a granular manganese-based catalyst to improve performance and ease of use.

[0097] Enzymes, especially amylases, can be present in the detergent composition in an amount between about 0.0001 wt.% to about 10 wt.%, preferably between about 0.001 wt.% to about 5 wt.%, more preferably between about 0.01 wt.% to about 2 wt.%, most preferably between about 0.1 wt.% to about 1.5 wt.% of the detergent composition.

[0098] Chelating agents, sequestrants, water conditioners

[0099] The composition may include one or more water conditioning agents or building agents (e.g., builders), also known as chelating agents or sequestrants, including but not limited to condensed phosphates, alkali metal carbonates, phosphonates, aminocarboxylic acids, polycarboxylic acid polymers and / or polyacrylates. Typically, chelating agents are molecules that can coordinate (i.e., bind) metal ions commonly found in natural water to prevent the metal ions from interfering with the action of other detergency ingredients of the cleaning composition. Similarly, builders and water conditioning agents also help remove metal compounds. Exemplary water conditioning agents include anti-redeposition agents, chelating agents, sequestrants, and inhibitors.

[0100] Examples of condensed phosphates include, but are not limited to, sodium and potassium orthophosphates, sodium and potassium pyrophosphates, sodium tripolyphosphate, and sodium hexametaphosphate.Condensed phosphates may also aid in the curing of the composition to a limited extent by fixing free water present in the composition as water of hydration.

[0101] Examples of phosphonates include, but are not limited to, 2-phosphinobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-1,1-diphosphonic acid, CH2C(OH)[PO(OH)2]2; aminotri(methylenephosphonic acid), N[CH2PO(OH)2]3; aminotri(methylenephosphonate), sodium salt (ATMP), N[CH2PO(ONa)2]3; 2-hydroxyethyliminobis(methylenephosphonic acid), HOCH2CH2N[CH2PO(OH)2]2; diethylenetriaminepentyl(methylenephosphonic acid), (HO)2POCH2N[CH2N[CH2PO(OH)2]2]2; diethylenetriaminepentyl(methylenephosphonate), sodium salt (DTPMP), C9H (28-x) N3Na x O 15 P5 (x = 7); hexamethylenediamine (tetramethylenephosphonate), potassium salt, C 10 H (28-x) N2K x O 12 P4 (x = 6); bis (hexamethylene) triamine (pentamethylenephosphonic acid), (HO2)POCH2N[(CH2)2N[CH2PO(OH)2]2]2; and phosphorous acid H3PO3. Preferred phosphonates are PBTC, HEDP, ATMP and DTPMP. Preferred are neutralized or alkaline phosphonates, or a combination of a phosphonate and an alkali metal source prior to addition to the mixture such that when phosphoric acid is added, there is little or no heat or gas generated by the neutralization reaction. However, in one embodiment, the composition is phosphorus-free.

[0102] Suitable aminocarboxylic acid materials containing little or no NTA include, but are not limited to, N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic acid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS), 3-hydroxy-2-2'-iminodisuccinic acid (HIDS), and other similar acids or salts thereof having an amino group with a carboxylic acid substituent. However, in one embodiment, the composition does not contain an aminocarboxylate.

[0103] Suitable organic water conditioning agents may include polymers and small molecule water conditioning agents. Small organic molecule water conditioning agents are typically organic carboxylate compounds or organic phosphate water conditioning agents. Polymer inhibitors often include polyanionic compositions, such as polyacrylic acid compounds. Recently, sodium carboxymethylcellulose has been found to be used as an anti-redeposition agent. This is discussed more extensively in U.S. Pat. No. 8,729,006 to Miralles et al., which is incorporated herein in its entirety.

[0104] Small molecule organic water conditioners include, but are not limited to, sodium gluconate, sodium gluconate heptanoate, N-hydroxyethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid (TTHA) and their corresponding alkali metal, ammonium and substituted ammonium salts, ethylenediaminetetraacetic acid tetrasodium salt (EDTA), nitrilotriacetic acid trisodium salt (NTA), ethanol diglycinedisodium salt (EDG), diethanol glycine sodium salt (DEG) and 1,3-propylenediaminetetraacetic acid (PDTA), dicarboxymethyl glutamic acid tetrasodium salt (GLDA), methylglycine-NN-diacetic acid trisodium salt (MGDA) and iminodisuccinic acid sodium salt (IDS). All of these are known and commercially available.

[0105] Suitable inorganic water conditioning agents include, but are not limited to, sodium tripolyphosphate and other higher linear and cyclic polyphosphate species. Suitable condensed phosphates include alkali metal phosphates such as sodium and potassium orthophosphates, sodium and potassium pyrophosphates, sodium tripolyphosphate and sodium hexametaphosphate, etc. Condensed phosphates can also assist in the solidification of solid detergent compositions to a limited extent by fixing the free water present in the composition as water of hydration.

[0106] In embodiments, the composition may be substantially free of phosphorus, phosphates, and / or phosphonates.

[0107] In addition to aminocarboxylates that are almost free of or free of NTA, water-adjusting polymers can be used as phosphorus-free builders. Polycarboxylic acid polymer chelating agents are phosphorus-free chelating agents. Polycarboxylates include those chelating agent polymers with pendant carboxylate (--CO2-) groups, such as polyacrylic acid homopolymers, polymaleic acid homopolymers, maleic acid / olefin copolymers, sulfonated copolymers or terpolymers, acrylic acid / maleic acid copolymers or terpolymers, polymethacrylic acid homopolymers, polymethacrylic acid copolymers or terpolymers, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers and combinations thereof. For further discussion of chelating agents / sequestrants, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 5, pp. 339-366, and Vol. 23, pp. 319-320, the disclosures of which are incorporated herein by reference. These materials may also be used at substoichiometric levels to act as crystal modifiers.

[0108] Polycarboxylic acid polymer chelating agents can include polyacrylic acid homopolymers and polymaleic acid homopolymers, and polymers modified by fatty acid end groups. Exemplary polyacrylic acid homopolymers include molecular weights between about 500 and 100,000 g / mol, or between about 1,000 and 50,000 g / mol, or between about 1,000 and 25,000 g / mol. Exemplary commercially available polyacrylic acid polymers suitable for include Acusol 445N (fully neutralized acrylic acid homopolymer), Acusol 448 and Acusol 944 purchased from Dow Chemical. Exemplary commercially available polymaleic acid chelating agents / water conditioning agents suitable for include, for example, Belclene 200, which is commercially available from BWA.

[0109] In other embodiments, mixtures of acrylic homopolymers and / or polymers containing acrylate monomers may be employed.

[0110] In an embodiment, the one or more chelating / sequestrants / water conditioning agents comprise a phosphate and one or more aminocarboxylates. In yet another embodiment, the phosphate is sodium tripolyphosphate and the one or more aminocarboxylates are MGDA and GLDA.

[0111] In some embodiments, the detergent composition comprises one or more chelating agents, which are present in an amount between about 10 wt.% to about 70 wt.%, preferably between about 15 wt.% to about 60 wt.%, more preferably between about 25 wt.% to about 45 wt.%, and most preferably between about 35 wt.% to about 40 wt.% of the composition. In an embodiment, the one or more chelating agents / sequestrants / water conditioning agents include phosphates, aminocarboxylates, and phosphonates. In embodiments comprising phosphate and one or more aminocarboxylates, the composition comprises between about 5 wt.% to about 50 wt.% of phosphate, preferably between about 10 wt.% to about 40 wt.%, more preferably between about 15 wt.% to about 30 wt.%, most preferably between about 20 wt.% to about 25 wt.% of the detergent composition; about 0.5 wt.% to about 45 wt.% of aminocarboxylates, preferably between about 1 wt.% to about 35 wt.%, more preferably between about 5 wt.% to about 25 wt.%, most preferably between about 10 wt.% to about 15 wt.%; and about 0.01 wt.% to about 20 wt.% of secondary aminocarboxylates, preferably between 0.1 wt.% to about 15 wt.%, more preferably between about 0.5 wt.% to about 8 wt.%, most preferably between about 1 wt.% to about 3 wt.%.

[0112] Surfactants

[0113] In some embodiments, the detergent composition described herein comprises one or more surfactants. Suitable surfactants for use include but are not limited to nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants. In a preferred embodiment, the composition includes one or more nonionic surfactants. In a further preferred embodiment, one or more nonionic surfactants include nonionic polyoxyethylene-polyoxypropylene (EO / PO) block copolymers. In a further preferred embodiment, the EO / PO block copolymer is poloxamer (EO / PO / EO).

[0114] In some embodiments, the detergent composition includes one or more surfactants between about 0.01 wt.% and about 50 wt.%, including, for example, about 0.01 wt.%, 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.% of one or more nonionic, anionic, cationic, amphoteric and / or zwitterionic surfactants. In an embodiment, the detergent composition comprises one or more nonionic surfactants in an amount between about 0.01 wt.% and about 50 wt.%, preferably between about 0.5 wt.% and about 20 wt.%, more preferably between 1 wt.% and about 10 wt.%, most preferably between about 2 wt.% and 6 wt.%.

[0115] Nonionic surfactants

[0116] Suitable nonionic surfactants suitable for use include, for example, alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, blocked EO / PO copolymers, alcohol alkoxylates, blocked alcohol alkoxylates, mixtures thereof, and the like. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers, such as and inverting Surfactants; alcohol alkoxylates; capped alcohol alkoxylates; mixtures thereof, etc.

[0117] Suitable nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are generally produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic basic oxide moiety, which is generally ethylene oxide or its polyhydration product, polyethylene glycol. Virtually any hydrophobic compound having hydroxyl, carboxyl, amino or amide groups with reactive hydrogen atoms may be condensed with ethylene oxide or its polyhydration adducts or a mixture thereof with an alkylene oxide such as 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 produce a water-dispersible or water-soluble compound having a desired degree of balance between hydrophilicity and hydrophobicity.

[0118] Block polyoxypropylene-polyoxyethylene polymeric compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compounds are suitable nonionic surfactants.

[0119] Some embodiments of polyoxyethylene-polyoxypropylene block copolymers include those having the formula:

[0120] (EO)x(PO)y(EO)x

[0121] (PO)y(EO)x(PO)y

[0122] (PO) y (EO) x (PO) y (EO) x (PO) y

[0123]

[0124] Wherein, EO represents an ethylene oxide group, PO represents a propylene oxide group, and x and y represent the average molecular ratio of each alkylene oxide monomer in the entire block copolymer composition. In some embodiments, x is in the range of about 10 to about 130, y is in the range of about 15 to about 70, and x plus y is in the range of about 25 to about 200. It should be understood that each x and y in the molecule can be different. In some embodiments, the total polyoxyethylene component of the block copolymer can be in the range of at least about 20 mol-% of the block copolymer, and in some embodiments, in the range of at least about 30 mol-% of the block copolymer. In some embodiments, the molecular weight of the material can be greater than about 400, and in some embodiments, its molecular weight can be greater than about 500. For example, in some embodiments, the molecular weight of the material can be in the range of about 500 to about 7000 or more, or in the range of about 950 to about 4000 or more, or in the range of about 1000 to about 3100 or more, or in the range of about 2100 to about 6700 or more.

[0125] Although the exemplary polyoxyethylene-polyoxypropylene block copolymer structures provided above have 3-8 blocks, it is understood that the nonionic block copolymer surfactants may contain more or less than 3 or 8 blocks. In addition, the nonionic block copolymer surfactants may contain additional repeating units, such as butylene oxide repeating units. In addition, suitable nonionic block copolymer surfactants may be characterized as mixed-block polyoxyethylene-polyoxypropylene block copolymers. Examples of polymeric compounds made by sequential propoxylation and ethoxylation of initiators can be found under the trade name BASF Corp. and Commercially available, especially N-3, 25-R2 and others.

[0126] For example, suitable nonionic surfactants include, but are not limited to, those sold under the trade name Adeka Adeka Adeka Adeka Antarox Antarox Antarox and Antrarox Available Poloxamers (EO / PO / EO).

[0127] The compound is a difunctional (two reactive hydrogen) compound formed by the condensation of ethylene oxide with a hydrophobic matrix formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. The molecular weight of this hydrophobic portion of the molecule is from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10% by weight to about 80% by weight of the final molecule.

[0128] The compound is a tetrafunctional block copolymer obtained by sequentially adding propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrophobe ranges from about 500 to about 7,000; and the hydrophile ethylene oxide is added to constitute about 10% by weight to about 80% by weight of the molecule.

[0129] Semi-polar nonionic surfactant

[0130] Semi-polar type nonionic surfactants are another class of nonionic surfactants useful in the detergent compositions described herein. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and alkoxylated derivatives thereof.

[0131] Amine oxides are tertiary amine oxides corresponding to the following general formula:

[0132]

[0133] where the arrow is a conventional representation of a semipolar bond; and R 1 , R 2 and R 3 It can be an aliphatic group, an aromatic group, a heterocyclic group, an alicyclic group or a combination thereof. Generally speaking, for detergent-related amine oxides, R 1 is an alkyl group having from about 8 to about 24 carbon atoms; R 2 and R 3 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a mixture thereof; R 2 and R 3 can be attached to each other, for example, via an oxygen atom or a nitrogen atom, to form a ring structure; R 4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms; and n is in the range of 0 to about 20. The amine oxide can be generated from the corresponding amine and an oxidizing agent such as hydrogen peroxide.

[0134] Suitable semi-polar nonionic surfactants also include water-soluble phosphine oxides having the following structure:

[0135]

[0136] wherein the arrow conventionally represents a semipolar bond; and R 1 is an alkyl, alkenyl or hydroxyalkyl moiety having a chain length ranging from 10 to about 24 carbon atoms; and R 2 and R 3 Each is an alkyl moiety independently selected from an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.

[0137] Examples of suitable 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. Suitable water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut or animal fat alkyl di-(low carbon number alkyl) amine oxides, and specific examples thereof are octyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, isododecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide. 1-hydroxypropylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-tri(octadecyl)dimethylamine oxide and 3-dodecyloxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0138] Semi-polar nonionic surfactants suitable for use herein also include water-soluble sulfoxide compounds having the following structure:

[0139]

[0140] wherein arrows conventionally represent semipolar bonds; and, R 1 is an alkyl or hydroxyalkyl moiety having from about 8 to about 28 carbon atoms, 0 to about 5 ether linkages, and 0 to about 2 hydroxy substituents; and R 2The alkyl group is an alkyl moiety composed of an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group. Suitable examples of these sulfoxides include dodecylmethylsulfoxide; 3-hydroxytridecylmethylsulfoxide; 3-methoxytridecylmethylsulfoxide; and 3-hydroxy-4-dodecyloxybutylmethylsulfoxide.

[0141] Suitable semi-polar nonionic surfactants include, but are not limited to, dimethylamine oxides, such as lauryl dimethylamine oxide, myristyl dimethylamine oxide, cetyl dimethylamine oxide, combinations thereof, and the like. Alkoxylated amines or, most particularly, alcohol alkoxylated / aminated / alkoxylated surfactants are also suitable. These nonionic surfactants may be at least partially composed of the general formula: R 20 --(PO) S N--(EO) t H.R 20 --(PO) S N--(EO) t H(EO) t H and R 20 --N(EO) t H represents; where R 20 is an alkyl, alkenyl or other aliphatic group or alkyl-aryl group having 8 to 20, preferably 12 to 14 carbon atoms, EO is ethylene oxide, PO is propylene oxide, 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 in the range of these compounds can be obtained by alternative formulas: R 20 --(PO) V --N[(EO) w H][(EO) z H] indicates that R 20 As 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 represented commercially by a series of products sold by Huntsman Chemicals as nonionic surfactants.

[0142] Anionic surfactants

[0143] 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 oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C5-C 17Acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) reduced glucosamine sulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides, etc. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (usually having 1 to 6 ethylene oxide groups per molecule).

[0144] 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 which may or may not have substitution groups.

[0145] Anionic carboxylate surfactants suitable for use in the present composition include carboxylic acids (and salts) such as alkanoic acid (and alkanoate), carboxylates (e.g., alkyl succinates), carboxylic acid ethers, etc. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylates surfactants, and soaps (e.g., alkyl carboxyls). Secondary carboxylates that can be used in the composition of the present invention include those carboxylates containing carboxyl units connected to secondary carbons. Secondary carbons can be in a ring structure, for example, as in p-octylbenzoic acid, or as in alkyl-substituted cyclohexyl carboxylates. Secondary carboxylates surfactants are generally free of ether bonds, ester bonds, and hydroxyl groups. In addition, they are generally lacking nitrogen atoms in the head group (amphiphilic moiety). Suitable secondary soap surfactants generally contain a total of 11-13 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 (eg, N-acyl sarcosinates), taurates (eg, N-acyl taurates and methyltauryl fatty acid amide), and the like.

[0146] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula:

[0147] RO-(CH2CH2O) n (CH2) m -CO2X(3)

[0148] Where R is C8 to C 22 Alkyl or Among them, R 1 It is C4-C 16 alkyl; n is an integer from 1 to 20; m is an integer from 1 to 3; and X is a counter ion such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10, and m is 1. In some embodiments, R is C8-C 16 In some embodiments, R is C 12 -C14 An alkyl group, n is 4, and m is 1.

[0149] In other embodiments, R is And R 1 It is C6-C 12 In some other embodiments, R 1 is a C9 alkyl group, n is 10 and m is 1.

[0150] Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are generally available in the acid form which can be readily converted to the anionic or salt form. Commercially available carboxylates include Neodox 23-4, C 12-13 Alkyl polyethoxy (4) carboxylic acid (Shell Chemical), and Emcol CNP-110, C9 alkylaryl polyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are also available from Clariant, for example as product DTC, C 13 Alkylpolyethoxy(7)carboxylic acid.

[0151] Amphoteric surfactant

[0152] Amphoteric or amphoteric surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups. These ionic entities can be any anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In several surfactants, sulfonates, sulfates, phosphonates or phosphates provide negative charges.

[0153] Amphoteric surfactants can be generally described as derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic radical can be straight or branched and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water-soluble group, such as a carboxyl, sulfonic acid, sulfate, phosphate, or phosphono group. Amphoteric surfactants are subdivided into two main categories, which are known to those of ordinary skill in the art and described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989), which is incorporated herein by reference in its entirety. The first category includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and salts thereof. The second category includes N-alkyl amino acids and salts thereof. It is conceivable that some amphoteric surfactants conform to these two categories.

[0154] Amphoteric surfactants can be synthesized by methods known to those of ordinary skill in the art. For example, 2-alkylhydroxyethyl imidazolines are synthesized by condensation and ring closure of long-chain carboxylic acids (or derivatives) with dialkylethylenediamines. Commercial amphoteric surfactants are derivatized by sequential hydrolysis and ring opening of the imidazoline ring by alkylation, for example, using chloroacetic acid or ethyl acetate. During the alkylation, one or both carboxyl-alkyl groups react with different alkylating agents to form tertiary amines and ether linkages to produce different tertiary amines.

[0155] Suitable long chain imidazole derivatives may generally have the general formula:

[0156] (Mono)acetate (di)propionate

[0157]

[0158] Neutral pH Zwitterions

[0159] Amphoteric sulfonate

[0160]

[0161] Wherein R is a non-cyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation, generally sodium, for neutralizing the charge of an anion. Commercially famous imidazoline derived amphoteric surfactants that can be used in the present composition include, for example: cocoylamphopropionate, cocoylamphocarboxypropionate, cocoylamphoglycinate, cocoylamphocarboxyglycinate, cocoylamphopropylsulfonate, and cocoylamphocarboxypropionic acid. Amphoteric carboxylic acids can be produced by fatty imidazolines, wherein the dicarboxylic acid functional group of amphoteric dicarboxylic acids is diacetic acid and / or dipropionic acid.

[0162] The carboxymethylated compounds (glycinates) described herein above are often referred to as betaines. Betaines are a special class of amphoteric surfactants discussed below in the section entitled Zwitterionic Surfactants.

[0163] Easily passed through RNH2, where R = C8-C 18 Long-chain N-alkyl amino acids are prepared by the reaction of straight or branched alkyl groups, fatty amines and halogenated carboxylic acids. Alkylation of the primary amino groups of amino acids produces secondary and tertiary amines. The alkyl substituents may have additional amino groups that provide more than one reactive nitrogen center. Most commercial N-alkylamines are alkyl derivatives of β-alanine or β-N (2-carboxyethyl) alanine. Examples of suitable commercial N-alkyl amino acid ampholytes include, but are not limited to, β-aminodipropionate, RN (C2H4COOM) 2 and RNHC2H4COOM. In an embodiment, R may be a non-cyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation for neutralizing the charge of an anion.

[0164] Suitable amphoteric surfactants include amphoteric surfactants derived from coconut products such as coconut oil or coconut fatty acids. Other suitable coconut-derived surfactants include as part of their structure an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, such as glycine, or a combination thereof; and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants can also be considered alkyl amphoteric dicarboxylic acids. These amphoteric surfactants can include a chemical structure represented as follows: 12 -alkyl-C(O)-NH-CH2-CH2-N + (CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -alkyl-C(O)-N(H)-CH2-CH2-N + (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is a suitable amphoteric surfactant and is available under the trade name Miranol TM FBS was purchased from Rhodia Inc., Cranbury, NJ. Another suitable coconut-derived amphoteric surfactant, chemically known as disodium cocoamphodiacetate, is available under the trade name Mirataine TM JCHA is sold by Rhodia Corporation of Cranbury, N.J. A typical listing of amphoteric classes and types of these surfactants is given in U.S. Pat. No. 3,929,678, issued to Laughlin and Hecuring on Dec. 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II, by Schwartz, Perry and Berch), which is incorporated herein by reference in its entirety.

[0165] Cationic surfactants

[0166] If the charge on the hydrotrope part of the molecule is positive, the surfactant is classified as cationic. Also included in this group are surfactants in which the hydrotrope is uncharged unless the pH is reduced to near neutrality or lower, but then cationic (e.g., alkylamine). In theory, cationic surfactants can be synthesized by any combination of elements containing the "onium" structure RnX+Y--, and can include non-nitrogen (ammonium), such as compounds of phosphorus (phosphonium) and sulfur (sulfonium). In fact, nitrogen-containing compounds dominate the cationic surfactant field, which may be because the synthetic route of nitrogen-containing cationic surfactants is simple and direct, and the yield of the product obtained is high, which can make its cost lower.

[0167] Cationic surfactants preferably comprise, 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 group may be directly attached to the nitrogen atom by simple substitution; or more preferably indirectly attached to the nitrogen atom by one or more bridging functional groups in so-called interrupted alkylamines and amidoamines. Such functional groups may make the molecule more hydrophilic and / or more water dispersible, more easily soluble in water by a co-surfactant mixture, and / or soluble in water. To increase water solubility, additional primary, secondary or tertiary amino groups may be introduced, or the amino nitrogen may be quaternized using low molecular weight alkyl groups. Furthermore, the nitrogen may be part of a branched or straight chain portion of a saturated or unsaturated heterocycle with varying degrees of unsaturation. In addition, cationic surfactants may contain complex linkages with more than one cationic nitrogen atom.

[0168] Surfactant compounds classified as amine oxides, amphoteric surfactants, and zwitterionic surfactants are themselves generally cationic in near neutral to acidic pH solutions and may overlap with surfactant classifications. Polyoxyethylated cationic surfactants generally behave similarly to nonionic surfactants in alkaline solutions and similarly to cationic surfactants in acidic solutions. The simplest cationic amines, amine salts, and quaternary ammonium compounds can be schematically drawn like this:

[0169]

[0170] wherein R represents a long alkyl chain, R', R" and R"' may be long alkyl chains or smaller alkyl groups or aryl groups or hydrogen, and X represents an anion. 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 described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Vol. 104(2) 86-96 (1989), which is incorporated herein by reference in its entirety. The first class includes alkylamines and their salts. 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 a variety of 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, antimicrobial efficacy, thickening or gelling in coordination with other agents, and the like. Suitable cationic surfactants include but are not limited to those having the formula R 1 mxD 2 Those cationic surfactants of xYLZ, where each R 1is an organic group containing a straight or branched alkyl or alkenyl group, which is optionally substituted with up to three phenyl or hydroxy groups and optionally with up to four of the following structures:

[0171]

[0172] or isomers or mixtures thereof, and contain from about 8 to about 22 carbon atoms. 1 The group may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. Preferably, when m is 2, no more than one R 1 The group has 16 or more carbon atoms, or when m is 3, more than 12 carbon atoms. Each R 2 is an alkyl or hydroxyalkyl or benzyl group containing 1 to 4 carbon atoms, and there is not more than one R 2 is benzyl. x is a number from 0 to 11, preferably from 0 to 6. Any remaining carbon atom positions on the Y group are filled with hydrogen. Y can be a group including but not limited to the following:

[0173]

[0174] or mixtures thereof. Preferably, L is 1 or 2, wherein when L is 2, the Y group is selected from R having 1 to about 22 carbon atoms and two free carbon single bonds. 1 and R 2 Z is a water-soluble anion, such as a halide, sulfate, methyl sulfate, hydroxide or nitrate anion, particularly preferably a chloride, bromide, iodide, sulfate or methyl sulfate anion, in an amount that is electrically neutral with the cationic component.

[0175] Zwitterionic surfactants

[0176] Zwitterionic surfactants can be considered a subgroup of amphoteric surfactants and can include anionic charges. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Zwitterionic surfactants generally contain a positively charged quaternary ammonium ion, or in some cases, a sulfonium or phosphonium ion; a negatively charged carboxyl group; and an alkyl group. Zwitterionic surfactants generally contain cationic and anionic groups, which are ionized to almost the same extent in the isoelectric region of the molecule and which can generate strong "inner salt" attractions between the positive-negative charge centers. Embodiments of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, wherein the aliphatic group can be linear or branched, and wherein one of the aliphatic substituents contains 8 to 18 carbon atoms, and one of the aliphatic substituents contains an anionic water-soluble group, such as a carboxyl, sulfonate, sulfate, phosphate or phosphonate.

[0177] Betaine surfactants and sultaine surfactants are exemplary zwitterionic surfactants for use herein. The general formula of these compounds is:

[0178]

[0179] Where R 1 An alkyl, alkenyl or hydroxyalkyl group containing 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moieties; Y is selected from the group consisting of a nitrogen atom, a phosphorus atom and a sulfur atom; R 2 is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and x is 2 when Y is a nitrogen or phosphorus atom, R 3 is an alkylene or hydroxyalkylene or hydroxyalkylene group of 1 to 4 carbon atoms and Z is a group selected from the group consisting of a carboxylate, a sulfonate, a sulfate, a phosphonate and a phosphate group.

[0180] Examples of zwitterionic surfactants having the structures listed above include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonium]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecyldihydrosulfanyl]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxa-tetracosylphospho]-2-hydroxypropane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; The detergent surfactants include 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate; 3-[S-ethyl-S-(3-dodecyloxy-2-hydroxypropyl)dihydrosulfide]-propane-1-phosphate; 3-[P,P-dimethyl-P-dodecylphosphino]-propane-1-phosphonate; and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in the detergent surfactants may be straight or branched and may be saturated or unsaturated.

[0181] Suitable zwitterionic surfactants for use in the present composition include betaines having the following general structure:

[0182]

[0183] These surfactant betaines generally exhibit neither strong cationic or anionic properties at pH extremes nor reduced water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic surfactants. Examples of suitable betaines include cocoamidopropyl dimethyl betaine; hexadecyl dimethyl betaine; C 12-14 Acylamidopropyl betaine; C 8-14 Acylamidohexyl diethyl betaine; 4-C 14-16 Acylmethylamidodiethylammonium-1-carboxybutane; C 16-18 Acylamidodimethylbetaine; C 12-16 Acylamidopentane diethyl betaine; and C 12-16 Acylmethylamidodimethylbetaine.

[0184] Suitable sulfobetaines may include, but are not limited to, sulfobetaines having the formula (R(R 1 )2N + R 2 SO 3- Those compounds wherein R is C6-C 18 Hydrocarbon, each R 1are usually independently C1-C3 alkyl, for example, methyl, and R 2 It is a C1-C6 hydrocarbon group, such as a C1-C3 alkylene group or a hydroxyalkylene group.

[0185] A typical list of zwitterionic classes and species of these surfactants is given in U.S. Pat. No. 3,929,678, the entire contents of which are incorporated herein by reference. Additional examples are given in "Surfactants and Detergents" (Vol. I and II, Schwartz, Perry and Berch), the entire contents of which are incorporated herein by reference.

[0186] Corrosion Inhibitors / Etch Protectants

[0187] In some embodiments, the detergent compositions described herein may optionally include one or more etch protectants for preventing surface corrosion and / or one or more corrosion inhibitors for treating calcium carbonate-based scale or other types of mineral scale, including calcium sulfate, calcium phosphate, barium sulfate, strontium sulfate, iron hydroxide, silica dioxide (silica), calcium oxalate, and others. Examples of suitable corrosion inhibitors / etch protectants include, but are not limited to, combinations of aluminum ion sources and zinc ion sources, and alkali metal silicates or hydrates thereof.

[0188] Corrosion inhibitor / etching protectant can refer to the combination of aluminum ion source and zinc ion source. When the solid detergent composition is provided in the form of a use solution, the aluminum ion source and the zinc ion source provide aluminum ions and zinc ions, respectively. The amount of the corrosion inhibitor / etching protectant is calculated based on the combined amount of the aluminum ion source and the zinc ion source. Any substance that provides aluminum ions in the use solution can be called an aluminum ion source, and any substance that provides zinc ions when provided in the use solution can be called a zinc ion source. The aluminum ion source and / or the zinc ion source do not have to react to form aluminum ions and / or zinc ions. Aluminum ions can be regarded as aluminum ion sources, and zinc ions can be regarded as zinc ion sources. Aluminum ion sources and zinc ion sources can be provided as organic salts, inorganic salts and mixtures thereof.

[0189] Exemplary sources of aluminum ions include, but are not limited to, aluminum salts such as sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate, potassium aluminum sulfate, and aluminum zinc sulfate. Exemplary sources of zinc ions include, but are not limited to, zinc salts such as zinc chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc fluorosilicate, zinc dichromate, zinc chlorate, sodium zincate, zinc gluconate, zinc acetate, zinc benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc bromide, zinc fluoride, zinc fluorosilicate, and zinc salicylate.

[0190] In some embodiments, the detergent composition contains one or more corrosion inhibitors, which are present in an amount between about 0.001 wt.% and about 10 wt.%, preferably between about 0.001 wt.% and about 5 wt.%, more preferably between about 0.01 wt.% and about 1 wt.%, and most preferably between 0.01 wt.% and about 0.04 wt.%.

[0191] Antimicrobial Agents

[0192] The detergent composition may optionally further comprise one or more antimicrobial agents. Any suitable antimicrobial agent or combination of antimicrobial agents may be used, including but not limited to bleaching agents such as sodium hypochlorite; hydrogen peroxide; peracids such as peracetic acid, performic acid, peroctanoic acid, sulfoperoxyacids, and any peracid produced by a carboxylic acid and an oxidizing agent; and / or quaternary ammonium acid.

[0193] Some examples of classes of compounds that can serve as chlorine sources for antimicrobial agents include hypochlorites, chlorinated phosphates, chlorinated isocyanurates, chlorinated melamines, chlorinated amides, and the like, or mixtures of combinations thereof.

[0194] Some specific examples of the chlorine source may include sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, lithium hypochlorite, chlorinated trisodium phosphate, sodium dichloroisocyanurate, potassium dichloroisocyanurate, pentaisocyanurate, trichloromelamine, sulfonyl dichloroamide, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosuccinimide, N,N'-dichloroazodicarbonimide, N,N'-chloroacetyl urea, N,N'-dichlorobiurea, trichloroisocyanuric acid and hydrates thereof, or combinations or mixtures thereof.

[0195] In some embodiments, the composition is free of chlorine.

[0196] Any suitable peracid or peroxycarboxylic acid may be used as an antimicrobial agent. Peracids include those of the formula R--(COOOH) n Any compound of , wherein R can be hydrogen, alkyl, alkenyl, alkynyl, acyl, alicyclic group, aryl, heteroaryl or heterocyclic group, and n is 1, 2 or 3, and is named by adding a peroxy prefix before the parent acid. Preferably, R includes hydrogen, alkyl or alkenyl. The terms "alkyl", "alkenyl", "alkyne", "acyl", "alicyclic group", "aryl", "heteroaryl" and "heterocyclic group" are as defined herein.

[0197] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, including straight-chain alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl (or "cycloalkyl" or "alicyclic" or "carbocyclyl") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched alkyl (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.) and alkyl substituted (e.g., alkyl substituted cycloalkyl and alkyl substituted cycloalkyl). Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl". As used herein, the term "substituted alkyl" refers to an alkyl having a substituent replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents can include, for example, alkenyl, alkynyl, halo, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxy, phosphate (phosphate), phosphonate (phosphonato), phosphinate (phosphinato), cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and urea), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl or aromatic (including heteroaromatic) groups. In some embodiments, the substituted alkyl group can include a heterocyclic group. As used herein, the term "heterocyclyl" includes closed ring structures similar to carbocyclyls in which one or more of the carbon atoms in the ring is an element other than carbon, such as nitrogen, sulfur, or oxygen. The heterocyclic group may be saturated or unsaturated. Exemplary heterocyclyls include, but are not limited to, aziridine, oxirane (epoxide, oxirane), thiirane (epoxysulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithietene, aziridine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0198] The term "alkenyl" includes unsaturated aliphatic hydrocarbon chains having 2 to 12 carbon atoms, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, etc. The alkyl or alkenyl group may be substituted at the terminal with heteroatoms such as nitrogen, sulfur or oxygen atoms to form aminoalkyl, alkoxy or thioalkyl groups, for example aminomethyl, thioethyl, propoxy, etc. Similarly, the above alkyl or alkenyl groups may be interrupted by heteroatoms in the chain to form alkylaminoalkyl, alkylthioalkyl or alkoxyalkyl groups, for example methylaminoethyl, ethylthiopropyl, methoxymethyl, etc.

[0199] Further, as used herein, the term "alicyclic" includes any cyclic hydrocarbon radical containing 3 to 8 carbon atoms. Suitable embodiments of alicyclic radicals include cyclopropane, cyclobutane, cyclopentane, etc. The term "heterocycle" includes any closed ring structure similar to the carbocyclic radical of nitrogen, sulphur or oxygen atom in which one or more carbon atoms in the carbon atom in the ring are elements (heteroatoms) other than carbon, for example, nitrogen, sulphur or oxygen atoms. Heterocyclic groups can be saturated or unsaturated. Suitable embodiments of heterocyclic radicals include, for example, aziridine, oxirane (epoxide, oxirane), thioethane (epiosulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithietene, azetidine, pyrrolidine, pyrroline, oxolan, dihydrofuran and furan. Additional examples of suitable heterocyclic groups include groups derived from tetrahydrofuran, furan, thiophene, pyrrolidine, piperidine, pyridine, pyrrole, picoline, coumarin, and the like.

[0200] In some embodiments, the alkyl, alkenyl, alicyclic and heterocyclic groups may not be replaced by, for example, aryl, heteroaryl, C 1-4 Alkyl, C 1-4 Alkenyl, C 1-4 substituted or substituted by alkoxy, amino, carboxyl, halogen, nitro, cyano, --SO3H, phosphono or hydroxyl. When the alkyl, alkenyl, alicyclic or heterocyclic group is substituted, the substituent is preferably C 1-4 Alkyl, halogen, nitro, amide, hydroxyl, carboxyl, sulfo or phosphono. In one embodiment, R comprises an alkyl substituted with a hydroxyl. The term "aryl" comprises an aromatic hydrocarbon group, comprising a fused aromatic ring, such as phenyl and naphthyl. The term "heteroaryl" comprises a heterocyclic aromatic derivative with at least one heteroatom such as nitrogen, oxygen, phosphorus or sulfur, and comprises, for example, furyl, pyrrolyl, thienyl, oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, etc. The term "heteroaryl" also comprises a fused ring in which at least one ring is aromatic, for example, indolyl, purinyl, benzofuranyl, etc.

[0201] In some embodiments, aryl and heteroaryl groups may be unsubstituted or substituted on the ring by, for example, aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxyl, halogen, nitro, cyano, --SO3H, phosphono or hydroxyl groups. When aryl, aralkyl or heteroaryl groups are substituted, the substituent is preferably C 1-4 In one embodiment, R comprises a C 1-4 Alkyl substituted aryl.

[0202] Applicable peroxycarboxylic acid compositions can include any C1-C22 peroxycarboxylic acid, including a mixture of peroxycarboxylic acids, including, for example, peroxyformic acid, peracetic acid, peroxyoctanoic acid and / or peroxysulfonated oleic acid. As used herein, the term "peracid" may also be referred to as "percarboxylic acid," "peroxycarboxylic acid" or "peroxyacid." Sulfoperoxycarboxylic acids, sulfonated peracids and sulfonated peroxycarboxylic acids are also included in the terms "peroxycarboxylic acids" and "peracids" used herein. The terms "sulfoperoxycarboxylic acids," "sulfonated peracids" or "sulfonated peroxycarboxylic acids" refer to the peroxycarboxylic acid form of sulfonated carboxylic acids, as disclosed in U.S. Patents No. 8,344,026 and No. 8,809,392, and U.S. Patent Publication No. 2012 / 0052134, which are incorporated herein by reference in their entirety. As known to those skilled in the art, peracid refers to an acid in which the hydrogen of a hydroxyl group in a carboxylic acid is replaced by a hydroxyl group. Oxidized peracids may also be referred to as peroxycarboxylic acids in this article.

[0203] Another class of suitable antimicrobial agents is quaternary ammonium compounds. The term "quaternary ammonium compound" or "quaternary ammonium salt" generally refers to any composition having the formula:

[0204]

[0205] Wherein R1-R4 are substituted or unsubstituted, saturated or unsaturated, branched or unbranched and cyclic or non-cyclic alkyl groups which may be the same or different, and may contain ether, ester or amide bonds; they may be aromatic or substituted aromatic groups. On the one hand, the groups R1, R2, R3 and R4 each typically have a C1-C20 chain length. X- is an anionic counterion. The term "anionic counterion" includes any ion that can form a salt with a quaternary ammonium. Examples of suitable counterions include halides such as chloride and bromide, propionate, methylsulfate, sugar acid, ethylsulfate, hydroxide, acetate, phosphate, carbonate (such as commercially available from Lonza as Carboquat H) and nitrate. Preferably, the anionic counterion is chloride.

[0206] The embodiment of suitable quaternary ammonium compound includes but is not limited to dialkyl dimethylamine and ammonium chloride, such as alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride and didecyl dimethyl ammonium chloride etc. A single quaternary ammonium or a combination of more quaternary ammoniums may be included in the embodiment of the solid composition. Other embodiments of quaternary ammonium compounds include but are not limited to amidoamine, imidazoline, epichlorohydrin, benzethonium chloride, ethyl benzyl ammonium chloride, myristyl trimethyl ammonium chloride, methyl benzethonium chloride, cethamonium chloride, cetrimonium bromide (CTAB), carnitine, dofadumium chloride, tetraethylammonium bromide (TEAB), domiphene, benzododecyl bromide, benzozonium chloride, choline, cocamidopropyl betaine (CAPB), denatonium and mixtures thereof.

[0207] Additional functional ingredients

[0208] The components of detergent composition can be optionally combined with various additional functional ingredients. Functional ingredients provide desired characteristics and functions for detergent composition. For the purpose of this application, the term "functional ingredient" includes when dispersed or dissolved in use and / or concentrate, such as in aqueous solution, the composition of beneficial properties is provided in a specific application. Some embodiments of functional ingredients are discussed in more detail below, but the specific material discussed is only given by way of example, and various other functional ingredients can be used. For example, many functional ingredients discussed below relate to the materials used in cleaning applications. However, other embodiments may include functional ingredients for other applications.

[0209] Exemplary additional functional ingredients include, for example: builders or water conditioners, including detergent builders; hardeners; bleaches; fillers; defoamers; anti-redeposition agents; stabilizers; dispersants; enzymes; glass and metal corrosion inhibitors; fragrances and dyes; thickeners; etc. A further description of suitable additional functional ingredients is set forth in U.S. Pat. No. 8,748,364, which is incorporated herein by reference in its entirety.

[0210] For example, the composition can include various aesthetic enhancing agents, such as dyes and odorants, including perfumes, and other aesthetic enhancing agents can be included in the composition. Dyes can be included to change the appearance of the composition, such as Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), Metamine Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandol Blue / Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), and Acid Green 25 (Ciba-Geigy).

[0211] Fragrances or fragrances that may be included in the composition include, for example, terpenoids, such as citronellol; aldehydes, such as amyl cinnamaldehyde; jasmine, such as C1S-jasmine or benzyl acetate, and vanillin.

[0212] One or more additional functional ingredients may be present in an amount up to about 85 wt.%, preferably between 0.001 wt.% and 65 wt.%, more preferably in an amount between 0.001 wt.% and about 30 wt.%, most preferably between 0.001 wt.% and about 20 wt.%.

[0213] Form of composition

[0214] The detergent compositions described herein may be formulated as solids, liquids, pastes, and / or gels, among others.

[0215] The components for forming the concentrated detergent composition can include aqueous media (such as water) as a processing aid. It is expected that the aqueous medium will help provide components with desired viscosity for processing. In addition, it is expected that when it is desired to shape the concentrated detergent composition into a solid, the aqueous medium can provide assistance in the solidification process. When the concentrated detergent composition is provided in solid form, it can be provided, for example, in the form of a block or a pellet. It is expected that the block will have a size of at least about 5 grams, and can include a size greater than about 50 grams. By the gross weight of the concentrated detergent composition, it is expected that the concentrated detergent composition will include 1 to 50% by weight, preferably 2 to 20% by weight of the amount of water.

[0216] Detergent compositions can be provided as liquids, including liquid concentrates. When provided as concentrates, the composition can be diluted to form a use composition. In general, concentrates refer to compositions that are intended to be diluted with water to provide a use solution for contacting an object, thereby providing the desired cleaning, rinsing, etc. The detergent composition that contacts the article to be washed can be referred to as a concentrate or a use composition (or use solution), depending on the formulation used in the method as described herein.

[0217] A use solution can be prepared from a concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having the desired cleaning properties. The water used to dilute the concentrate to form the use composition can be referred to as dilution water or diluent, and can vary from location to location. Preferably, the concentrated detergent composition is diluted at a concentration of 0.1 to 10 g / l, preferably 0.5 to 5 g / l, and most preferably 1 to 4 g / l to obtain a use solution.

[0218] In addition to liquid, detergent of the present disclosure can also be provided as solid.Solid detergent composition provides some commercial advantages.For example, compared with larger liquid products, the use of concentrated solid detergent composition reduces transportation costs due to compact solid form.In some embodiments, solid product can be provided in the form of multi-purpose solids such as block or multiple pellets, and can be reused to produce the aqueous use solution of detergent composition, for multiple circulations or predetermined number of distribution cycles.In some embodiments, the mass of solid detergent composition can be greater than about 5 grams, for example, about 5 grams to 10 kilograms.In some embodiments, the mass of the solid detergent composition of multi-purpose form is about 1 kilogram to about 10 kilograms or larger.

[0219] Suitable solid compositions produced according to the present application can take a variety of forms, including but not limited to granular and agglomerated solid compositions, flakes, powders, microparticles, granules, tablets, lozenges, wafers, agglomerates, bricks, unit doses, flowable solids and / or block compositions, whether compressed, extruded or cast.

[0220] In the pressed solid process, a flowable solid such as a granular solid or other particulate solid is combined under pressure to form a solid composition. In the pressed solid method, the flowable solid of the composition is placed in a forming part (e.g., a mold or container). The method may include gently pressing the flowable solid in the forming part to produce a solid cleaning composition. Pressure may be applied by a block machine or a rotary press, etc.

[0221] Detergent composition can be optionally solidified to produce solid composition.As mentioned herein, the uncured composition comprising flowable solid is compressed to provide sufficient surface contact between the particles constituting flowable solid, so that the uncured composition will be cured into stable solid composition.Sufficient amount of particles (such as granules) contact each other to provide effective preparation of the combination of particles of stable solid composition.Including the curing step can include allowing the solidification of pressed solid for a period of time, such as several hours or about 1 day (or longer).In other aspects, the method can include the flowable solid vibrated in the formed part or mold, such as the method disclosed in U.S. Patent No. 8,889,048, which is incorporated herein by reference in its entirety.

[0222] Compared to conventional solid block or tablet compositions that require high pressure in a tablet press, or casting that requires melting of the composition, consuming a significant amount of energy, and / or extrusion that requires expensive equipment and advanced technical knowledge, the use of compressed solids provides a variety of benefits. Compressed solids overcome the various limitations of other solid formulations that require the preparation of solid compositions. In addition, compressed solid compositions retain their shape under conditions where the composition can be stored or disposed of.

[0223] In an embodiment, detergent composition of the present disclosure can provide in the form of granules.On the one hand, granulation material can be formed by compressing the solid granular or agglomeration complex of urea and acid in a suitable granulation device to produce a granulation material of appropriate size.Solid block material and cast solid block material can be manufactured by introducing a prehardened block or a solid block hardened in a container into a container.Preferred containers comprise disposable plastic containers or water-soluble film containers.Other applicable packaging of composition comprises flexible bags, packets, shrink packaging and water-soluble films such as polyvinyl alcohol.

[0224] In other respects, solid composite can be formed by combining materials described herein using batch or continuous mixing system.In exemplary embodiments, use single-or double-screw extruder to combine and mix one or more components at high shear force, to form homogeneous mixture.In some embodiments, processing temperature is at or lower than the melt temperature of component.Can distribute the processed mixture from mixer by shaping, casting or other suitable modes, detergent composition hardens into solid form afterwards.In general, the solid composite processed according to these methods is basically homogeneous and dimensionally stable in the composition distribution in its whole mass.

[0225] In the extrusion process, the components of the composition are introduced into the final mixing system and continuously mixed until the components form a substantially uniform semi-solid mixture in which the components are distributed throughout their mass. The mixture is then discharged from the mixing system into or through a die or other forming means. The product is then packaged. In an exemplary embodiment, the formed composition begins to harden into a solid form.

[0226] In the casting process, the components of the composition are introduced into the final mixing system and continuously mixed until the components form a substantially uniform liquid mixture in which the components are distributed throughout their mass. Once mixing is complete, the product is transferred to a packaging container where solidification occurs. In an exemplary embodiment, the casting composition begins to harden into a solid form.

[0227] How to use

[0228] The detergent compositions described herein are suitable for use in a variety of applications and methods, including any application suitable for detergent compositions. More specifically, the detergent compositions described herein can be used in any industry that requires the use of alkaline detergents and is beneficial for removing soils, especially starch-based soils, from surfaces. The methods described herein help remove soils, especially starch-based soils, on the surfaces of treated substrates, thereby beneficially cleaning the surfaces and preventing soil accumulation.

[0229] The method of using the detergent composition described herein is particularly suitable for institutional ware washing. Exemplary disclosures of ware washing applications are described in U.S. Patent Application Serial Nos. 13 / 474,771, 13 / 474,780 and 13 / 112,412, including all references cited therein, which are incorporated herein by reference in their entirety. The method can be carried out in any household or institutional dishwasher, including those described in U.S. Patent No. 8,092,613, which includes all drawings and drawings incorporated herein by reference in their entirety. Some non-limiting embodiments of dishwashers include door machines or hood machines, channel machines, undercounter machines, glass washers, long dragon machines, cooking utensils machines, utensil washers and household dishwashers. The dishwasher can be a single-trough machine or a multi-trough machine.

[0230] A door-type dishwasher, also known as a hood-type dishwasher, refers to a commercial dishwasher in which dirty dishes are placed on racks and the racks are then moved into the dishwasher. Door-type dishwashers clean one or two racks at a time. In this type of machine, the racks are fixed and the wash and rinse arms move. Door-type machines contain two sets of arms, one set of wash arms and one set of rinse arms or one set of rinse arms.

[0231] Door-type machines can be high temperature machines or low temperature machines. In high temperature machines, dishes are sterilized with hot water. In low temperature machines, dishes are sterilized with chemical disinfectants. Door-type machines can be recirculating machines or dump and fill machines. In recirculating machines, detergent solutions are reused or "recirculated" between wash cycles. The concentration of detergent solutions is adjusted between wash cycles to maintain sufficient concentration. In dump and fill machines, detergent solutions are not reused between wash cycles. New detergent solutions are added before the next wash cycle. Some non-limiting embodiments of door-type machines include Ecolab Omega HT, Hobart AM-14, Ecolab ES-2000, Hobart LT-1, CMA EVA-200, American Dish Service L-3DW and HT-25, Autochlor A5, Champion D-HB and Jackson Tempstar.

[0232] In one aspect, the detergent composition is used as a warewashing detergent to remove starchy soils at a temperature of 20°C to 85°C, preferably at 50°C to 75°C. Using the described concentrated detergent composition as a warewashing detergent also allows for shorter wash times, which are defined as the time the warewashing detergent is in contact with the ware before being rinsed off. The wash time for the warewashing detergent is preferably from 10 seconds to 5 minutes, preferably from 15 seconds to 2 minutes, more preferably from 30 to 60 seconds, and most preferably from 30 to 45 seconds.

[0233] Additionally, the method of using the detergent composition is also suitable for use in CIP and / or COP processes to replace the use of bulk detergents that leave hard water residues on the treated surface. In other applications where industry standards focus on the quality of the treated surface, the method of using may be desirable to prevent hard water scale accumulation provided by the detergent composition. Such applications may include, but are not limited to, vehicle care, industrial, hospital, and textile care.

[0234] Other industries in which detergent compositions can be used include food and beverage applications, restaurant / catering industry, textile care / laundry, healthcare industry (e.g., hospitals, nursing facilities, clinics, etc.), and / or pest elimination. Examples of use applications of detergent compositions include, for example, alkaline detergents that are effective as grill and oven cleaners, dishwashing detergents, laundry detergents, laundry prepregs, drain cleaners, hard surface cleaners, surgical instrument cleaners, transportation vehicle cleaning, vehicle cleaners, dishwashing prepregs, dishwashing detergents, beverage machine cleaners, concrete cleaners, building exterior cleaners, metal cleaners, floor cleaners, counter cleaners, table cleaners, degreasers, stain removers, textiles, and / or fabrics. In various of these applications, detergent compositions with high alkalinity are the most desirable and effective, but damage caused by hard scale accumulation is undesirable.

[0235] Various methods of use as described herein employ detergent compositions which may be formed by combining the components of the detergent compositions in the weight percentages disclosed herein before or during use. The detergent compositions may be provided in various formulations. Methods of use may employ any of the disclosed formulations, including, for example, liquid, semi-solid and / or other solid formulations as described herein.

[0236] The methods may also employ concentrates and / or use solutions that constitute aqueous solutions or dispersions of concentrates as described herein.Such use solutions may be formed during a washing process, such as during a warewashing process.

[0237] In all respects, adopt the solid detergent composition of packaging, product may first need to be removed from any applicable packaging (for example, film).After this, according to some use method, composition can be directly inserted into distribution equipment and / or provided to water source for cleaning.The embodiment of such distribution system includes for example United States Patent No. 4,826,661, No. 4,690,305, No. 4,687,121, No. 4,426,362 and United States Patent No. 32,763 and No. 32,818, the disclosures of these patents are all incorporated herein by reference.Ideally, solid detergent composition is configured or produced with the specific shape of close-fit distribution system, to prevent incorrect solid product from being introduced and distributed in equipment.

[0238] In certain embodiments, the detergent composition can be mixed with a water source prior to or during use. In other embodiments, the detergent composition does not require formation of a use solution and / or further dilution, and can be used without further dilution.

[0239] In various aspects, a solid detergent composition is employed and a water source contacts the detergent composition to convert the solid detergent composition (particularly a powder) into a use solution. Additional dispensing systems may also be utilized that are more suitable for converting alternative solid detergent compositions into a use solution. The method includes the use of a variety of solid detergent compositions, including, for example, extruded blocks or "capsule" type packaging.

[0240] On the one hand, the distributor can be used to spray water (e.g., in a spray pattern from a nozzle) to form a detergent use solution. For example, water can be sprayed to an equipment or other holding reservoir with a detergent composition, wherein the water reacts with a solid detergent composition to form a use solution. In certain embodiments of the method, the use solution can be configured to drip downward due to gravity until a dissolved solution of the detergent composition is distributed for use. On the one hand, the use solution can be distributed in the washing solution of a dishwashing machine.

[0241] All publications and patent applications in this specification are indicative of the levels of ordinary technicians in the field to which the present disclosure relates. All publications and patent applications are incorporated herein by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

[0242] Example

[0243] The embodiments of the compositions described herein are further defined in the following non-limiting examples. It should be understood that these examples, although indicating certain embodiments, are given only by way of illustration. Through the above discussion and these examples, those skilled in the art can determine the essential features of the compositions and methods described herein, and can make various changes and modifications to the embodiments without departing from the spirit and scope of the present invention, so that the embodiments are suitable for various uses and conditions. Therefore, in addition to those shown and described herein, various modifications to the embodiments described above will be apparent to those skilled in the art. Such modifications are intended to also fall within the scope of the appended claims.

[0244] Example 1

[0245] Cleaning performance tests were conducted to evaluate the starch removal efficacy of a base detergent formula, a detergent + bleach formula, a detergent + enzyme formula, and a detergent + bleach + enzyme formula. These formulas are provided in Tables 3-6 below.

[0246] Table 3. Formulation A: Basic detergent composition

[0247] Components Amount (wt.%) Thick Gray 35-45 Sodium tripolyphosphate 15-25 MGDA 5-15 <![CDATA[GLDA (Na4 solution, 47%)]]> 1-8 Sodium aluminate (45%) 0.1-0.5 ATMP (50%) 1-5 Antarox 25-R-2 1-8

[0248] Table 4. Formulation B: Basic detergent + bleach composition

[0249] Components Amount (wt.%) Recipe A ～85 Sodium Percarbonate 15 Mn catalyst 0.025

[0250] Table 5. Formulation C: Basic Detergent + Enzyme

[0251] Components Amount (wt.%) Recipe A ～85 Amylase (Termamyl 120T) 1

[0252] Table 6. Formulation D: Basic Detergent + Bleach + Enzyme Composition

[0253] Components Amount (wt.%) Recipe A ～85 Sodium Percarbonate 15 Mn catalyst 0.025 Amylase (Termamyl 120T) 1

[0254] Stain removal testing was performed using melamine tiles coated with potato starch (DM-79) (Testfabrics, Inc.) Potato starch is colorless but has an orange tint that allows for quantitative stain removal measurements using a colorimeter.

[0255] Four starch-stained melamine tiles were provided and their initial reflectance was recorded using a colorimeter (Mach5, HunterLab) to assess the baseline of the stain. The tiles were then fixed in a holder and placed in a Peggy dish rack at a 45° angle. The tiles were washed in a door-type dishwasher (Hobart AM15, 53L wash tank, 2.6L rinse volume) for 10 cycles, where each cycle included a 38-second wash phase and a 10-second rinse phase (at 20 psi).

[0256] For the basic detergent + bleach + enzyme composition, the composition was used at a concentration of 2.0 g / L for each cycle. Between each individual cycle, 5% more detergent was added to maintain the detergent concentration. For the composition without sodium percarbonate and Mn catalyst, only 1.7 g / L detergent was added, making the concentration of all other components the same as the concentration of the 2.0 g / L detergent + bleach + enzyme composition.

[0257] After the wash cycle is complete, the percentage of soil removed is measured using a colorimeter. The percentage of soil removed is calculated according to the following formula:

[0258] % Dirt removal rate = [(L 最终 -L 初始 ) / (L 最佳 -L 初始 )]*100

[0259] In the formula, "L" is the light-dark contrast value measured by the colorimeter, where L 最佳 =88.05,L 初始 is the light-dark contrast value before the washing cycle, L 最终 All wash cycles were completed for the light-dark contrast value after the wash cycle. The results of this evaluation are shown in Table 7 and Figure 1 shown.

[0260] Table 7. Decontamination efficacy

[0261] formula Decontamination rate (%) Formula A (detergent) 11.2％ Formula B (detergent + bleach) 21.1％ Formula C (detergent + enzyme) 18.3％ Formula D (detergent + bleach + enzyme) 60.8％

[0262] As shown in Table 7 and Figure 1 As shown, the basic detergent provides about 11% of the stain removal efficacy. The addition of bleach (sodium percarbonate and Mn catalyst) increases the stain removal efficacy by 9.9% (21.1%-11.2%=9.9%) over the stain removal efficacy of the detergent alone. Adding amylase to the detergent can increase the stain removal rate by about 7% (18.3%-11.2%=7.1%). In view of these results, the expected efficacy of the detergent + bleach + enzyme composition (based only on the efficacy of the additives) is about 28% (11.2%+9.9%+7.1%=28.2%). However, surprisingly, the actual efficacy of the detergent + bleach + enzyme composition is 60.8%, more than twice the expected stain removal. The significant improvement in dirt removal indicates that there is an unexpected synergistic effect between detergents, bleaches and enzymes.

[0263] Example 2

[0264] In view of the surprising efficacy demonstrated by the combination of detergent, bleach and enzyme, further evaluation was performed to assess whether the synergistic effect demonstrated was applicable to all amylases. The same comparative formulations (formulations A and B) were prepared according to the table in Example 1. According to Tables 8 and 9, additional detergent + bleach compositions and detergent + bleach + enzyme compositions were further prepared using different amylases.

[0265] Table 8. Formulation E: Basic Detergent + Enzyme Composition

[0266] Components Amount (wt.%) Recipe A ～85 Amylase (Achieve Choice 150T) 0.5

[0267] Table 9. Formulation F: Basic detergent + bleach + enzyme composition

[0268] Components Amount (wt.%) Recipe A ～85 Sodium Percarbonate 15 Mn catalyst 0.025 Amylase (Achieve Choice 150T) 0.5

[0269] Formulations A, B, E and F were evaluated using the procedure outlined in Example 1. The results of this evaluation are shown below in Table 10 and Figure 2 middle.

[0270] Table 10. Decontamination efficacy

[0271] formula Decontamination rate (%) Formula A (detergent) 11.2％ Formula B (detergent + bleach) 21.1％ Formula E (detergent + enzyme) 37.9％ Formula F (detergent + bleach + enzyme) 73.2％

[0272] As shown in Table 10, Achieve Choice 150T provides an additional 26.7% improvement in stain removal, exceeding the base stain removal of the detergent composition alone (37.9% - 11.2% = 26.7%). Consistent with Example 1, the addition of the bleach composition increased stain removal by 9.9%, exceeding the stain removal of the detergent composition alone (21.1% - 11.2% = 9.9%). Therefore, the expected efficacy of the detergent + bleach + enzyme composition (based on additive efficacy alone) is approximately 47.8% (11.2% + 9.9% + 26.7% = 47.8%). However, surprisingly, the actual efficacy of the detergent + bleach + enzyme composition is 73.2%, an increase of more than 50% in efficacy compared to the expected value. The significant improvement in stain removal confirms the unexpected synergy between the detergent and bleach composition described herein and all amylases.

[0273] Example 3

[0274] Other commercially available detergent formulations were tested with the addition of amylase to evaluate whether amylase can be simply added to any detergent composition to achieve synergy. The exemplary compositions described herein were prepared together with four comparative compositions similar to commercially available online detergent compositions. 10 ppm of Termamyl 300L (a liquid form of Termamyl 120T) was added to the wash solution at 1000 ppm for each formulation. "These comparative compositions are shown in Tables 11-15 below.

[0275] Table 11. Formulation G

[0276] Components Amount (wt.%) Main alkalinity source 35-45 Second alkalinity source 10-20 Aminocarboxylic acid 10-20 Phosphonic acid 20-30 Phosphonates 1-5 Nonionic surfactants 1-8 Mn catalyst 0.01-0.3 Corrosion Inhibitors 0.1-1

[0277] Table 12. Comparative composition 1

[0278] Components Amount (wt.%) Main alkalinity source 81 Second alkalinity source 1 Water conditioning polymers 7 EO / PO block copolymer 4 Phosphonates 1.5 Aminocarboxylates 2 Corrosion Inhibitors 2.5 Emulsifier / stabilizer 1

[0279] Table 13. Comparative Composition 2

[0280] Components Amount (wt.%) Main alkalinity source 71 Second alkalinity source 2.5 Polycarboxylate Chelating Agent 4.5 Phosphonic acid 1 Nonionic surfactants 6 filler 1 Cellulose 0.5 Corrosion Inhibitors 10 Bleach 1.5 water 2

[0281] Table 14. Comparative Composition 3

[0282] Components Amount (wt.%) Main alkalinity source 20 Second alkalinity source 55 Water Conditioner 12.5 Nonionic surfactants 2 filler 0.1 Corrosion Inhibitors 0.2 water 10

[0283] Table 15. Comparative Composition 4

[0284] Components Amount (wt.%) Main alkalinity source 80 Water Conditioner 7.5 Nonionic surfactants 2 Corrosion Inhibitors 5 Emulsifier / stabilizer 6

[0285] Formulation G and the comparative compositions were evaluated using the procedure outlined in Example 1, except that each composition was tested twice, one using a dosage concentration of 1000 ppm detergent and 10 ppm amylase, and the other test using 1000 ppm detergent but no amylase. The evaluation was conducted over 20 wash cycles. The results of this evaluation are shown in Table 1. Figure 3 and as shown in Table 16.

[0286] Table 16. Decontamination efficacy

[0287] Composition Detergency without amylase (%) Decontamination rate with amylase (%) Formulation G 22.8 73.2 Comparative composition 1 13.0 43.3 Comparative composition 2 11.7 12.1 Comparative composition 3 9.8 8.3 Comparative composition 4 10.2 17.6

[0288] Figure 3 Amylases were shown to be incompatible with all warewashing formulations. Comparative Composition 1 is an enzyme-compatible ash-based detergent that exhibited improved stain removal performance after the addition of amylase. However, the performance of Comparative Composition 1 was not synergistic and was substantially lower than the stain removal performance of Formulation G. Comparative Composition 2 is a chlorine-containing ash-based detergent. Without being bound by theory, it is believed that amylases are incompatible with chlorine: the stain removal rate of Comparative Composition 3 only increased by 0.4% after the addition of amylase. Comparative Composition 3 is a highly corrosive detergent. Without being bound by theory, it is believed that amylases are ineffective under the highly corrosive conditions of Comparative Composition 3, as the stain removal rate actually decreased after the addition of amylase. Comparative Composition 4 is also an ash-based detergent. It is believed that one or more components of Comparative Composition 4 are incompatible with enzymes, as the stain removal efficacy only increased by about 7% after the addition of amylase.

[0289] These data indicate only additive or even negative interactions between inline detergent compositions and amylases. Given the minimal benefit provided by the enzymes in the comparative compositions, it was unexpected that amylases would interact synergistically with the detergent compositions described herein to significantly improve soil removal. The synergistic effect is particularly surprising because starch-based soils are more difficult to remove than many other types of soils.

[0290] Example 4

[0291] In addition to the soil removal data, the stability of the compositions as solids under various temperature conditions was evaluated. Three humidity chambers were used to generate these temperatures: the first at ambient temperature (72°F, 50% RH), the second at 100*F (65% RH), and the third at 122°F (<50% RH). Formulations D, F, and G described in Examples 1-3 were made into solid blocks, and blocks of each formulation were placed in the humidity chamber for a period of 8 weeks.

[0292] Formulations D, F, and G were also subjected to cycling temperature, simulating storage conditions, where the humidity chamber was held at 80°F (65% RH) for 11 hours, then increased to 105°F (30% RH) in one hour, then held at 105°F for another 11 hours, and finally decreased to 80°F (65% RH) in one hour.

[0293] For both tests, the solid blocks were evaluated for expansion (greater than 3%) and cracking.After 8 weeks of testing, Formulations D, F and G showed good dimensional stability: there were no substantial physical issues with the blocks.

[0294] Embodiments having thus been 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 disclosure, and all such modifications are intended to be included within the scope of the appended claims.

Claims

1. A detergent composition comprising: Alkalinity source; one or more surfactants; amylase; and one or more chelating agents; Oxygen source; Bleach activators, wherein The bleach activator comprises one or more compounds according to formula (I), (II), (XIX) and (XX): [(L p M q ) n X r Y s (Formula (I)) wherein each L is independently an organic ligand containing at least three nitrogen atoms and / or at least two carboxyl groups; wherein "M" is a metal, and wherein the metal is a transition metal; wherein "X" is a coordinating group or a bridging group, wherein "Y" is a counterion, wherein "p" is an integer from 1 to 4, "q" is an integer from 1 to 2, "r" is an integer from 0 to 6, and "s" is the number of counterions; wherein L1 and L2 are separate ligands or wherein L1 and L2 are combined; wherein "M" is a metal, and wherein the metal is manganese or iron; wherein "Y" is a counterion; and wherein "X" is a coordinating group or a bridging group; 2. The detergent composition according to claim 1, wherein The alkalinity source is an alkali metal carbonate.

3. The detergent composition according to any one of claims 1 or 2, wherein At least one of the one or more surfactants is a nonionic surfactant, and wherein the nonionic surfactant comprises a poloxamer.

4. The detergent composition according to claim 3, further comprising one or more additional enzymes.

5. The detergent composition according to any one of claims 1 to 4, wherein The bleach composition is a peroxygen bleach.

6. The detergent composition according to claim 5, wherein The peroxygen bleach is sodium percarbonate, sodium perborate, hydrogen peroxide and / or peracid.

7. The detergent composition according to any one of claims 1 to 6, wherein The bleach activator comprises formula (I) and wherein the coordinating group or bridging group is H2O, OH - SH - HO2 - , O 2- 、O2 2- , S 2- 、F - , Cl - Br - ,I - 、NO3 - 、NO2 - 、SO4 2- 、SO3 2- PO4 3- 、N3 - , CN - 、NR3、NCS - , RCN, RS - , RCO2 - ,RO - or wherein R is hydrogen or a C1 to C6 alkyl group; or wherein the bleach activator comprises formula (II), wherein the coordinating group or bridging group is O 2- 、O2 2- 、CH3O-、CH3CO 2- , Or Cl-.

8. The detergent composition according to any one of claims 1 to 7, wherein The one or more chelating agents include phosphates and aminocarboxylates.

9. The detergent composition according to claim 8, wherein The phosphate is an alkali metal phosphate and the aminocarboxylate is EDTA, HEDTA, DTPA, EDDS, HEIDA, IDS, HIDS, MGDA and / or GLDA.

10. The detergent composition according to claim 9, wherein The alkali metal phosphate is sodium orthophosphate, potassium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate and / or sodium hexametaphosphate.

11. The detergent composition according to any one of claims 1 to 10, further comprising a corrosion inhibitor, the corrosion inhibitor comprising sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate, potassium aluminum sulfate, aluminum zinc sulfate, zinc chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc fluorosilicate, zinc dichromate, zinc chlorate, sodium zincate, zinc gluconate, zinc acetate, zinc benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc bromide, zinc fluoride, zinc fluorosilicate, zinc salicylate or a combination thereof.

12. The detergent composition according to any one of claims 1 to 11, further comprising one or more additional functional ingredients, wherein: The one or more additional functional ingredients are builders or water conditioners, hardeners, bleaches, thickeners, fillers, defoamers, anti-redeposition agents, stabilizers, dispersants, enzymes, perfumes and / or dyes.

13. The detergent composition of any one of claims 1-12, comprising from about 20 wt.% to about 60 wt.% of the alkalinity source; from about 5 wt.% to about 30 wt.% of the oxygen source; from about 0.001 wt.% to about 5 wt.% of the bleach activator; from about 0.01 wt.% to about 10 wt.% of the amylase; from about 0.5 wt.% to about 20 wt.% of the one or more nonionic surfactants; and from about 15 wt.% to about 60 wt.% of one or more chelating agents.

14. The detergent composition of any one of claims 1-12, comprising from about 40 wt.% to about 45 wt.% of the alkalinity source; from about 12 wt.% to about 18 wt.% of the oxygen source; from about 0.02 wt.% to about 0.03 wt.% of the bleach activator; from about 0.4 wt.% to about 1.1 wt.% of the amylase; from about 2 wt.% to about 6 wt.% of the one or more nonionic surfactants; and from about 35 wt.% to about 40 wt.% of one or more chelating agents.

15. The detergent composition according to claim 14, wherein The one or more chelating agents include about 20 wt.% to about 25 wt.% phosphate, about 10 wt.% to about 15 wt.% aminocarboxylate, and about 1 wt.% to 3 wt.% secondary aminocarboxylate.

16. The composition according to any one of claims 1 to 15, wherein The composition is a pressed solid or a flowable solid.

17. The composition according to any one of claims 1 to 15, wherein The compositions are either liquid concentrates or diluted use solutions.

18. A method of cleaning a surface, comprising: mixing the detergent composition according to any one of claims 1 to 17 with water to form a use solution; as well as The detergent composition is contacted with a surface, wherein the surface is soiled with a starch-based soil; wherein the composition removes the starch-based soil.

19. The method according to claim 18, wherein: The surface is a food processing surface and / or utensil.

20. The method according to claim 19, wherein: The surface is ware and includes one or more of cutlery, plates, bowls, pots, pans, glassware.

21. The method according to claim 20, wherein: The vessel is glass, plastic, ceramic and / or metal.

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