CZ20011641A3 - Ultrasonic cleansing device - Google Patents

Abstract

The present invention relates to a hand held ultrasonic cleaning device comprising a housing, said housing comprising a griping means; a cleaning head adapted to rest on and be moved over surface to be cleaned, wherein said cleaning head is adapted to be removably mounted to said housing and the minimum surface area of said cleaning head to rest on said surface is greater than 6.25 cm squared; A transducer means mounted in said housing for oscilating said cleaning head at an ultrasonic frequency; and a power for supplying direct current to said transducer means, wherein said power supply means is associated with said device. Further disclosed is a method of removing tough food soil from a hard surface comprising the steps of: (i) contacting said soil with a cleaning composition; (ii) contacting said soil with said cleaning head of said ultrasonic cleaning device; (iii) rinsing said hard surface with an aqueous solution. Further the invention relates to an ultrasonic cleaning product comprising: (a) a cleaning composition comprising a cleaning agent; and (b) the hand held ultrasonic cleaning device.

Description

The present invention generally relates to devices and methods for removing dirt using ultrasonic waves.

BACKGROUND OF THE INVENTION

Ultrasonic cleaning is a well-known industrial process. It is used, for example, for cleaning electronic components after or during immersion in a cleaning solution, for example in azeotropic mixtures of fluorocarbons. It is also used to a small extent in household hygiene as an ultrasonic toothbrush. However, in households, except for this limited use, ultrasonic cleaning did not find much acceptance.

Therefore, there remains a need for a device that is capable of providing ultrasonic energy or waves of usable frequency and power for numerous cleaning applications.

Prior art documents:

US 4 183 011, US 4 103 519, US 4 225 803, US 3 946 599, US 5 770 801, US 5 640 960, US 3 849 195, US 4 168 560, US 4 250 586, US 5 247 716, 3,937,326, 4,069,541, 4,307,484; JP 10,165,228, JP 61,199,829; EP 856 277.

SUMMARY OF THE INVENTION

The invention satisfies the above needs by providing a device that is capable of providing ultrasonic energy or waves of usable frequency and power for a large number of cleaning applications.

A first embodiment of the present invention is an ultrasonic cleaning device comprising a housing that forms a gripping device; a cleaning head adapted to rest on and move over the surface to be cleaned, wherein the cleaning head is adapted to be removably mounted on the housing, and the minimum surface area of the cleaning head to rest on the surface has been greater than 6.25 cm; a converter mounted in a housing for

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A second embodiment of the present invention is an ultrasonic cleaning device comprising a first housing that includes a gripping device; a cleaning head adapted to rest on and move over the surface to be cleaned, and the cleaning head adapted to be detachably mounted on the first housing, and the minimum surface area of the cleaning head to rest on the surface was greater than 6.25 cm ² ; a second housing, wherein the first housing is associated with said second housing and said second housing comprises a second housing mounted on ^one transducer for oscillating said cleaning head at an ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.

A third embodiment of the present invention is an ultrasonic cleaning product comprising:

(a) a liquid or gel detergent composition comprising a detergent; and (b) a hand-held ultrasonic cleaning device comprising a housing forming a gripping device; a cleaning head adapted to rest on and move over the surface to be cleaned, wherein the cleaning head is adapted to be removably mounted on the housing, and the minimum surface area of the cleaning head to rest on the surface has been greater than 6.25 cm ² ; a transducer mounted in the housing for oscillating the cleaning head at ultrasonic frequency; and from the power supply to power the converter

A direct current, wherein the feeder is associated with said device.

"A fourth embodiment of the present invention is an ultrasonic cleaning product comprising:

(a) a liquid or gel detergent composition comprising a cleaning agent; and (b) an ultrasonic cleaning device comprising a first housing that includes a gripper; a cleaning head adapted to rest on and move over the surface to be cleaned and the cleaning head adapted to be removably mounted on the first housing; and a minimum surface area of the cleaning head f to rest on the surface was greater than 6.25 cm 2; from a second housing, wherein the first housing is associated with the second housing and the second housing comprises a second housing mounted transducer for oscillating the cleaning head at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.

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A fifth embodiment of the present invention is an ultrasonic cleaning device comprising a housing that optionally includes a gripping device, a holding device for detachably holding tableware; a transducer mounted in the housing for oscillating said housing at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.

*

A sixth embodiment of the present invention is an ultrasonic cleaning device comprising a housing adapted to be at least partially submerged in an aqueous environment and said housing optionally comprising a gripping device, a holding device for detachably holding tableware; a transducer, which is mounted in the housing, for oscillating the aqueous environment ¹ at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.

By using the device as an ultrasonic energy source, stains and firmly adhering dirt can be removed without applying excessive force, scrubbing, pressure, or other manipulation that causes wear and tear on the soiled material or surface. In such a procedure, the user does not have to expend manual energy to remove dirt, which contributes to the user's comfort. The invention also includes processes by which stains or dirt are removed from either locally restricted areas or from the entire article to be cleaned.

The present invention also encompasses methods of hard cleaning by contacting a surface with a cleaning composition and then contacting the surface with a cleaning head of the device or ultrasonic cleaning product as described above and imparting ultrasonic energy to the dirt.

The invention also includes methods removing tough food soil from a hard surface by contacting the soil with a cleaning composition and placing soil into • contact with the cleaning head device or the ultrasonic cleaning product, as hereinbefore described, and granting _W ultrasonic energy to said soil.

As used herein, the term "ultrasonic waves" means mechanical pressure or stress waves that can penetrate the medium of any material, where the frequency spectrum of these waves can vary from several cycles per second (Hz) to several billion Hz.

All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise specified. All documents cited herein are hereby incorporated by reference in their entirety.

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Brief description of the drawings

FIGURE 1 is a perspective view of a handheld ultrasonic device, with a cleaning solution reservoir adapted to be removably mounted to the device. Also shown are a removably mounted cleaning head and additional cleaning solution reservoir.

FIGURE 2 is a perspective view of two different handheld pencil-shaped ultrasonic devices that are used in the invention to impart ultrasonic waves to a stain or dirt.

FIGURE 3 is a perspective view of a handheld pencil-shaped ultrasonic device that is shown when imparting ultrasonic dirt waves.

FIGURE 4 is a perspective view of an ultrasonic device used in the invention for imparting ultrasonic waves to a stain or dirt. The ultrasonic generator and power source are in a second housing that is associated with a cleaning head that is in the first housing.

DETAILED DESCRIPTION OF THE INVENTION

As mentioned above, a first embodiment of the present invention is an ultrasonic cleaning device comprising a housing that forms a gripping device; a cleaning head adapted to rest on and move over the surface to be cleaned, wherein the cleaning head is adapted to be removably mounted on the housing, and the minimum surface area of the cleaning head to rest on the surface has been greater than 6.25 cm; preferably greater than 20 cm; the gripping device is preferably at the proximal - proximal end of the housing and the cleaning head is at the distal - distal - end of the housing; a transducer mounted in the housing for oscillating the cleaning head at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device, preferably the feeder is mounted in a housing.

It is also preferred that the cleaning device further comprise at least one, more preferably at least two, solution containers associated with said device, and that said containers comprise at least one, more preferably at least two, cleaning means suitable for surface cleaning; and at least one, more preferably at least two dispensing means mounted in the housing for delivering at least one cleaning agent from the at least one solution reservoir to the surface before or simultaneously when the surface is in contact with the cleaning head. In one aspect, it is preferred that the solution reservoir be adapted for removable mounting into the housing. According to another aspect, it is preferable that: • · · · · ·······

-5 The solution reservoir has been mounted in the housing. The advantage of two or more cartridges is that incompatible cleaning agents, such as bleaching agents and enzymes, can be placed in different cartridges, which normally cannot be combined in the detergent composition without loss of cleaning performance. This allows the compositions to obtain a cleaning benefit from these incompatible ingredients when they only come into contact with each other either just prior to dosing or when they are applied to the surface. This means that any loss of cleaning potential has been minimized.

As mentioned above, the second embodiment of the present invention is an ultrasonic cleaning device comprising a first housing that includes a gripping device; a cleaning head adapted to rest on and move over the surface to be cleaned, and the cleaning head adapted to be detachably mounted on the first housing, and the minimum surface area of the cleaning head to rest on the surface was greater than 6.25 cm ² ; the gripping device is preferably at the proximal end of the first housing and the cleaning head is at the distal end of the first housing; from a second housing, wherein the first housing is associated with the second housing and the second housing comprises a second housing mounted transducer for oscillating the cleaning head at ultrasonic frequency; and from a feeder for supplying the converter with direct current, wherein the feeder is associated with said device, the feeder is preferably mounted in the second housing.

It is also preferred that the cleaning device according to the second aspect further comprises at least one solution reservoir associated with the device and at least one, more preferably at least two solution reservoirs comprising at least one, more preferably at least two cleaning means which are suitable for surface cleaning; and at least one, more preferably at least two dispensing means, which are mounted in the first housing, for delivering at least one cleaning agent from the at least one solution reservoir to the surface before or simultaneously when the surface is in contact with the cleaning head. In one aspect, it is preferred that the solution reservoir be adapted for removable mounting in the first housing. In one aspect, it is preferred that the solution reservoir be adapted for removable mounting in the second housing. In another aspect, it is preferred that the solution reservoir be mounted in the first housing. In another aspect, it is preferred that the solution reservoir be mounted in the second housing. This use of more than one solution reservoir has all the advantages of using incompatible additives, as noted above.

According to a second aspect, it is preferred that the first sleeve be held in the hand. In one preferred embodiment, the first housing, when not in use, forms the second housing. In use, the first housing is used to clean the surface, while the second housing stores and supplies the detergent (s), force and ultrasonic energy to the first surface cleaning housing.

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As mentioned above, the third and fourth embodiments of the present invention are ultrasonic cleaning products which consist of a liquid cleaning composition comprising a cleaning agent; and a manual ultrasonic cleaning device according to the first aspect or an ultrasonic cleaning device according to the second aspect.

Preferably, the cleaning agent is present in the liquid detergent composition in an effective amount, more preferably from 0.000% to 99.9%, even more preferably from 0.001% to 55%, and even more preferably from 0.005% to 45% by weight. These detergent compositions may additionally contain detergent ingredients and are exemplified in greater detail hereinbelow. The liquid detergent in ultrasonic cleaning products may be, for example, in an optionally at least one solution container, in another container in the same product and designed to be added to the optional at least one solution container, in another container in the same product and directly added to the surface to be cleaned, in another container in the same product and made into an aqueous solution into which the surface is immersed, in another container in the same product and applied by the user from another the container to the cleaning head either undiluted or in another container in the same product and as an aqueous solution. These are just some possible examples and are not intended to be limiting.

It is preferred that these ultrasonic cleaning products further include instructions for use of the product. One preferred set of instructions includes the steps of:

(i) applying an effective amount of a liquid cleaning composition to the surface;

(ii) imparting ultrasonic waves to the surface using said device; and (iii) optionally, rinsing the surface with an aqueous solution.

Another preferred set of instructions includes the steps of:

(i) using an apparatus for applying an effective amount of a liquid cleaning composition to the surface simultaneously and adjacent to the cleaning head;

(ii) moving the scrub head over the surface and maintaining contact of the scrub head with the surface; and (iii) optionally, rinsing the surface with an aqueous solution.

These instructions are suitable for integration with ultrasonic cleaning products which are based on a device according to either the first or second embodiment.

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As mentioned above, the fifth embodiment of the present invention is an ultrasonic cleaning device comprising a housing that optionally includes a gripping device, a holding device for detachably holding tableware; a transducer mounted in the housing for oscillating said housing at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.

As mentioned above, a sixth embodiment of the present invention is an ultrasonic cleaning device comprising a housing adapted to be at least partially immersed in an aqueous environment and said housing optionally comprising a gripping device, a holding device for detachably holding tableware; a transducer, which is mounted in the housing, for oscillating the aqueous environment at the ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.

For ultrasonic devices, the power source may be a conventional power source, such as an electrical network, a rechargeable battery, a disposable battery, and rechargeable batteries or disposable batteries are preferred.

It is preferred that the surface that comes into contact with the scrub head is a hard surface. "Hard surface" means any surface that is traditionally considered hard, ie tableware, such as plates, glasses, cutlery, crockery, and also includes other surfaces, such as kitchen shelves, sinks, glass, windows, enamelled surfaces, metal surfaces, tiles, bathtubs, floors, etc. More preferably, the hard surface is table utensils.

The cleaning composition may contain conventional cleaning ingredients, and these are exemplified in further detail. The detergent can be dispensed from the container automatically or as required by the user of the machine. The detergent can be dispensed from the cartridge to the cleaning head and applied directly to the surface with the cleaning head. Alternatively, the cleaning agent may be dispensed on a surface that is not in contact with the cleaning head. For example, before, along either side or behind in the direction that the cleaning head moves over the surface. It is preferred that the cleaning agent be delivered to the surface adjacent to the cleaning head. Furthermore, if the device does not contain a cartridge, the cleaning agent may be applied by the operator either to the surface, to the dirt / dirt to be cleaned, or directly to the cleaning head. The cleaning agent can be used undiluted or as an aqueous solution.

The cleaning head may have any shape that is suitable for cleaning. The cleaning head could be, for example, a sponge, a steel wool, a scouring cloth, a foam structure or a brush. However, regardless of the design of the cleaning head, it is critical that the surface area is greater than 6.25 cm ² .

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The cleaning head is adapted for removable mounting, for ease of replacement, replacement of the type of head depending on the surface to be cleaned or the dirt to be removed and for general performance and flexibility of use.

The converter oscillates at a frequency of from 100 Hz to 20,000 kHz, more preferably oscillates from 100 Hz to 10,000 kHz, more preferably from 150 Hz to 2,000 kHz, more preferably from 150 Hz to 1,000 kHz, more preferably from 150 Hz to 100 kHz, more preferably from 200 Hz. Hz to 50 kHz. It is preferred that the average frequency be from 1000 Hz to 100 kHz, more preferably from 10,000 Hz to 70 kHz. It is also preferred that the device provide an output power per unit area of the scrub head of at least 0.02 W / cm ² , more preferably at least 0.05 W / cm ² , even more preferably at least 0.07 W / cm ² , even more preferably at least 0 W / cm ² . .08 W / cm ² .

Although not necessary, it is preferred that the device be adapted to operate when partially immersed in an aqueous environment, more preferably the device is adapted to be operable when fully immersed in an aqueous environment. Optionally, it is preferred that the device be water resistant, more preferably waterproof. That is, when the device is made for cleaning in an aqueous environment, for example, for washing dishes, dishes, etc., the device may be partially or fully immersed without damaging or harming the user. While a device that would only be used to clean hard surfaces, such as floors or tables, would not need to be adapted to operate partially submerged in an aqueous environment, it is preferable that the device be adapted to operate fully submerged in an aqueous environment, that the device is at least adapted to operate when partially immersed in an aqueous environment.

The present invention also includes a method of removing firmly adhered dirt from a hard surface food comprising the steps of:

(i) contacting the dirt with the detergent;

(ii) contacting the dirt with the cleaning head of the device according to either the first or second aspect and imparting ultrasonic energy to the dirt; and (iii) optionally, rinsing the hard surface with an aqueous solution.

Optionally, step (ii) may be performed first, then step (i), with the possibility of repeating this order until the dirt or steps in order (ii), (i) and (iii) are removed. Another method within the scope of the present invention is a method wherein the dirt is softened by applying a cleaning agent and the softened dirt is removed by applying ultrasonic energy to the softened dirt.

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Cleaner:

The cleaning composition comprises cleaning ingredients. The composition may be in any conventional form, for example, liquids, gel pastes, etc. The compositions may additionally contain aqueous solvents, for example water or low molecular weight alcohols, for example methanol or ethanol.

Cleaning additives

The cleaning composition comprises cleaning ingredients. These cleaning additives are for promoting or enhancing cleaning performance, treating the substrate to be cleaned, or adjusting the aesthetic aspect of the detergent composition (e.g., perfumes, pigments, dyes, etc.). Some suitable cleaning ingredients include builders, surfactants, enzymes, bleach activators, bleach catalysts, bleach enhancers, bleaching agents, alkalinity sources, antibacterial agents, pigments, perfumes, lime soap dispersants, polymeric dye transfer inhibitors, crystal growth inhibitors, photo-whitening agents, heavy metal ion masking agents, matting preservatives, antimicrobial agents, antioxidants, repositioning agents, soil release polymers, electrolytes, pH modifiers, thickening agents, abrasives, divalent ions, metal ion salts , enzyme stabilizers, anticorrosion inhibitors, diamines, foam stabilizing polymers, solvents, processing aids, fabric softening agents, optical brighteners, hydrotropes and mixtures thereof. The following section explains examples of supplemental materials.

Detergent components

The present invention may include an optional component in the manufactured composition. The level of detergent salt / component may vary widely depending upon the end use of the composition and its desired physical form. If present, the compositions will typically comprise at least 1% of a detergent component, and more typically from 10% to 80% and even more typically from 15% to 50% by weight of the detergent component. This does not mean that lower or higher levels are excluded.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, alkali metal, ammonium, and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates, and carbonates (including hydrogen sulfates) alumina-10- · · · t t t t t t t t t t t t t t t t t 10 10 10 10 10 10 · Ič ič ič ič ič ič ič ič ič ič. However, non-phosphate salts are required in some locations. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" components (as compared to phosphates), such as citrates, or in so-called "underbuilt" situations that may occur with zeolites or layered silicate ingredients. Mixtures of components are also contemplated.

Examples of silicate components are alkali metal silicates, especially those having a SiO 2: Na 2 O ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates, for example sodium layer silicates, described in US Patent 4,664,839, Η. P. Rieck, issued 1987-05-12. NaSKS-6 is a trademark for crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite components, the NaSKS-6 silicate component does not contain aluminum. NaSKS-6 has the delta-Na2SiC> 5 morphological form of the layered silicate. It can be prepared by the methods described, for example, in DE-A-3 417 649 and DE-A-3 742 043. SKS-6 is a highly preferred layered silicate for use in the present invention, but other layered silicates can be used, e.g. those having the general formula NaMSix O2x + _x l.yH ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as alpha, beta and gamma forms. As noted above, delta-Na 2 SiO 5 (form Na-SKS-6) is most preferred for use in the present invention. Other silicates can also be used, for example, magnesium silicate, which can serve as a brittleness in granular formulations, as a stabilizer for oxygen bleaching agents, and as a component for controlling the foam system.

Examples of carbonate salts as components are alkali earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001, published 1973-11-15.

Aluminosilicate builders may also be added as detergent salts of the present invention. Aluminosilicate builders are of great importance in most marketed high performance granular detergent compositions. Aluminosilicate components include those having the empirical formula:

M _z (zA10 _{2) y]} H ₂ 0 wherein the emanations are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5 and x is an integer from 15 to 264th

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Aluminosilicate ion exchange materials are available for sale. These aluminosilicates may have a crystalline or amorphous structure and may be naturally occurring aluminosilicates or synthetically produced. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel et al., issued 1976-1012. Preferred are Zeolite A, Zeolite P (B), Zeolite MAP, and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the general formula:

Nai ₂ [(AlO ₂ ) i ₂ (SiO ₂ ) ₁₂ ] -xH ₂ O where x is from 20 to 30, especially 17. This material is known as Zeolite A. Dehydrated zeolites (x = 0 to 10) are also in of the present invention. The aluminosilicate preferably has a particle size of 0.1 to 10 microns in diameter.

Organic detergent builders suitable for use in the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, the term "polycarboxylate" refers to compounds having multiple carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate component can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When the salt form is used, alkali metal salts such as sodium, potassium and lithium or alkanolammonium salts are preferred.

A wide selection of categories of useful materials are included in the polycarboxylate components. One important category of polycarboxylate detergent components includes ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287, Berg, issued 1964-04-07 and Lamberti et al. No. 3,635,830, issued 1972-01-18. See also " TMS / TDS " No. 4,663,071, Bush et al., issued 1987-05-05. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds, for example those described in U.S. Pat. U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergent ingredients include etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acid ethers, such as ethylacetic acid ethers. nitrilotriacetic acid as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

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Citrate components such as citric acid and soluble salts thereof (especially sodium salt) are polycarboxylate components of particular importance. Oxydisuccinates are also particularly useful in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in U.S. Pat. No. 4,566,984, Bush, issued 1986-01-28. Useful succinic acid components include C5-C20 alkyl and acenylsuccinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinic acid-derived components include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate (preferably), 2-pentadecenylsuccinate and the like. 1986-11-05.

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226, Crutchfield et al., issued 1979-03-13, and U.S. Patent 3,308,067, Diehl, issued 1967-03-07. See also Diehl, U.S. Pat. No. 3,723,322.

Aliphatic acids, such as C12-C18 monocarboxylic acids, may also be incorporated into the compositions alone or in combination with the aforementioned cleansing components, especially citrate and / or succinate components, to provide additional cleansing efficiency. Such use of aliphatic acids will generally result in reduced foam formation, which must be taken into account by the chemist who builds the composition.

Surfactants

Surfactants may be incorporated into the compositions of the present invention as an ultrasonic cleaning agent. The surfactant may comprise from 0.01% to 99.9% by weight of the composition, depending on the particular surfactants used and the desired effects. More typical levels are from 0.1% to 80%, more preferably from 0.5% to 60% by weight of the composition. Examples of suitable surfactants can be found in EMULSIFIERS AND DETERGENTS - Emulsifiers and Detergents, North American edition, 1997, McCutcheon Division, MC Publishing Company, U.S. Pat. No. 3,929,678, Laughlin et al., 1975-12-30 and U.S. Pat. 4,259,217, Murphy, 1981-03-31; Surfactant Science, Marcel Dekker, Inc, New York and Basel; "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd edition, 1994;

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99 9 99 99 9 9 99 9 "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987 and "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch), all of which are incorporated herein by reference.

The detersive surfactant may be nonionic, anionic, amphoteric, zwitterionic or cationic. Mixtures of these surfactants can also be used. Preferred detergent compositions include anionic detersive surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants or amphoteric surfactants.

Non-limiting examples of surfactants that are useful in the present invention include conventional C 11 -C 18 alkylbenzene sulfonates and primary, secondary to random alkyl sulfates, C 10 -C 18 alkylalkoxysulfates, C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides, C 11 -C 18 alpha-sulfonated aliphatic acid esters , C12-C18 alkyl and alkylphenolalkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C12-C18 betaines and sulphobetaines ("sultains"), C ₁₀ -C ₁₈ amine oxides, C ₆ -C ₁₈ branched or unbranched alkyl benzene sulphates, C ₆ -C ₁₈ branched or unbranched alkylbenzene sulfonates, C 6 -C 18 branched or unbranched alkyl alkoxy sulfates, and mixtures thereof, and the like. Other conventional surfactants are listed in standard texts.

Anionic surfactants

The anionic surfactants which are useful in the present invention are preferably selected from the group consisting of unbranched alkylbenzenesulfonates, alpha-alkenesulfonates, alkanesulfonates, alkyl ester sulfonates, alkyl sulfates, alkylalkoxysulfates, alkyl sulfonates, alkylalkoxycarboxylates, alkylsalkoxosinates, alkylsalkoxosinates, alkylsalkoxosinates, alkylsulfonates more preferably C 6 -C 18 branched or unbranched alkyl sulphates, C 6 -C 18 branched or unbranched alkylbenzene sulphonates, C 6 -C 18 branched or unbranched alkyl alkoxy sulphates and mixtures thereof. An effective amount, typically from 0.5% to 90%, preferably 5% to 60%, more preferably from 10% to 30% by weight of the anionic detersive surfactant may be used in the present invention.

Alkyl sulfate surfactants are another type of anionic surfactants that are of importance for use in the present invention. In addition to providing excellent general cleaning performance when used in combination with amides of aliphatic polyhydroxy acids (see below), including good grease / oil cleaning over a wide temperature range, washing • 4 4 4 4 4444

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By concentrating and washing times, dissolution of alkyl sulfates can be achieved, as well as improved formability in liquid detergent compositions are water-soluble salts or acids of formula ROSO3M, wherein R is preferably C10-C24, preferably alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably C 12 -C 18 alkyl or hydroxyalkyl and M is hydrogen or a cation, for example an alkali metal (Group IA) cation (eg, sodium, potassium, lithium), substituted or unsubstituted ammonium cations, eg methyl dimethyl and trimethylammonium and quaternary ammonium cations, e.g., tetramethylammonium and dimethylpiperidine and alkanolamine-derived cations, e.g. -16 and C1-6-alkyl alkyl chains are preferred for higher wash temperatures (n and above 50 ° C).

Alkylalkoxy sulfate sulfate surfactants are another category of useful anionic surfactants. These surfactants are water-soluble salts or acids of the general formula RO (A) _m SO 3 M, wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having an alkyl component C 10 -C 24, preferably C 12 -C 20 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation, for example a metal cation (for example sodium, potassium, lithium, etc.), ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated in this invention. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations, for example tetramethylammonium, dimethylpiperidine, and alkanolamine-derived cations, e.g., monoethanolamine, diethanolamine and triethanolamine, and mixtures thereof. Exemplary surfactants are C12-C18 alkylpolyethoxylate (1.0) sulfate, C12-C18 alkylpolyethoxylate (2.25) sulfate, C12-C18 alkylpolyethoxylate (3.0) sulfate, and C12-C18 alkylpolyethoxylate (4.0) sulfate, where M is suitably selected from sodium and potassium . Surfactants for use in the present invention can be prepared from natural or synthetic alcohol raw materials. Chain lengths represent the average hydrocarbon distribution, including branching.

Examples of suitable anionic surfactants are in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A wide selection of such surfactants is also generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al., issued 1975-12-30, at column 23, line 58 through column 29, line 23.

15 4 4 4 4 44 4 4 4 4 4 4 4 4 4 4 4 4

Other possible surfactants are dianionic. These are surfactants having at least two anionic groups present in the surfactant molecule. Some suitable dianionic surfactants are further described in co-pending U.S. Pat. serial numbers 60/020 503 (statement number 6160P), 60/020 772 (statement number 6161P), 60/020 928 (statement number 6158P), 60/020 832 (statement number 6159P) and 60/020 773 (statement number 6162P) ), all filed 1996-06-28 and 60/023 539 (statement number 6192P), 60/023 493 (statement number 6194P), 60/023 540 (statement number 6193P) and 60/023 527 (statement number 6195P), filed 1996-08-08, the disclosures of which are incorporated herein by reference. Other commonly used surfactants are listed in standard texts.

Nonionic surfactants

Particularly preferred are nonionic surfactants. The nonionic surfactants may be present in an amount of from 0.01% to 40% by weight, preferably from 0.1% to 30%, and most preferably from 0.25% to 20%.

Particularly preferred in the present invention are mixed nonionic surfactants. Although a wide range of useful nonionic surfactants can be selected from mixed nonionic surfactant systems, for purposes of the compositions of the present invention, it is preferred that the nonionic surfactants include both low haze surfactants, e.g., represented by ether-terminated poly ( oxyalkylated alcohol surfactants as well as high haze nonionic surfactant (s) as described below. "Turbidity temperature" as used herein is a known property of nonionic surfactants resulting from the surfactants becoming less soluble with increasing temperatures. The temperature at which the discovery of the second phase is observable is called the "turbidity temperature" (see Kirk Othmer, pp. 360-362, supra).

As used herein, a "low cloud point" nonionic surfactant is defined as an additive of a nonionic surfactant system having a cloud point less than 30 ° C, preferably less than 20 ° C, and most preferably less than 10 ° C a is represented by ether-terminated poly (oxyalkylated) alcohols as described herein.

· - φ φ · · · · · · · · · · · · · · - - - -

Naturally, other low-temperature surfactants can be incorporated in conjunction with ether-terminated poly (oxyalkylated) surfactants. Such optional low-temperature surfactants include nonionic alkyloxylated surfactants, especially primary alcohol ethoxylates and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Such optional low clouding surfactants also include, for example, an ethoxylated-propoxylated alcohol (e.g., Poly-Tergent® SLF18 from Olin Corporation) and epoxy-terminated poly (oxyalkylated) alcohols (e.g., Poly-Tergent® SLF18B series of nonionic from Olin Corporation, as described, for example, in WO 94/22 800, Olin Corporation, published 1994-10-13). These nonionic surfactants may optionally contain propylene oxide in an amount of up to 15% by weight. Other preferred nonionic surfactants can be prepared by the methods described in U.S. Pat. No. 4,223,163, Builloty, issued 1980-09-16, incorporated herein by reference.

Optional low cloud point nonionic surfactants include a polyoxyethylene-polyoxypropylene block polymer compound. Block polyoxyethylene-polyoxypropylene polymer compounds include compounds based on ethylene glycol, propylene glycol, glycerol, trimethylpropane, and ethyldiamine as the starting reactive hydrogen compound. Some of the block polymeric surfactant compounds designated PLURONIC ®, REVERSED PLURONIC ® and TETRONIC ®, from BASF-Wyandotte Corp., Wyandotte, Michigan, USA, are suitable in the compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. These surfactants are typically useful in the present invention as low-temperature non-ionic surfactants.

As used herein, a "high cloud point" nonionic surfactant is defined as an additive of a nonionic surfactant system having a cloud point greater than 40 ° C, preferably greater than 50 ° C and most preferably greater than 60 ° C . The nonionic surfactant system preferably comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing up to 20 carbon atoms with 6 to 15 moles of ethylene oxide per alcohol or alkylphenol molecule, based on the diameter. Such high haze nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by Shell).

• * · » »· and «· t • • 9 9 99 • • • • ··· 9 • • · • • • · • · ·· • * · ·· 99

For the purposes of the present invention, it is also preferred that the high haze nonionic surfactants further have a hydrophilic-lipophilic balance ("HLB - Hydrophile-Lipophile Balance", see Kirk Othmer supra) herein in the range of 9 to 15, preferably Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by Shell).

Another preferred high-temperature, non-ionic surfactant is derived from an unbranched or preferably branched chain or a secondary aliphatic alcohol containing from 6 to 20 carbon atoms (C6-C20 alcohol), including secondary alcohols and branched chain primary alcohols. High-temperature nonionic surfactants are preferably branched or secondary alcohol ethoxylates, more preferably mixed C9 / 11 or Cii / 15 branched alcohol ethoxylates condensed with an average of 6 to 15 moles, preferably 6 to 12 moles, and most preferably 6 to 9 moles of ethylene oxide per mole of alcohol. The ethoxylated nonionic surfactant thus derived preferably has a narrow ethoxylate distribution in relation to the diameter.

Preferred nonionic surfactant systems useful in the present invention are mixed high and low cloud point nonionic surfactants, combined in a weight ratio preferably in the range of from 10: 1 to 1: 10.

Another type of preferred nonionic surfactant is an alkyl alkoxylate-terminated surfactant. Suitable alkylalkoxylate-terminated surfactants are epoxy-terminated poly (oxyalkylated) alcohols, represented by the general formula: R 10 [CH 2 CH (CH 3) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ₂ ] (I) is a straight or branched aliphatic hydrocarbon substituent having from 4 to 18 carbon atoms; R ₂ is a straight or branched aliphatic hydrocarbon substituent having from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I has at least 10 carbon atoms in the terminal epoxy unit [CH ₂ CH (OH) R ₂ ]. Suitable surfactants of the formula I according to the invention are the nonionic POLY-TERGENT® SLF-18B surfactants from Olin Corporation, as described, for example, in WO 94/2280, Olin Corporation, published 1994-10-13.

···· · ·· ·· ·· · ··

One preferred ether-terminated poly (oxyalkylated) alcohol has the general formula:

R ¹ O [CH 2 CH (R ³ ) O] x [CH ₂ ] _to CH (OH) [CH ₂ ] _j OR ² ] wherein R ¹ and R ² are unbranched or branched, saturated or unsaturated, aliphatic or annulene hydrocarbon substituents, having from 1 to 30 carbon atoms; R ³ is H or a straight-chain aliphatic hydrocarbon substituent having from 1 to 4 carbon atoms; x is an integer having an average value of from 1 to 30, wherein when x is 2 or greater, R may be the same or different as integers having an average value of from 1 to 12, and more preferably 1 to 5.

R 1 and R ² are preferably unbranched or branched, saturated or unsaturated, aliphatic or annulene hydrocarbon substituents having from 6 to 22 carbon atoms with 8 to 18 carbon atoms as most preferred. H or an unbranched aliphatic hydrocarbon substituent having from 1 to 2 carbon atoms is most preferred for R. x is preferably an integer having an average value of from 1 to 20, more preferably from 6 to 15.

As described above, when in preferred embodiments x is greater than 2, R ³ may be the same or different. That is, R ³ can make modifications to any of the alkyleneoxy units described above. For example, if x is 3, R ³ can be selected from ethyleneoxy (EO) or propylenoxy (PO) and vary in order (EO) (PO) (EO; (EO) (EO) (PO); (EO) (EO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) (PO) if a higher integer value for x and include, for example, more units (EO) and a much smaller number of units (PO).

Particularly preferred surfactants as described above include surfactants having a low cloud point of less than 20 ° C. Low haze temperature surfactants can then be used in conjunction with high haze temperature surfactants, as described in more detail below, for an excellent cleaning benefit.

The ether-terminated poly (oxyalkylated) alcohol surfactants are most preferably surfactants wherein k is 1 and is 1 such that the surfactants have the general formula:

R ¹ O [CH 2 CH (R ³ ) O] x CH ₂ CH (OH) CH ₂ OR ² wherein R ¹ , R ² and R ³ are defined as above and x is an integer with an average value of 1 to 30, preferably 1 to 30 20, and more preferably from 6 to 18. The most preferred are surfactants, such as surfactants.

Where R ¹ and R ² range from 9 to 14, R ³ is H forming ethyleneoxy and x ranges from 6 to 15.

The ether-terminated poly (oxyalkylated) alcohol surfactants consist of three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end group. The alkyl ether end group and the alcohol serve as the hydrophobic, oil-soluble portion of the molecule, while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.

These surfactants show significant improvements in stain and film properties and greasy soil removal compared to conventional surfactants, especially when used in conjunction with high haze surfactants.

Another suitable class of nonionic surfactants includes sugar-derived surfactants, for example amides of aliphatic polyhydroxy acids of the formula: O ₂ II r ² cnz

Wherein: R ¹ is H, C 1 -C 4,2-hydroxyethyl, 2-hydroxylpropyl or mixtures thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (ie methyl); and R ² is C 5 -C 31, preferably unbranched C 7 -C 19 alkyl or alkenyl, more preferably unbranched C 9 -C 17 alkyl or alkenyl, most preferably unbranched C 1 -C 4 alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxy group having an unbranched hydrocarbon chain with at least 3 hydroxyls directly attached to the chain or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. Concentrated dextrose corn syrup, concentrated fructose corn syrup and concentrated maltose corn syrup, as well as the individual sugars listed above, can be used as raw materials. Corn syrups may provide a mixture of sugar components for Z. It must be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be won from the group consisting of -CH2- (CHOH) _n -CH2 OH, -CH (CH2OH) - (CHOH) _{n .i-CH2} OH, _-CH2 - (CHOH) ₂ (CHOR ' (CHOH) -CH ₂ OH and alkoxylated derivatives thereof, wherein a is an integer from 3 to 5 inclusive, R 'is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially -CH 2 (CHOH) 4-CH 2 OH.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·· ·· ·

R 'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ² -CO-N = can be, for example, coconut amide, stearic acid amide, oleic acid amide, lauric acid amide, myristic acid amide, capric acid amide, palmitic acid amide, tallow amide, etc.

Z may be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl etc.

Methods for preparing aliphatic polyhydroxy acid amides are known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine and then reacting the N-alkyl polyhydroxyamine with an aliphatic ester or triglyceride in a condensation / amidation step to form the Nalkylamide aliphatic N-polyhydroxy acid product. Processes for preparing compositions containing amides of aliphatic polyhydroxy acids are disclosed, for example, in British Patent Specification 809,060, Thomas Hedley & Co., published 1959-02-18, U.S. Pat. No. 2,965,576, E.R. Wilson, issued 1960-12-20, U.S. Pat. No. 2,703,798, Anthony M. Schwartz, issued 1955-03-08 and U.S. Pat. No. 1,985,424, Piggott, issued 1934-12-25, all of which are incorporated herein by reference.

Preferred alkyl polyglycosides have the general formula:

R ² O (C _n H 2 _n O) t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form a glucoside (attachment to the 1- position). Further glycosyl units can then be attached between their 1- position and the preceding glycosyl units of 2-, 3-, 4- or 6-, preferably predominantly 2-.

These and other nonionic surfactants are known in the art and are described in more detail in the Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, p.360-379, " Surfactants and Detersive Systems ", incorporated herein by reference.

Other useful nonionic detergent surfactants are generally disclosed in U.S. Pat. U.S. Patent 3,929,678, Laughlin et al., issued 1975-12-30, at column 13, line 14 to column 16, line 6, which is incorporated herein by reference.

Cationic surfactants

Cationic surfactants suitable for use in the compositions of the present invention include surfactants having a long chain hydrocarbon group. Examples of such cationic co-surfactants include ammonium, co-surfactants such as alkyldimethylammonium halides and co-surfactants having the general formula:

[R ² (OR ³ ) y] [R ⁴ (OR ³ ) y] ₂ R ⁵ N ⁺ X 'wherein R ² is an alkyl or alkylbenzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R ³ is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH (CH) 3 -, CH 2 CH (CH 2 OH) - -CH 2 CH 2 CH 2 -, and mixtures thereof; each R ⁴ is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzylic cyclic structures formed by linking two groups R ⁴ , -CH ₂ CHOHCHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or hexose polymer having a molar moiety a mass of less than 1000 and hydrogen when y is not 0; R ⁵ is the same as R ⁴ or is an alkyl chain wherein the total number of carbon atoms R plus R is not more than 18; each y is from 0 to 10 and the sum of y values is from 0 to 15; and X is any compatible anion.

Examples of other suitable cationic surfactants are described in the following documents, all of which are incorporated herein by reference in their entirety:

, M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers (Detergents & Emulsifiers, North American Edition 1997); Schwartz et al., Surface Active Agents, Their Chemistry and Technology, New York, USA, Inter-Publishers; U.S. Pat. U.S. Patent 3,155,591; U.S. Pat. U.S. Patent 3,929,678; U.S. Pat. U.S. Patent 3,959,461; U.S. Pat.

U.S. Patent 3,959,461; U.S. Pat. U.S. Patent 4,387,090 and U.S. Pat. No. 4,228,044.

Examples of suitable cationic surfactants are those which correspond to the general formula:

+

X '• · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Wherein R 1, R 2, R 3 and R 4 are independently selected from an aliphatic group of 1 to 22 carbon atoms or an annulene, alkoxy, polyoxyalkylene, alkylamide, hydroxylalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a salt-forming anion, for example, an anion selected from halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkyl sulfate. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether bonds and other groups, for example amino groups. Long-chain aliphatic groups, for example groups having 12 carbons or more, may be saturated or unsaturated. Preferably, R 1, R 2, R 3 and R 4 are independently selected from C 1 -C 22 alkyl. Particularly preferred are cationic materials comprising two long alkyl chains and two short alkyl chains or materials containing one long alkyl chain and three short alkyl chains. The long alkyl chains in the compounds described in the preceding sentence have from 12 to 22 carbon atoms, preferably from 16 to 22 carbon atoms, and the short alkyl chains in the compounds described in the preceding sentence have from 1 to 3 carbon atoms, preferably from 1 to 2 carbon atoms.

Suitable levels of the cationic detergent surfactant of the present invention, if present, are from 0.1% to 20%, preferably from 1% to 15%, although much higher levels may be used, e.g., up to 30% or more, especially in formulations of a nonionic surfactant composition with a cationic (i.e., a limited amount of anionic surfactant or without anionic surfactant).

Other surfactants

Amphoteric or zwitterionic detersive surfactants, if present, are generally applicable at levels ranging from 0.1% to 20% by weight of the detergent composition. Levels will often be limited to 5% or less, especially when the amphoteric surfactant is expensive.

Suitable amphoteric surfactants include amine oxides that correspond to the general formula

Wherein R is a primary alkyl group containing 6 to 24 carbons, preferably 10 to 18 carbons, and wherein R 'and R are each independently an alkyl group containing 1 to 6 carbon atoms. The arrow in the formula is the usual representation of a semipolar bond.

• · · · · · · · · · · · ·

-23Aminoxides are semi-polar surfactants and contain water-soluble amine oxides containing one alkyl group of 10 to 18 carbon atoms and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 1 3 carbon atoms; water-soluble phosphine oxides containing one alkyl group of 10 to 18 carbon atoms and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides which contain one alkyl group having 10 to 18 carbon atoms and a group selected from the group consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

Preferred amine oxide surfactants have the general formula

O

R ³ (OR ⁴ ) XN (R ⁵ ) 2 wherein R ³ is an alkyl, hydroxyalkyl or alkylphenyl group or a mixture thereof containing from 8 to 22 carbon atoms; R ⁴ is an alkylene or hydroalkylene group containing from 2 to 3 carbon atoms or a mixture thereof; x is from 0 to 3; each R ⁵ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. The R ⁵ groups may be linked to each other, for example by an oxygen or nitrogen atom, or may form a cyclic structure.

In particular, these amine oxide surfactants comprise C 10 -C 18 alkyldimethylamine oxides and C 8 -C 18 alkoxyethyldihydroxyethylamine oxides. The amine oxide is preferably present in the composition in an effective amount, more preferably 0.1% to 20%, even more preferably from 0.1% to 15% and even more preferably from 0.5% to 10% by weight.

Some suitable zwitterionic surfactants which can be used in the present invention include betaine and betaine-like surfactants, wherein the molecule contains both basic and acidic groups that form an internal salt giving the molecule both cationic and anionic groups over a wide range pH. Some common examples of such surfactants are described in U.S. Pat. and U.S. Pat. Nos. 2,082,275,2702,279 and 2,255,082, incorporated herein by reference. One zwitterionic compound has the general formula

R2

R3

X

-24 · ···· ♦ · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ····· · · · · 4 ·· ·· ·····

1Τ '!

wherein R is an alkyl substituent containing from 8 to 22 carbon atoms, R and R contain from 1 to 3 carbon atoms, R ⁴ is an alkylene chain containing from 1 to 3 carbon atoms, X is selected from the group consisting of hydrogen or a hydroxyl substituent, Y is selected from the group consisting of carboxyl or sulfonyl substituents wherein the sum of the R ¹ , R ² and R ³ substituents is from 14 to 24 carbon atoms.

Zwitterionic surfactants as mentioned above contain both a cationic and anionic moieties and are substantially electrically neutral, where the numbers of anionic charges and cationic charges in the surfactant molecule are substantially the same. Zwitterions, which typically contain both a quaternary ammonium group and an anionic group that is selected from sulfonate and carboxylate groups, are desirable because they retain amphoteric character over most of the pH range of interest in hard surface cleaning. The sulfonate group is preferably an anionic group.

Antimicrobial agents

An antimicrobial agent is a compound or substance that kills or prevents or inhibits the growth and reproduction of microorganisms. A properly selected antimicrobial agent maintains stability under the conditions of use and storage (pH, temperature, light, etc.) for a desired period of time. A desirable property of an antimicrobial agent is that it is safe and non-toxic in handling, formulation and use, is environmentally acceptable and cost effective. Classes of antimicrobial agents include, but are not limited to, chlorophenols, aldehydes, biguanides, antibiotics, and biologically active salts. Some preferred antimicrobial agents are bronopol, chlorhexide indiacetate, TRICOSAN ™, hexetidine or parachlorometaxylenol (PCMX). More preferably, the antimicrobial agent is TRICOSAN ™, chlorhexide indiacetate or hexetidine.

The antimicrobial agent, when used, is present in a microbially effective amount, more preferably from 0.01% to 10.0%, more preferably from 0.1% to 8.0% even more preferably from 0.5% to 2.0% by weight means.

-25 Bleaching agents

Sources of hydrogen peroxide are described in detail in the publication incorporated herein by the Kirk Othmer's Encyclopedia of Chemical Technology - Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed. (1992, John Wiley & Sons), Vol. 4, pp. 271-300, "Bleaching Agents (Survey)," and include various forms of sodium perborate and sodium percarbonate, including various coated and modified forms. An "effective amount" of a hydrogen peroxide source is any amount that is capable of measurably improving stain removal (especially tea stains) from a soiled tableware as compared to a non-hydrogen peroxide source where the consumer washes dirty dishes in a household automatic dishwasher in the presence of alkali .

More generally, the source of hydrogen peroxide in the present invention is a suitable compound or mixture that provides an effective amount of hydrogen peroxide under consumer conditions. Levels can vary widely and typically range from 0.1% to 70%, more typically from 0.5% to 30% by weight of the composition of the invention.

The preferred hydrogen peroxide source used in the present invention may be any suitable source, including hydrogen peroxide itself. For example, perborate, such as sodium perborate (any hydrate, but preferably mono- or tetrahydrate), sodium percarbonate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used in the present invention. Active oxygen sources such as persulfate bleach (e.g., OXONE, manufactured by DuPont) are also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of conventional sources of hydrogen peroxide can also be used.

A preferred percarbonate bleaching agent consists of dry particles having an average particle size in the range of 500 microns to 1000 microns, with no more than 10% by weight of said particles less than 200 microns, and no more than 10% by weight of said particles larger than 1%. 250 micrometers. Optionally, the percarbonate may be coated with a silicate, borate or water-soluble surfactant. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Although this is not preferred for compositions of the present invention that contain cleaning enzymes, compositions of the present invention may also contain a bleaching material as a bleaching agent.

26 · toto ♦ ♦ 99 to to to to to to to to to to to

9 99 99 999 99

9 9 9 9 9 99

999 9 99 99 99 999 chlorine type. Such agents are known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC").

Organic peroxides, especially diacyl peroxides

These compounds are widely elucidated in the Kirk Othmer's Encyclopedia of Chemical Technology. 17, John Wiley & Sons, 1982 on pages 27 to 90, and in particular pages 63 to 72, all of which are incorporated herein by reference. If diacyl peroxide is used, it will preferably be one that exhibits minimal adverse effect on staining and coating formation. Preferred diacyl peroxides include dibenzoyl peroxide.

Bleach catalysts containing metal

The compositions and methods of this invention utilize metal bleach catalysts that are effective for use in ADD compositions. Bleach catalysts containing manganese and cobalt are preferred.

One type of metal-containing bleach catalyst is a catalyst system which comprises a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese, a cationic metal cation with little or no bleaching activity, for example cations zinc or aluminum and a masking agent with defined constants of stability for the catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Patent Nos. 5,246,621 and 5,244,594. Preferred examples of such catalysts include Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-1,4,7 -triazacyclononane) 2- (PF6) 2 ("MnTACN"), Mn ⁱⁿ 2 (µ-O) and (µ-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- ( ClO4) 2, Mn ^IV 4 (u O) ₆ (1,4,7triazacyklononan) 4- (ClO4) 2, Mn ^{in MnIV4} (u O) i (u-OAc) 2 (l, 4,7-trimethyl-l 4,7-triazacyclononane) 2- (ClCl 4) 3 and mixtures thereof. See also European Patent Application Publication No. 549 272. Other ligands suitable for use in the present invention include 1,5,9-trimethyl-159-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononate and mixtures thereof.

• 9 9 9 9 9 · 9 9 27 27 27 27 27 .... .... .... .... .... .... .... .... .... ....

Bleach catalysts that are useful in automatic dishwashing compositions and concentrated powdered detergent compositions can also be selected as suitable for the present invention. For examples of suitable bleach catalysts, see U.S. Pat. Nos. 4,246,612 and 5,227,084.

Other bleach catalysts are described, for example, in European Patent Application Publication No. 408 131 (cobalt complex catalysts), European Patent Application Publication Nos. 384,503 and 306,089 (Metal-Poririnine Catalysts), U.S. Pat. No. 4,728,455 (manganese / multidentate ligand catalyst); No. 4,711,748 and European Patent Application Publication No. 224,952 (manganese absorbed onto aluminosilicate); No. 4,601,845 (aluminosilicate carrier with manganese and zinc or magnesium salt); No. 4,626,373 (manganese / ligand catalyst); No. 4,119,557 (ferric complex catalyst); U.S. Patent 2,054,019 (cobalt chelate catalyst), Canadian 866,191 (transition metal salts), U.S. Pat. 4,430,243 (chelates with manganese and non-catalytic metal cations) and U.S. Pat. No. 4,728,455 (manganogluconate catalyst).

Preferred are cobalt catalysts having the general formula:

[Co (NH ₃ ) n (M ') _m ] Y _y wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M 'is a labile coordination group, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably m is 1); m + n = 6; and Y is a suitably selected counter ion, present in the number of y, wherein y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2, when Y is a charged -1 anion) to obtain a charge balanced salt.

Preferred cobalt catalysts of this type which are useful in the present invention are cobaltopentaamine chloride salts having the general formula [Co (NH ₃ ) ₅ Cl] Y _y, and in particular [Co (NH ₃ ) ₅ Cl] Cl ₂ .

More preferred are compositions of the present invention which employ cobalt (III) bleach catalysts having the general formula:

[Co (NH ₃ ) _n (M) _m (B) _b ] wherein _y is cobalt in the oxidation stage +3; n is 4 or 5 (preferably 5); M is one or more cobalt-coordinated ligands at two sites; b is 0 or 1 (preferably 0); B is a ligand coordinated with cobalt at two sites; b is 0 or 1 (preferably 0) and when b = 0 then m + n - 6 and when b = 1 then m = 0 and n = 4; aT is one or more suitably selected counterions which are · ♦ · ♦

-28 present in the number of y, where y is an integer to obtain a charge balanced salt (preferably y is 1 to 3; most preferably 2 when T is a charged anion of -1); and wherein said catalyst further has a base hydrolysis rate constant of less than 0.23 M ^-1 (25 ° C).

Preferred T are selected from the group consisting of chloride, iodide, I3 ', formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ₆ ', BF ₄ ', B (Ph) 4' , phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T may be protonated if there is more than one anionic group in T, e.g. HPO4 ² ·, HCO3 ·, H2PO4 · etc. Furthermore, T may be selected from the group consisting of non-traditional inorganic anions, for example anionic surfactants (e.g., unbranched alkylbenzene sulfonates (LAS), alkylsulfates (AS), alkyl ethoxy sulfonates (AES), etc.) or anionic polymers (e.g. polyacrylates, polymethacrylates, etc.).

For example, M groups include, but are not limited to, F ', SO ₄ ² '. NCS ', SCN, S2O3 ² ·, NH3, PO ₄ ³ ' and carboxylates (which are preferably monocarboxylates but more than one carboxylate per group may be present, in which case the other carboxylate in group M may be protonated or in salt form) . Optionally, M may be protonated if there is more than one anionic moiety in M (eg, HPO4 ² ·, HCO ³ ·, H ² PO ⁴ ', HOC (O) CH 2 C (O) -, etc.). Preferred M groups are substituted and unsubstituted C 1 -C 30 carboxylic acids having the general formula:

RC (O) Where R is preferably selected from the group consisting of hydrogen and C 1 -C 30 (preferably C 1 -C 6) unsubstituted or substituted alkyl, C 6 -C 30 (preferably C 6 -C 6) unsubstituted or substituted aryl, and C 3 -C 30 (preferably C 5 -C 18) unsubstituted or substituted heteroaryl wherein the substituents are selected from the group consisting of -NR'3, -NR'4 ⁺ , -OR ', -C (O) OR', -C (O) NR '2 wherein R' is selected from the group consisting of hydrogen and C 1 -C 6 groups. Thus substituted R includes groups - (CH ₂ ) _n OH and - (CE bnNRV), wherein n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.

Most preferred M are carboxylic acids having the above general formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, unbranched or branched C 4 -C 12 alkyl and benzyl. Most preferably R is methyl. Preferred M carboxylic acids include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenic, oleic,

4444 · 4 44 44 4 • 4 4 · 4 4 44

4 44444 φ 4 4

4,444 4 4 · _ 29 - ..............

palmitic, triflate, tartaric, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic acid.

Groups B include carbonates, di- and higher carboxylates (e.g., oxalate, malonate, malate, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, betaalanine, phenylalanine).

Cobalt bleach catalysts useful in the present invention are known, for example, together with their basic hydrolysis rates, in ML To You, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94. For example, Table 1 on page 17 provides basic hydrolysis rates (denoted coH there) for cobalt-pentaamine catalysts complexed with oxalate (k _OH = 2.5 x 10 ^ M). ¹ / (25 ° C)), NOS '(kOH = 5.0 x 10 ^ MV ¹ (25 ° C)), formate (koH = 5.8 x 10 ^ MV ¹ (25 ° C)) and acetate (kOH = 9.6 x 10 4 M + ¹ (25 ° C)). Most preferable cobalt catalysts which are useful in this invention are kobaltpentaamin acetate salts having the formula [Co (NH3) 5 OAc] T _y, wherein OAc represents an acetate group and especially chloride kobaltpentaaminacetátu [Co (NH3) ₅ OAc] C1 _2; as well as [CO (NH 3) 5 EtOAc] (OAc) 2; [CO (NH ₃ ) ₅ OAc] (PF ₆ ) 2; [CO (NH ₃ ) 5 EtOAc] (SO ₄ ); [CO (NH ₃ ) 5 EtOAc] (BF ₄ ) 2; and [CO (NH ₃ ) ₅ OAc] (NO ₃ ) 2.

The cobalt catalyst of the present invention can be produced by the synthetic route described in U.S. Pat. Nos. 5,559,261, 5,581,005 and 5,597,936, the disclosures of which are incorporated herein by reference.

Catalysts may be co-processed with supplementary materials to reduce the color impact, if desired, on the aesthetic aspect of the product or to be incorporated into particles containing enzymes as exemplified above or the compositions may be made to contain catalysts. "Speckles".

For convenience and not limitation, the cleaning compositions and cleaning methods of the present invention can be adapted to provide as required in an aqueous washing medium at least one part per hundred million active bleach catalyst components and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm and most preferably from 0.1 ppm to 5 ppm of the bleach catalyst component in the wash solution. In order to obtain such levels in the wash solution, the compositions of the present invention will contain from 0.000% to 0.2%, more preferably from 0.004% to 0.08% bleach catalyst, by weight of the cleaning compositions.

φ · φ «φ« · · • • • • • • • • • • • • • • • 9 9 9 9 9 9 9 9 9 9 9 9 9

Preferred bleach catalysts, together with methods for their use, can further be found in U.S. Pat. U.S. Patent Nos. 5,705,464, 5,804,542, 5,798,326, 5,703,030 and 5,599,781, all of which are incorporated herein by reference.

Bleach activators

If the composition comprises a peroxygen bleach component, the composition is preferably formulated with an activator (peroxyacid precursor). Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), benzoylbenzenesulfonate (NOB), (BZVL), octanoyloxybenzenesulfonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam, NOBS, TAED and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of from 8 to 9.5 are those having an OBS or VL leaving group.

Preferred bleach activators are those described in U.S. Pat. No. 5,130,045 to Mitchel et al., and at 4,412,934 to Chung et al. and in co-pending U.S. patent applications U.S. Pat. sér. Nos. 08/064 624, 08/064 623, 08/064 621, 08/064 562, 08/064 564, 08/082 270 and co-pending U.S. application Ser. sér. No. 08/133 691 (P&G Time 4890R), M. Bums, AD Willey, RT Hartshom, CKGhosh entitled "Bleaching Compounds Comprising Peroxyacid Activators Glued With Enzymes", all incorporated by reference of this document.

The molar ratio of peroxygen bleach compound (such as AvO) to bleach activator in the present invention generally ranges from at least 1: 1, preferably from 20: 1 to 1: 1, more preferably from 10: 1 to 3: 1.

Quaternary substituted bleach activators can also be incorporated. These detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peroxyacid (QSP); more preferably QSBA. Preferred QSBA structures are further described in co-pending U.S. Pat. sér. Nos. 08/298 903, 08/298 650, 08/298 906 and 08/298 904, filed 1994-08-31, incorporated herein by reference.

Φ Φ φφφφ φφφ φ φ φφφφφ φφ

-31φ · φφφφφφφφφφφφ φφφφφφφφφφ

The levels of bleach activators in the present invention can vary widely, e.g. from 0.01% to 90% by weight of the composition, although more typically lower levels are used, for example more preferably from 0.1% to 30%, even more preferably from 0.1% to 30%. 20%, more preferably from 0.5% to 10% and even more preferably from 1% to 8% by weight of the composition.

Preferred hydrophilic bleach activators include Ν, Ν, Ν ', Ν'-tetraacetyl ethylenediamine (TAED) or any of its close relatives that contain triacetyl or other asymmetric derivatives. TAED and acetylated carbohydrates such as glucosopentaacetate and tetraacetylxylose are preferred hydrophilic bleach activators. Depending on the application, acetyltriethyl citrate liquid as well as phenylbenzoate also have some benefits.

Preferred hydrophobic bleach activators include substituted amide types, described in further detail herein, for example, NAPAA-related activators and activators related to certain imidoperoxyacid bleaching agents, such as described in U.S. Pat. No. 5,061,807, Hoechst Aktiengesellchaft, Frankfurt, Germany, issued 1991-10-29.

Other suitable bleach activators include sodium 4-benzoyloxybenzenesulfonate (SBOBS); sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; sodium 4-methyl-3-benzoyloxybenzoate (SPCC); trimethylammoniumtoluyloxybenzenesulfonate or sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (STHOBS).

The bleach activators may be used in any amount, typically up to 20%, preferably from 0.1% to 10% by weight of the composition, although higher levels, 40% or more, are acceptable, for example in highly concentrated bleach additive product forms or automatic dosing in the device.

The highly preferred bleach activators useful herein are amide substituted and have one of the following general formulas:

OO 00

H IIII II

R ¹ -C-N-R2-Cl, R1-R2-NC-CL

R ⁵ R ⁵ or mixtures thereof, wherein R ¹ is alkyl, aryl or alkaryl containing from 1 to 14 carbon atoms, including both hydrophilic types (short R ¹ ) and hydrophobic types (R ¹ is especially from 6, preferably 8 to 12) R ² is alkylene, arylene or alkarylene containing from 1 to 14 carbon atoms,

-32R ⁵ is H or alkyl, aryl, or alkaryl containing 1 to 10 carbon atoms and L is a leaving group as defined above in the document.

Preferred bleach activators also include those of the above formula wherein L is selected from the group consisting of:

wherein R ³ is as defined above and Y is -SCVM * or CC>2'M ⁺ , wherein M is as defined above.

Preferable examples of the bleach activators of the above formula include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.

Other useful activators which are disclosed in U.S. Pat. No. 4,966,723, are of the benzoxazine type, for example, the CeFL 1 cyclic chain to which they are attached at the 1,2-positions of the -C (O) OC (R ') = N-. A highly preferred benzoxazine type activator is:

O

II

Very useful in the present invention are acylalctam activators, in particular acyl caprolactams (see e.g. WO 94-28 102 A) and acylvalerolactams (see U.S. 5,503,639) of the general formula:

wherein R ⁶ is H, an alkyl, aryl, alkoxyaryl and alkaryl group containing from 1 to 12 carbon atoms or substituted phenyl having from 6 to 18 carbons. See also U.S. Pat. No. 4,545,784, which discloses acyl caprolactams, including benzoyl caprolactam absorbed into sodium perborate.

Non-limiting examples of additional activators useful in the present invention are found in U.S. Pat. No. 4,915,854, U.S. Pat. 4,412,934 and U.S 4,634,551.

Other activators useful in the present invention include those of U.S. Pat. Examples include esters of an organic acid and ethylene glycol, diethylene glycol or glycerin, or an acid imide of an organic acid and ethylenediamine; wherein the organic acid is selected from methoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid, butoxyacetic acid, 2- butoxypropionic acid, p-butoxybenzoic acid, 2-methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid, 2-methoxy-2-methylethoxyacetic acid, 2-ethoxyethoxyacetic acid, 2- (2-ethoxyethoxy) propionic acid, p- (2 -ethoxyethoxy) benzoic acid, 2-ethoxy-1-methylethoxyacetic acid, 2-ethoxy-2-methylethoxyacetic acid, 2-propoxyethoxyacetic acid, 2-propoxy-1-methylethoxyacetic acid, 2propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid, 2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid, 2- (2-methoxyethoxy) ethoxyacetic acid, 2- (2-methoxy-1-methylethoxy) ethoxyacetic acid 2- (2-methoxy-2-methylethoxy) ethoxyacetic acid and 2- (2-ethoxyethoxy) ethoxyacetic acid.

Useful in the present invention as oxygen bleaching agents are inorganic peroxides such as Na 2 CO 2, hyperoxides such as KO 2, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide and inorganic peroxoacids and salts thereof such as peroxosulfuric acid, especially potassium peroxodisulfate and more preferably peroxo (mono) sulfur, including the commercial form of the triple salt of CUROX from Akzo or CAROAT from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may be used, particularly as an additive rather than a basic oxygen bleaching agent.

Mixed oxygen bleach systems are generally applicable, as are mixtures of any oxygen bleaching agents with known bleach activators, organic catalysts, enzymatic catalysts, and mixtures thereof; moreover, such compositions may further comprise brightening agents, photo-bleaching agents and color transfer inhibitors of the types known in the art.

• · · ** 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 .......

Other peroxyacids and bleach activators useful in the present invention are from the family of imidoperoxyacids and imide bleach activators. These include phthaloylimidoperoxycaproic acid and related arylimido-substituted acyl nitrogen derivatives. For a listing of such compounds, their preparation and their incorporation into laundry detergents, including both granular and liquid detergents, see U.S. Pat. 5,487,818; U.S. Pat. 5,470,988; U.S. Pat. 5,466,825; U.S. Pat. 5,419,846; U.S. Pat. 5,415,796; U.S. Pat. 5,391,324; U.S. Pat. 5,328,634; U.S. Pat. 5,310,934; U.S. Pat. 5,279,757; U.S. Pat. 5,246,620; U.S. Pat. 5,245,075; U.S. Pat. 5,294,362; U.S. Pat. 5,423,998; U.S. Pat. 5,208,340; U.S. Pat. No. 5,132,431 and U.S. Pat. 5,087,385.

Additional bleach activators are described in U.S. Pat. No. 5,130,045 to Mitchell et al. and U.S. Pat. No. 4 412 937, Chung et al. and in co-pending U.S. patent applications U.S. Pat. sér. No. 08/064 624; 08/064 621; 08/064 562; 08/064 564; No. 08 / 082,270 and U.S. patent application Ser. sér. No. 08/133 691 (P&G Time 4890R), "Bleaching Compounds Comprising Peroxyacid Activators Ued With Enzymes", M. Bums, AD Willey, RT Hartshom, CKGhosh, incorporated herein by reference document.

Quaternary substituted bleach activators may also be included. The detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably QSBA. Preferred QSBA structures are further described in co-pending U.S. Pat. U.S. Patent Nos. 5,460,747; 5,584,888 and 5,578,136, incorporated herein by reference.

Useful diperoxy acids include, for example, 1,12-diperoxydodecanedioic acid (DPDA); 1,9-diperoxynonanedioic acid; diperoxybrasidic acid; diperoxysebacic acid and diperoxyisophitalic acid; 2-decyldiperoxybutane-1,4-dioic acid and 4,4'-sulfonylbisperoxybenzoic acid. Due to structures in which two relatively hydrophilic groups are deposited at the ends of the molecule, diperoxy acids are sometimes classified separately from hydrophilic and hydrophobic monoperoxy acids, for example, as "hydrotropic". Some of the diperoxy acids are hydrophobic in a very literal sense, especially when they have a long chain group that separates the peroxy acid groups.

····························

9 · · 999

9 99 99 999

9 9 9 9 9 9 9 9 _36- ·· * · * .........

Reducing whitening agents

Another class of useful bleaching agents are so-called reducing bleaching agents. These are bleaching agents that "reduce" pollution in the electrochemical sense, instead of oxidizing dirt, as conventional bleaching agents do. Examples of suitable reducing bleaching agents can be found in the publication

Kirk Othmer, "Encyclopedia of Chemical Technology", Vol. 17, John Wiley & Sons, 1982.

Enzymatic sources of hydrogen peroxide

Another way, unlike the oxygen bleaching agents explained above, another suitable system that generates hydrogen peroxide is a combination of a C1-C4 alkanol oxidase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are disclosed in WO 94/03003. Other enzymatic materials that pertain to bleaching, such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalase and enhancers thereof, or more generally inhibitors, can be used as optional ingredients in instant formulations.

Oxygen transfer reagents and precursors

Also useful in the present invention are any of the known organic bleach catalysts, oxygen transfer agents, or precursors thereof. These include compounds per se or precursors thereof, for example any suitable ketone for the preparation of dioxiranes or any heteroatom containing analogs of dioxirane precursors or dioxiranes, for example sulfonimines R ¹ R ² C = NSO ² R ³ , see EP 446 982 A, 1991 edition and sufonyloxaziridines, for example:

2 A 3

Preferred examples of these materials include hydrophilic or hydrophobic ketones, used in particular in conjunction with monoperoxosulphates for the preparation of dioxirans in situ (or in situ) or imines, which are described in U.S. Pat. No. 5,576,282 and the references described therein. Oxygen bleaching agents, preferably used in conjunction with these oxygen-transfer agents or precursors, include peroxycarboxylic acids and salts, peroxycarbonic acids and salts, peroxomonosulphuric acid and salts, and mixtures thereof. See also U.S. Pat. 5 360568; U.S. Pat. No. 5,360,569 and U.S. Pat. No. 5,370,826. In a highly preferred embodiment, the present invention relates to a detergent composition, wherein the detergent composition comprises a detergent composition. φ · · _36- ..... .........

which connects a transition metal bleach catalyst in accordance with the present invention and an organic bleach catalyst, such as any of the above, a basic oxidizing agent such as a hydrogen peroxide source, a hydrophilic bleach activator and at least one additional detergent, hard surface cleaner or automatic dishwashing additive . Preferred of these compositions are those further comprising a precursor for the hydrophobic oxygen bleaching agent.

PH of the composition

The compositions of the invention will have a pH range of from 2 to 13, preferably the pH is basic, more preferably from 7 to 12.5, more preferably from 8 to 12, even more preferably from 9 to 11.5. If the composition above pH 7 is to be more effective, it should preferably contain a buffering agent capable of providing a generally more basic pH in the composition and in the diluted compositions, i.e. 0.1% to 0.4% aqueous solution by weight of the composition. The pKa of this buffering agent should be 0.5-1.0 pH units below the desired pH of the composition (determined as described above). The pKa of the buffering agent should be from 7 to 10. Under these conditions, the buffering agent most effectively controls the pH using the smallest amount thereof.

The buffering agent may be an active detergent per se or a low molecular weight organic or inorganic material that is used in the composition only to maintain a basic pH. Preferred buffering agents for the compositions of the present invention are nitrogen containing materials. Some examples are amino acids, for example lysine or lower alkoholamines, such as mono- di- and triethanolamine. Other suitable nitrogen-containing buffering agents are tri (hydroxymethyl) aminomethane (HOCH 3 CNHs (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2 amino-2-methylpropanol, 2-amino-2-methyl-1,3- propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diaminopropanol, N, N'-tetramethyl-1,3-diamino-2-propanol, N, N-bis (2-hydroxyethyl) glycine (bicine) and N- Mixtures of any of the above compounds are also acceptable Suitable inorganic buffers / alkalinity sources include alkali metal carbonates and alkali metal phosphates such as sodium carbonate, sodium polyphosphate For additional buffers see EMULSIFIERS AND DETERGENTS - Emulsifiers and detergents, North American edition, 1997, McCutcheon Division, MC Publishing Company, and WO 95/07 971, which are incorporated herein by reference.

The buffering agent, when used, is present in the compositions of the present invention at a level of from 0.1% to 15%, preferably from 1% to 10%, most preferably from 2% to 8% by weight of the composition.

37 ·· ···· • to • to • to • to • to to

Diaminy

It is preferred that the diamines used in the present invention are substantially free of impurities. By " substantially free " is meant that the diamines are more than 95%, i.e. preferably 97%, more preferably 99% even more preferably 99.5% pure. Examples of impurities that may be present in commercially available diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidine. Furthermore, it is believed that diamines should be free of oxidizing compounds to prevent degradation and formation of ammonia.

It is further preferred that the compositions of the present invention are odorless, i.e., the odor does not produce a negative olfactory response from the consumer. This can be accomplished in a number of ways, including the use of perfumes to mask unwanted odors, the use of stabilizers such as antioxidants, chelating agents, etc., or the use of diamines that are substantially free of impurities. Without intending to be limited by theory, it is believed that impurities in the diamines cause most odors in the compositions of the present invention. These impurities may form during the preparation and storage of diamines. They may also be formed during the preparation and storage of the inventive composition. The use of stabilizers, e.g., antioxidants and chelating agents, inhibits or prevents the formation of such impurities in the composition from preparation to final use by the consumer and thereafter. Therefore, it is most advantageous to eliminate, suppress or prevent the formation of these odors by the addition of perfumes, stabilizers or by the use of diamines which are substantially free of impurities.

Preferred organic diamines are diamines in which pK1 and pK2 are in the range of 8.0 to 11.5, preferably in the range of 8.4 to 11, even more preferably of 8.6 to 10.75. Preferred materials for performance evaluation and delivery of 1,3-bis (methylamine) cyclohexane, 1,3-propanediamine (pK1 = 10.5; pK2 = 8.8), 1,6-hexanediamine (pK1 = 11; pK2 = 10) 1,3-pentanediamine (Dytek EP) (pK1 = 10.5; pK2 = 8.9), 2-methyl-1,5-pentanediamine (Dytek A) (pK1 = 11.2; pK2 = 10.0) . Other preferred materials are primary / primary diamines with alkylene spacers ranging from C4 to C8. It is generally believed that primary diamines are preferable to secondary and tertiary diamines.

0 · 00 00 0 0 0 0 0 0 00 00 0 0 0 0 0 0 0

-37- *** · * ** * '”

Definition of pK1 and pK2

As used herein, "pK1" and "pK2" are quantities commonly known to those skilled in the art as "pKa". The pKa symbol is used herein in the same manner as is generally known to those skilled in the art of chemistry. The values mentioned in this document can be obtained from literature, for example, Smith, Martel, Critical Stability Constants, Volume 2, Amines, Plenum Press, New York and London, 1975. Further information on pKa values can be obtained from the corresponding literature. , for example, from information supplied by DuPont, a diamine supplier.

As a working definition herein, the pKa of the diamines specified in an aqueous solution at 25 ° C and for an ionic concentration between 0.1 and 0.5 M. pKa is an equilibrium constant that can vary by temperature and ion concentration; therefore, the values reported in the literature are sometimes inconsistent, depending on the measurement method and conditions. To avoid ambiguity, the conditions and / or references used for the pKa variables of the present invention correspond to those defined herein or in "Critical Stability Constants", Volume 2, Amines. One typical measurement method is potentiometric titration of acid with sodium hydroxide and determination of pKa by a suitable method as described and mentioned in Shugar, Dean "The Chemists Ready Reference Handbook" McGraw Hill, New York, USA, 1990.

It has been determined that substituents and structural modifications that lower pK1 and pK2 below 8.0 are undesirable and cause a loss of performance. This may include substitutions that lead to ethoxylated diamines, hydroxyethyl substituted diamines, diamines with oxygen in beta (and partially also gamma) positions to nitrogen in the intervening groups (for example Jeffamine EDR 148). In addition, ethylenediamine-based materials are unsuitable.

The diamines that are useful in the present invention can be defined by the following general formulas:

R 2, C _{x 4} C _in R 4 NAN R a 'R 5.

wherein R ₂ -5 are independently selected from H, methyl, -CH ₃ CH ₂ and ethylene oxides; C _x and C _v are independently selected from methylene groups or branched alkyl groups wherein x + y is from 3 to 6; and A is optionally present and is selected from electron delivery or collection groups selected

39 ·· ···· · * ·· ·· *

9 · ♦ ♦ * * * * * * * * * * * * * * * * * * * * * * * * «* · «·· to set the diamine pKa values to the desired range. If A is present, then x and y must both be 1 or greater.

Optionally, diamines that have a molecular weight of less than or equal to 400 g / mol may be preferred. It is preferred that these diamines have the general formula:

wherein each R ⁶ is independently selected from the group consisting of hydrogen, C 1 -C 4 branched or unbranched alkyl, an alkyleneoxy group having the general formula:

- (R ⁷⁰ ) _m R ⁸ , wherein R ⁷ is C 2 -C 4 straight or branched alkylene or a mixture thereof; R ⁸ is hydrogen, C 1 -C 4 alkyl, and mixtures thereof; m is from 1 to 10; X is a unit selected from:

(i) C3-C10 unbranched alkylene, C3-C10 branched alkylene, C3-C10 cyclic alkylene, C3-C10 branched cyclic alkylene, an alkyleneoxyalkylene group having the general formula:

- (R ⁷⁰ ) _m R ⁷ -, wherein R ⁷ and _m are as defined herein above;

(ii) C3-C10 unbranched, C3-C10 branched, C3-C10 cyclic, C3-C10 branched cyclic alkylene,

C 6 -C 10 arylene, wherein said unit comprises one or more electron delivery or withdrawal groups that provide said diamine with a pK a greater than 8; and (iii) mixtures of (i) and (ii) provided that the diamine has a pK a of at least 8.

Examples of some preferred diamines include the following:

dimethylaminopropylamine:

1,6-hexanediamine:

·· ···· ·· ·· • 9 · · • • • • « ·· • · • • ·· < • · • • · • · • • ♦ • · • • • · • · • · • * • ···· · ·· > · «··

1,3-propanediamine:

2-methyl-1,5-pentanediamine:

1,3-pentanediamine, sold under the brand Dytek EP:

Jeffamine EDR 148

hAA ^0, isophorone diamine:

1,3-bis (methylamine) -cyclohexane: and mixtures thereof.

CH ₂ NH ₂

-41Solvents

Optionally, the compositions of the invention may further comprise one or more solvents. These solvents may be used in conjunction with an aqueous liquid carrier or may be used in the absence of any aqueous liquid carrier. Solvents are broadly defined as compounds which are liquid at temperatures of 20 ° C to 25 ° C and are not considered to be surfactants. One distinguishing feature is that solvents tend to exist as separate entities rather than as mixtures of compounds. Some solvents that are useful in the hard surface cleaning compositions of the present invention contain from 1 carbon atom to 35 carbon atoms and contain the following unbranched, branched or cyclic hydrocarbon groups with no more than 8 carbon atoms. Examples of suitable solvents for this invention include methanol, ethanol, propanol, isopropanol, 2-methylpyrrolidinone, benzyl alcohol and morpholine-n-oxide. Preferred among these solvents are methanol and isopropanol.

The compositions used in the present invention may optionally contain an alcohol having a carbon chain of 8 to 18 carbon atoms, preferably 12 to 16. The hydrocarbon chain may be branched or unbranched and may be mono- or polyalcohols. The compositions used in the present invention may optionally contain such alcohols or mixtures thereof from 0.1% to 3% by weight of the total composition, preferably from 0.1% to 1%.

Solvents that can be used in the present invention include all hard surface cleaners known to those skilled in the art. Suitable solvents for use herein include ethers and diethers having preferably from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms. Also other suitable solvents are glycols or alkoxylated glycols, alkoxylated aliphatic branched alcohols, alkoxylated unbranched C 1 -C 5 alcohols, unbranched C 1 -C 5 alcohols, C ₆ -C ₆ alkyl- and cycloalkyl hydrocarbons and halohydrocarbons, C ₆ -C ₆ glycol ethers and mixtures thereof.

Suitable glycols that can be used in this invention correspond to the general formula HO-CR ¹ R ² -OH, wherein R ¹ and R ² are independently H or C 2 -C 10 saturated or unsaturated aliphatic or cyclic hydrocarbon chains. Suitable glycols for use in the present invention are dodecangylcol and / or propanediol.

Suitable alkoxylated glycols which can be used in the present invention correspond to the general formula R- (A) n-R'-OH, wherein R is H, OH, a unbranched saturated or unsaturated alkyl of 1 to 20. The carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R ¹ is H or a straight or saturated saturated or unsaturated alkyl of 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 15 And A is an alkoxy group, preferably ethoxy, methoxy or propoxy and n is from 1 to 5, preferably from 1 to 2. Suitable alkoxylated glycols for use in the present invention are methoxyoctadecanol or ethoxyethoxyethanol.

Suitable alkoxylated annulene alcohols which may be used in this invention correspond to the general formula R (A) _n -OH, wherein R is an alkyl or a non-alkyl substituent, a substituted aryl group having 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10, wherein A is an alkoxy group, preferably butoxy, propoxy or ethoxy and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated annulene alcohols are benzoxyethanol or benzoxypropanol.

Suitable annulene alcohols which may be used in the present invention correspond to the general formula R-OH, wherein R is an alkyl or a non-alkyl substituent, a substituted aryl group having 1 to 20 carbon atoms, preferably 1 to 15, and more preferably 1 to 15 carbon atoms. For example, a suitable annulene alcohol for use in the present invention is benzyl alcohol.

Suitable aliphatic branched alcohols which can be used in the present invention correspond to the general formula R-OH, wherein R is a branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 5 to 12. aliphatic branched alcohols for use in the present invention include 2-ethylbutanol or 2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols which may be used in the present invention correspond to the general formula R (A) _n -OH, wherein R is a branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 5 and A is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated annulene alcohols include 1-methylpropoxyethanol or 2-methylbutoxyethanol.

Suitable alkoxylated unbranched C 1 -C 5 alcohols which can be used in the present invention correspond to the general formula R (A) _n -OH, wherein R is a unbranched saturated or unsaturated alkyl group having 1 to 5 carbon atoms, preferably 2 to 4, wherein A is an alkoxy group, preferably butoxy, propoxy or ethoxy and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic unbranched C 1 -C 5 alcohols are butoxy-propoxypropanol (n-BPP), butoxyethanol, but · · · · · · · · · · · · · · · · · · · · · · · • · • · · ·· ···

-43oxypropanol, ethoxyethanol or mixtures thereof. Butoxy-propoxypropanol is sold by Dow Chemical Company under the brand n-BPP®.

Suitable unbranched C1-C5 alcohols which can be used in this invention correspond to the general formula R-OH, wherein R is a unbranched saturated or unsaturated alkyl group having 1 to 5 carbon atoms, preferably 2 to 4. Suitable unbranched C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents include, but are not limited to, butyldiglycol ether (BDGE), butyltriglycol ether and the like. Particularly preferred solvents that can be used herein are butoxypropoxypropanol, butyldiglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.

The compositions used in the methods of the invention typically comprise up to 20% by weight of the total solvent composition or solvent mixtures, more preferably from 0.5% to 10%, even more preferably from 3% to 10%, and even more preferably from 1% to 8%.

Other suitable solvents for use in the present invention include propylene glycol derivatives, for example n-butoxypropanol or n-butoxypropoxypropanol, water-soluble CARBITOL® solvents or water-soluble CELLOSOLVE® solvents; the water-soluble CARBITOL® solvents are compounds of the 2- (2-alkoxyethoxy) ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble alcohol is 2- (2-butoxyethoxy) ethanol, also known as butylcarbitol. CELLOSOLVE® water-soluble solvents are compounds of the 2-alkoxyethoxyethanol class, with 2-butoxyethoxyethanol being preferred. Other suitable solvents include benzyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof. Some preferred solvents for use in the present invention are n-butoxypropoxypropanol, BUTYL CARBITOL® and mixtures thereof.

The solvents may also be selected from the group consisting of ether derivatives of mono-, di- and triethylene glycol, propylene glycol, butylene glycol ethers, and mixtures thereof. The molar mass of these solvents is preferably less than 350, more preferably 100 and even more preferably between 115 and 250. Examples of preferred solvents include, for example, monoethylene glycol n-hexyl ether, monopropylene glycol n-butyl ether and tripropylene glycol methyl ether. Dowanol 'and Areo Chemical Company under the brand name' Arcosolv '. Other preferred solvents include mono- and diethylene glycol n-hexyl ether and are available from Union Carbide.

-44Hydrophobic solvents

A hydrophobic solvent having cleaning performance can be used to improve cleaning with liquid compositions. The hydrophobic solvents that can be used in the hard surface cleaning compositions of the present invention can be any known "degreasing" solvents, generally used, for example, in the dry cleaning, hard surface cleaning and metalworking industries.

The applicable definition of these solvents can be derived from the solubility parameters as set out in Union Carbide's 'The Hoy', incorporated herein by reference. The hydrogen bond parameter, which is calculated according to the formula, appears to be the most useful parameter

1/2 g-1 α

where γΗ is the hydrogen bond parameter aa is the number of aggregations, (log α = 3,390 66 T _b / T _c - 0,158 48 - log M), and γΤ is the solubility parameter obtained from the formula:

1/2 where AH25 is heat at 25 ° C, R is gas constant (1,987 cal / mol / degree) (8,3-10 ³ J-KAkmol ^-1 ), T is absolute temperature in ° K, T _b is temperature boiling in ° K, T _c is the critical temperature in ° K, d is the density in g / ml and M is the molar mass.

For the compositions of the present invention, the hydrogen bond parameters are preferably less than 7.7, more preferably from 2 to 7 or 7.7, and even more preferably from 3 to 6. Solvents with lower numbers become increasingly more difficult to dissolve in the compositions and tend to cause fogging of glass. Higher numbers require more solvent to provide good cleaning of greasy or oily dirt.

· · · · · · · · · · · · · · · · · · · · · · · · · ·

Hydrophobic solvents are typically used, if present, at a level of from 0.5% to 30%, preferably from 2% to 15%, more preferably from 3% to 8%. The dilute compositions typically have solvents at levels of from 1% to 10%, preferably from 3% to 6%. The concentrated compositions comprise from 10% to 30%, preferably from 10% to 20% of the solvent.

Many of these solvents contain hydrocarbon or halogenated hydrocarbon groups of the alkyl or cycloalkyl type and have a boiling point well above room temperature, i. above 20 ° C.

A very preferred solvent is limonene, which has not only good degreasing properties but also a pleasant odor. A chemist who assembles compositions of this type will be guided in part by the need to provide good degreasing properties and in part by aesthetic considerations. For example, petroleum hydrocarbons degrease well in these compositions, but can smell. Kerosene must be extremely clean before use, even in commercial situations. For households where the smell would not be tolerated, the chemist would be more likely to choose solvents that have a relatively pleasant odor or odors that can be tolerated by perfuming.

C 6 -C 9 alkylanullene solvents, in particular C 6 -C 9 alkylbenzenes, preferably octylbenzene, exhibit excellent degreasing properties and have a low, pleasant odor. Similarly, alkene solvents having a boiling point of at least 100 ° C, especially alpha-alkenes, preferably 1-decene or 1-dodecene, are preferred grease-removing solvents.

Generically are glycol ethers that are useful in the present invention the general formula ^of R ⁿ O- (R ¹² O-) _m H wherein each R ¹¹ is an alkyl group containing 3 to 8 carbon atoms, each ^R12 is either ethylene or propylene and m ¹ is a number from 1 to 3. The most preferred glycol ethers are selected from the group consisting of monopropylene glycol monopropyl ether, dipropylene glycol monohexyl ether, ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, monoethylene glycol monohexyl ether, and monoethylene glycol ether.

A particularly preferred type of solvent for such hard surface cleaning compositions includes diols having 6 to 16 carbon atoms in the molecular structure. Preferred diol solvents have a water solubility of from 0.1 to 20 g / 100 g of water at 20 ° C. Diol solvents, in addition to good degreasing properties, give the compositions an increased ability to remove lime soap dirt from surfaces such as bathtubs and shower enclosure walls. This dirt is particularly difficult to remove, in particular compositions which do not contain abrasives. Other solvents such as benzyl alcohol, n-hexanol and phthalic esters of C1-C4 alcohols may also be used.

Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C1-C4 alcohols, butoxypropanol, Butyl Carbitol® and 1- (2-n-butoxy-1-methylethoxy) propan-2-ol (also called butoxypropoxypropanol or dipropylene glycol monobutyl ether), hexyldiglycol (Hexyl Carbitol®, butyltriglycol, diols, eg 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof) To improve the odor, the butoxypropanol solvent should have no more than 20%, preferably no more more than 10%, more preferably no more than 7% of the secondary isomer that is attached to the secondary propanol atom in the butoxy group.

The level of hydrophobic solvent is preferably, if present, from 1% to 15%, more preferably from 2% to 12%, even more preferably from 5% to 10%.

Hydrotropy

The compositions used in the methods of the invention may optionally comprise one or more materials that are hydrotropes. Hydrotropes suitable for use in the compositions of this invention include C1-C3 alkylarylsulfonates, C6-C12 alkanols, C1-C6 carboxylic sulfates and sulfonates, urea, C1-C6 hydrocarbylates, C1-C4 carboxylates, C2-C4 and organic diacids, and mixtures thereof hydrotropic materials. The compositions of the present invention preferably comprise from about 0.5% to about 8% by weight of a liquid hydrotrope detergent composition selected from alkali metal and calcium xylene and toluenesulfonates.

Suitable C1-C3 alkylarylsulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalenesulfonates and mixtures thereof.

Suitable C 1 -C 8 carboxylic sulfate or sulfonate salts are any water-soluble salts or organic compounds containing 1 to 8 carbon atoms (substituent groups not included) that are substituted with sulfate or sulfonate and have at least one carboxyl group. The substituted organic compound may be cyclic, acyclic or annulene, i. benzene derivatives. Preferred alkyl compounds have 1 to 4 carbon atoms substituted with sulfate or sulfonate and have 1 to 2 carboxyl groups. Examples of this type of hydrotrope include sulfosuccinate salts, sulfophthalate salts, sulfoacetate salts, acid salts. M-sulfobenzoic and diestersulfosuccinates, preferably sodium or potassium salts, as disclosed in U.S. Pat. No. 3,915,903.

Suitable C1-C4 hydrocarbylates and C1-C4 carboxylates for use in the present invention include acetates and propionates and citrates. Suitable C2-C4 diacids for use in the present invention include succinic, glutaric and adipic acids.

Other compounds that provide hydrotropic effects that are suitable for use herein as a hydrotrope include C 6 -C ₁₂ alkanols and urea.

Preferred hydrotropes for use in the present invention are sodium, potassium calcium and ammonium cumene sulfonates; sodium, potassium calcium and ammonium xylene sulfonates; sodium, potassium calcium and ammonium toluenesulfonates and mixtures thereof. These preferred hydrotropic materials may be present in the composition in the range of 0.5% to 8% by weight.

Polymeric foam stabilizers

The compositions of the invention may also comprise a polymeric foam stabilizer. The compositions preferably comprise at least an effective amount of the polymeric foam stabilizers described herein, more preferably from 0.01% to 10%, even more preferably from 0.05% to 5% even more preferably from 0.1% to 2% by weight of said composition. means. As used herein, an "effective amount of polymeric foam stabilizers" is understood to mean that the foam volume and foam stability produced by the compositions described herein are promoted over a longer period of time as compared to compositions not containing one or more of the foam stabilizers described herein. Further, the polymeric foam stabilizer may be present as a free base or as a salt. Typical counter ions include citrate, maleate, sulfate, chloride, etc.

Preferred polymeric foam stabilizers are polymers containing at least one monomeric unit of the formula:

^l _r 3 J

A-ZZ-1 / ZO

3 wherein each of R, R and R are independently selected from the group consisting of hydrogen, Cl to _C6 alkyl and mixtures thereof, preferably hydrogen, Cl to _C3 alkyl, more preferably hydrogen or methyl.

·· ·· ♦ ·

-48L is selected from the group consisting of a bond, O, NR ⁶ , SR ⁷ R ^8, and mixtures thereof, preferably O, NR ⁶ , wherein R ⁶ is selected from the group consisting of hydrogen, C 1-6 alkyl and mixtures thereof, preferably hydrogen, C 1 -C 3 and mixtures thereof, more preferably hydrogen, methyl; each of R and R are independently hydrogen, O, C 1 -C 8 alkyl and mixtures thereof, preferably hydrogen, C 1 -C 3 and mixtures thereof, more preferably hydrogen or methyl. The symbol "O" means oxygen which is attached by a double bond, eg as a carbonyl group. Furthermore, this means that when either or both of R ⁷ R ⁸ are "O", SR ⁷ R ⁸ may have the following structures:

Optionally, SR ⁷ R ⁸ forms a heterocyclic chain containing from 4 to 7 carbon atoms, optionally

R containing additional heteroatoms and optionally substituted. For example, SR R may be:

However, it is preferred that SR ⁷ R ⁸ , if present, is not a heterocycle.

When L is a bond, this means that there is a direct bond or bond between the carbonyl carbon atom on Z when z is not zero. For example:

If L is a bond and z is zero, then it means that L is a bond from the carbonyl atom to A. For example:

Z is selected from the group consisting of :-( CH 2) -, (CH 2 -CH = CH) -, - (CH ₂ -CHOH) -, (CH ₂ -CHNR ⁶ ) -, - (CH ₂ -CHR ¹⁴ -O) - and mixtures thereof, preferably - (CH 2) -. R ¹⁴ is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and mixtures thereof, preferably hydrogen, methyl, ethyl and mixtures thereof; z is an integer selected from 0 to 12, preferably 2 to 10, more preferably 2 to 6.

A is NR ⁴ R ⁵ , wherein each R ⁴ and R ⁵ are independently selected from the group consisting of hydrogen, C 1 -C 8 straight or branched alkyl, alkyleneoxy having the general formula:

-R (R ¹⁰ O) _y R ^n, wherein ^R10 is C2-C4 linear or branched alkylene, and mixtures thereof; R ¹¹ is hydrogen, C 1 -C 4 alkyl, and mixtures thereof; y is from 12 to 10. R ⁴ and R ⁵ are preferably independently hydrogen, C 1 -C 4 alkyl. Optionally, NR ⁴ R ^{5 may} form a heterocyclic chain containing 4 to 7 carbon atoms, optionally containing additional heteroatoms, optionally linked to a benzene chain and optionally substituted with a C 1 -C 4 group. Examples of suitable heterocycles, both substituted and unsubstituted, are indolyl, isoindiolinyl, imidazolyl, imidazolinyl, piperidinyl, pyrazolyl, pyrazolinyl, pyridinyl, piperazinyl, pyrrolidinyl, guanidino, amidino, quinidinyl, thiazolinyl, morpholine and mixtures thereof, such as morpholine and piperazinyl further preferably, the polymeric foam stabilizer has a molecular weight of from 1,000 to 2,000,000, preferably from 5,000 to 1,000,000, more preferably from 10,000 to 75,000, more preferably from 20,000 to 500,000, even more preferably from 35,000 to 1,000,000. 3000,000 Daltons. The molecular weight of the polymeric foam boosters can be determined by conventional gel-blending chromatography.

While it is preferred that the polymeric foam stabilizers be selected from homopolymers, copolymers and terpolymers, other polymers (or multimers) with at least one monomer unit obtained by polymerizing at least one monomer unit with a broader selection of monomers can also be envisaged. Ie, all the polymeric foam stabilizers may be homopolymers, copolymers, terpolymers, etc. of at least one monomer unit, or the polymeric foam stabilizers may be copolymers, terpolymers, etc. containing: 9 9 99 9 9 9 9 9 9

9 9 9 9 9 9 9 9 9 9 9 9

-509 9 9 9 9 9 9 9 9

9999 9 99 9 9 99 999 one, two or more of at least one of the monomer units and one, two or more of the monomer units other than the at least one monomer unit. In copolymers, terpolymers, etc., the monomer distribution may be either random or repetitive.

Some preferred foam stabilizing polymers are homopolymers, copolymers or terpolymers that contain at least one monomer unit selected from:

CHiCH? “Λ

N ch ₃ ch /

or

An example of a preferred homopolymer is 2-dimethylaminoethyl methacrylate (DMAM) having the formula:

Some preferred copolymers include:

CH ₃

An example of a preferred copolymer is a (DMA) / (DMAM) copolymer having the general formula:

wherein the ratio of (DMA) to (DMAM) is 1:10, preferably 1: 5, more preferably 1: 3.

An example of a preferred copolymer is a (DMAM) / (DMA) copolymer having the general formula:

wherein the ratio (DMAM) to (DMA) is 1: 5, preferably 1: 3.

Other preferred foam stabilizing polymers are protein foam stabilizers. They may be peptides, polypeptides, copolymers containing an amino acid, and mixtures thereof. Any suitable amino acid can be used to form the backbone of the peptides, polypeptides, or copolymers of the present invention that contain an amino acid, provided that at least 10% to 40% of said amino acids that form the peptides are capable of being protonated at pH from 7 do 1,5.

Amino acids suitable for use in forming the protein foam stabilizers of the present invention generally have from 2 to 22 carbon atoms, which amino acids have the general formula:

R2 R2 R2 R2

II

H ₂ N - (C) x C - (C) _{y -} C - OH

R 2 R 2 wherein R and R ¹ are each independently hydrogen, C 1 -C 6 straight or branched alkyl, C 1 -C 6 substituted alkyl or mixtures thereof. The indices x and y are each independently from 0 to 2.

An example of a more preferred amino acid of the invention is lysine, an amino acid having the formula: _ΧΤΈ τ

NH?

⁰

II H ₂ NC-C-OH

H wherein R is a substituted C1 alkyl group, and the substituent is 4-imidazolyl.

One type of suitable protein foam stabilizer consists entirely of amino acids. Said polyamino acid compounds may be naturally occurring peptides, polypeptides, enzymes, and the like, provided that said compounds have an isoelectric point of from 7 to 11.5 and a molar mass greater than or equal to 1,500 daltons. An example of a polyamino acid suitable as the protein foam stabilizer of the present invention is the enzyme lysozyme.

Other preferred polymeric foam stabilizers are homopolymers or copolymers wherein the monomers that make up said homopolymers or copolymers contain a group capable of being protonated at a pH of from 4 to 12 or a group capable of being deprotonated at a pH of from 4 to 12, mixtures of both types of groups.

A preferred class of zwitterionic polymers suitable for use as foam volume and stability enhancers has the general formula:

<*

n wherein R is C 1 -C 12 unbranched alkylene, C 1 -C 12 branched alkylene and mixtures thereof; preferably C1-C4 unbranched alkylene, C3-C4 branched alkylene, more preferably methylene and 1,2-propylene. R ¹ and R ² are as defined above. Index x is from 0 to 6; y is 0 or 1; z is 0 or 1. The index n is such that the zwitterionic polymers of the present invention have a molar mass of from 100 to 2,000,000, preferably from 5,000 to 1,000,000, more preferably from 10,000 to 750,000, more preferably from 20,000 to

500,000, more preferably from 35,000 to 30,000,000 daltons. The molecular weight of the polymeric foam enhancers can be determined by conventional gel-blending chromatography.

Anion units

R ¹ is a unit capable of having a negative charge at a pH of from 4 to 12. A preferred unit of R ¹ has the general formula:

- (L) 1 - (S) ³ R ³ , wherein L is a linker that is independently selected from the following:

OOOO

If IIII II -O-C-NR c - C ^- ~ --O O'- ™ C 'O ~ --C ^- O ™ ^- O''JI »and mixtures thereof; wherein R 'is independently hydrogen, C 1 -C 4 alkyl, and mixtures thereof; preferably hydrogen and optionally R 'and S can form a heterocycle of 4 to 7 carbon atoms, optionally containing additional heteroatoms and optionally substituted. Preferably, the linker group L can be introduced into the molecule as part of the original backbone monomer, for example a polymer having L units of the formula:

it may suitably have this group introduced into the polymer via a carboxylate containing monomer, for example via a monomer having the general formula:

CO ₂ H R 2

I I

---- (R) x- (CH) _y - (CH) _z ---- When index i is 0, L is absent.

9 · ·· 4 4

4,444 44 44

4,444 44 44 4

4 4 · ♦ ·· ♦ * · ·

4,444,444

4444 44 44 44 44 44 4

-54For anionic units, S is an "intermediate unit" wherein each S unit is independently selected from C1-C12 unbranched alkylene, C1-C12 branched alkylene, C3-C12 unbranched alkenylene, C3-C12 branched alkenylene, C3-C12 hydroxyalkylene, C4- C12 dihydroxyalkylene, C-Cio arylene, C ₈ -Ci2 dialkylarylene, - (R ⁵ O) k R ⁵ -, - (R ⁵ O) k R ⁶ (OR ⁵⁾ k-, -CH2CH ^(OR7) CH2-, and mixtures thereof ; wherein R ⁵ is C 2 -C 4 unbranched alkylene, C 3 -C 4 branched alkylene and mixtures thereof, preferably ethylene, 1,2-propylene and mixtures thereof, more preferably ethylene; R ⁶ is C 2 -C 12 unbranched alkylene and mixtures thereof, preferably ethylene; R ⁷ is hydrogen, C 1 -C 4 alkyl and mixtures thereof, preferably hydrogen. The index k is from 1 to 20.

R ³ is independently selected from hydrogen, -CO 3 M, -SO 3 M, -OSO 3 M, -CH 2 P (O) (OM) 2, -OP (O) (OM) ₂ , having the general formula:

-CR ⁸ R ⁹ R ¹⁰ wherein each R ^8, R ⁹ and R ¹⁰ is independently selected from the group consisting of hydrogen, - (CH2) ^m-n, and mixtures thereof, wherein R ¹¹ is -CO 2 H, -SO ₃ M, -OSO ₃ M, -CH (CO ₂ H) CH ₂ CO ₂ H, -CH ₂ P (O) (OH) ₂ , -OP (O) (OH) 2, and mixtures thereof, preferably -CO ₂ H, -CH (CO ₂ H) CH ₂ CO ₂ H, and mixtures thereof, more preferably -CO 2 H; provided that one R ⁸ , R ⁹ or R ¹⁰ is not hydrogen, preferably two R ⁸ , R ⁹ or R ¹⁰ are hydrogen. M is hydrogen or a cation forming salt, hydrogen. The index m has a value from 0 to 10.

Cation units

R ² is a unit capable of having a positive charge at a pH of from 4 to 12. Preferably the unit R ² has the formula:

- (L ^ r-CSV-R ⁴ , where L ¹ is a coupling unit independently selected from the following:

o Oo

II IIII —c — o—, —o — c—, —o — c — o— o R 'R' O R 'oR'

II-I-II-III-C-N-N-C-N-C-N

R 'S R ‘II II —N-C-N—

R '| R ' | R ' | N = C—, —C = N—, - 1 —N ·

-—O——, • φ · φ φ φ φ φ · · φ · Φ ·· φ φ

and mixtures thereof; wherein R 'is independently hydrogen, C 1 -C 4 alkyl, and mixtures thereof; preferably hydrogen and optionally R 'and S can form a heterocycle of 4 to 7 carbon atoms, optionally containing additional heteroatoms and optionally substituted. When the index i 'is equal to 0, L ¹ is missing.

For cationic units, S is an "intermediate unit" wherein each S unit is independently selected from C1-C12 unbranched alkylene, C1-C12 branched alkylene, C3-C12 unbranched alkenylene, C3-C12 branched alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C-Cio arylene, C ₈ -Ci2 dialkylarylene, - (R ⁵ O) k R ⁵ -, - (R ⁵ O) k R ⁶ (OR ⁵⁾ k-, -CH2CH ^(OR7) CH2-, and mixtures thereof; wherein R ⁵ is C 2 -C 4 unbranched alkylene, C 3 -C 4 branched alkylene and mixtures thereof, preferably ethylene, 1,2-propylene and mixtures thereof, more preferably ethylene; R ⁶ is C 2 -C 12 unbranched alkylene and mixtures thereof, preferably ethylene; R ⁷ is hydrogen, C 1 -C 4 alkyl and mixtures thereof, preferably hydrogen. The index k is from 1 to 20.

R ⁴ is independently selected from amino, alkylamino, carboxamide, 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl 5-pyrazolyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino and mixtures thereof, preferably dialkylamino having the general formula:

-N ^(Rn) 2, wherein each R ¹¹ is independently hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen or methyl or alternatively the two ^R11 can form a heterocycle of 4 to 8 carbon atoms, optionally containing other hetero atoms and optionally substituted .

An example of a preferred zwitterionic polymer according to the invention has the general formula:

EH ₂ CH 2 CH ₂ N ⁺ H (CH ₃₎ 2 wherein X is C, n has a value such that the average molar weight is from 5000 to 1 000 000th

Further preferred zwitterionic polymers of the present invention are polymers containing monomers wherein each monomer has only cationic units or anionic units and said polymers have the general formula:

• · ·· ····

Γ R ¹ Ί 1 Γ R ² Ί ~ (R) x (CH 2 nl i— | J

Wherein R, R, x, y and z are as defined above; η + n = n so that n has a value at which the resulting zwitterionic polymer has a molecular weight of from 5,000 to 1,000,000 daltons.

An example of a polymer having monomers with only an anionic unit or a cationic unit has the general formula:

ch ₂ —Ih

n

C = O i! H EH ₂ CH ₂ CH ₂ N ⁺ H (CH ₃₎ 2

Where the sum of n and n gives a polymer with an average molecular weight of 5,000 to 750,000 daltons.

Other preferred zwitterionic polymers of the invention are polymers having limited crosslinking and having the general formula:

R ¹ (R) x - (CH) y - (CH) t

- (R) x - (CH) y - (C

R1 R2 (RWCHJy-ICHk

wherein R, R ¹ , L ¹ , S, jx, y and z are the same as defined above; n 'is equal to n' + n is less than or equal to 5% of η ¹ + η ² = η; n provides a polymer with an average molecular weight of from 1,000 to 2,000,000 daltons. R ¹² is nitrogen, C] ₂ alkylenaminoalkylen branched, having the general formula:

-R ¹³ -NR ¹³ L ¹ and mixtures thereof, wherein each R ¹³ is independently L ¹ or ethylene.

φ · · · · · · · · · φ φ φ φ · • · · · · · · φ φ

The Zwitterionic polymers of the present invention may consist of any combination of monomer units, for example, to form a suitable foam stabilizer, several different monomers having different R 1 and R 2 groups may be combined. Alternatively, the same R1 unit can be used with a choice of different R2 units and vice versa.

Still another preferred type of polymeric foam stabilizers are polymers that contain units capable of having a cationic charge at a pH of from 4 to 12, provided that the foam stabilizer has an average cationic charge density of from 0.000 5 to 0.05 units per 100 units In addition, a polymeric foam stabilizer may be present as the free base or as a salt. Typical counter ions include citrate, maleate, sulfate, chloride, etc.

For the purposes of this invention, the term "cationic unit" is defined as "a group that when incorporated into the foam stabilizer structure of the present invention is capable of maintaining a cationic charge in the pH range of 4 to 12. The cationic unit is not required to be protonated at Non-limiting examples of units containing a cationic group include lysine, omithine, a monomer unit having the formula:

CH ₃

--CH 9 -CH 2 --CH-CH-T o = é Γ

₁ H ₂ CH ₂ CH ₂ CH ₂ N ⁺ H (CH ₃ ) ₂ .

a monomer unit having the formula:

a monomer unit having the formula:

čh ₂ ch ₂ ch ₂ n / ch ₃ ) ₃ ·· ···· · '. * · ♦ · ·· • * ·· * · 9 9 · · 9 9 999 9 9

-58 • 9 9 9 9 9 9

9999 9 9 9 9 9 9 9 99 9 monomer unit having the formula:

I NH

CH ₂ CH ₂ CH ₂ N ⁺ H {CH ₃ hs

and a monomer unit having the formula:

ch ₃ co ₂ h ch ₂ -ch-ch-ch-o = c

Ah ₂ H ₂ CH ₂ CH ₂ H N ⁺ (CH ₃ ) 3, the last of which also contains a group capable of having an anionic charge at pH 4 to 12.

For the purposes of the present invention, the term "anionic unit" is defined as "a group which, when incorporated into the foam stabilizer structure of the present invention, is capable of maintaining a cationic charge in the pH range of 4 to 12. The cationic unit is not required to be deprotonated at Non-limiting examples of units that contain an anionic group include acrylic acid, methacrylic acid, glutamic acid, aspartic acid, a monomeric unit having the formula:

a co _{2 -} ch ₂ -ch ₂ -ch-ch ₂ -a monomer unit having the formula:

CH ₃ CO ₂ '

CH ₂ -CH-CH-H-O = C

Ah

AND

CH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ toto to · · to · * · to · 9 ···· · • • • • • • • • • • • toto toto toto toto toto toto

-59 of which the last also contains a group capable of having a cationic charge at pH 4 to 12. The latter unit is defined herein as a unit capable of having anionic and cationic charge at a pH of 4 to 12. "

For the purposes of the present invention, the term "uncharged unit" is defined as "a group that when incorporated into the foam stabilizer structure of the present invention has no charge in the pH range of 4 to 12. The cationic unit is not required to be deprotonated at each value A pH in the range of 4-12. "Non-limiting examples of units that are uncharged units" are styrene, ethylene, propylene, butylene, 1,2-phenylene, ester amides, ketones, ethers, and the like.

Units containing the polymers of the invention may have any pKa as separate units or monomers.

The chemist may combine any suitable monomers or units to form a polymeric foam stabilizer, for example, amino acids may be combined with polyacrylate units.

Further information on these and other suitable foam stabilizing polymers and processes for their preparation is further described in PCT / US 98/24 853, filed 1998-11-20 (Publication No. 6,938), PCT / US 98/24 707. filed 1998-11-20 (ref. No. 6,939), PCT / US 98/24 699, filed 1998-11-20 (ref. No. 6,943) and PCT / US 98/24 852, filed 1998-1120 ( extract No. 6,944).

Enzymes

The detergent compositions of the invention may further comprise one or more enzymes that provide a gain in cleaning performance. These enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, lignases, pullulanases, tannases, pentosanases, glucanases, glucanases, glucanases, glucanases, glucanases , arabinosidases or mixtures thereof. A preferred combination is a detergent composition having a mixture of usually applicable enzymes such as protease, amylase, lipase, cutinase or cellulase. Enzymes, when present in the composition, are present from 0.000 1% to 5% active enzyme by weight of the detergent composition.

-60ΦΦ ···· »· • · 9 · ΦΦΦΦ

Φ Φ ····· · · ·

Φ Φ Φ · φ Φ φφφφ ΦΦΦ • ΦΦΦ · ΦΦ ΦΦ * · ΦΦΦ

Proteolytic enzymes

The proteolytic enzyme may be of animal, vegetable or (preferably) microorganism origin. Proteases for use in such detergent compositions include, but are not limited to, trypsin, subtilisin, chymotrypsin, and elastase type proteases. Preferred for use in the invention are proteolytic enzymes of the subtilisin type. Particularly preferred is a bacterial serine proteolytic enzyme obtained from Bacillus subtilis or Bacillus licheniformis.

Suitable proteolytic enzymes include Alcalase® (preferably), Esperase®, Savinase®, Novo Industri A / S, (Copenhagen, Denmark), Maxatase®, Maxacal® and Maxapem 15® (protein-modified Maxacal®), Gistbrocades (Delft, Netherlands) and subtilisin BPN and BPN '(preferred), which are commercially available. Preferred proteolytic enzymes are also modified bacterial serine proteases, e.g., manufactured by Genencor Intemational, Inc., (San Francisco, California, USA), as described in EP 251 446B, 1994-12-28 (especially pages 17, 24 and 98) and which are also referred to herein as "Protease B". U.S. Pat. U.S. Patent 5,030,378, Venegas, issued 1991-07-09, relates to a modified bacterial serine proteolytic enzyme (Genencor Intemational), which is referred to herein as "Protease A" (the same as BPN '). In particular, for a complete description, including amino sequences of Protease A and variants thereof, see columns 2 and 3 of U.S. Patent 5,030,378, U.S. Pat. Other proteases are sold under the trade names: Primase, Durazym, Opticlean, and Opimase. Thus, preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A / S), BPN ', Protease A and Protease B (Genencor) and mixtures thereof. Protease B is most preferred.

Of particular interest for use in the present invention are the proteases described in U.S. Pat. No. 5,470,733.

Also, the proteases described in our co-pending application USNN 08/136 797 can be incorporated into the detergent compositions of the present invention.

Another preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a carbonyl hydrolase precursor by substituting another amino acid so that the amount of amino acid residues at the position on said carbonyl hydrolase is equivalent to + 76, preferably also in combination with one or more amino acid residues at positions equivalent to positions selected from the group consisting of: +99, +101, +103, +104, +107, +123,

·· ·· »· H ·· <· · • • • * »» * · • · • • • • • · • • • · • • · * ·· · ·· 4 · ··

+27, +105, +109, +126, +128, +156, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222 , +260, +265, or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin as described in WO 95/10 615, published 1995-04-20, by Genencor Intemational (A. Baeck et al., Entitled "Protease-Containing Cleaning" Compositions - Protease-Containing Protease ”, US Serial No. 08 / 322,676, filed 1994-10-13.

The protease enzyme may be incorporated into the composition of the invention at a level of from 0.001% to 2% active enzyme by weight of the composition.

Amylases

Amylases (and / or β) can be incorporated to remove carbohydrate-based stains. Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be of any suitable origin, for example vegetable, animal, bacterial, fungal, and fermentative. Amylase enzymes are normally incorporated into the detergent composition at levels from 0.000 1% to 2%, preferably from 0.000 1% to 0.5%, more preferably from 0.000 5% to 0.1%, even more preferably from 0.001% to 0.05% of active enzyme per weight of detergent composition.

Amylase enzymes also include those described in WO 95/26 397 and co-pending application from Novo Nordisk PCT / DK 96/00 056. Therefore, other specific amylase enzymes for use in the detergent compositions of the present invention include:

(a) α-amylases, characterized in that they have a specific efficiency of at least 25% higher than that of Termamyf ^{R (} at a temperature range of 25 ° C to 55 ° C and a pH value of 8 to 10 measured by test The effectiveness of Phadebas® α-amylase is described on pages 9 to 10 of WO 95/26 397.

(b) the α-amylase of (a), which comprises the sequences set forth in SEQ ID NO in the above references, or the α-amylase which is at least 80% homologous to the amino acid sequence set forth in SEQ ID NO. (c) α-amylases according to (a), which were obtained from alkaline Bacillus species which include the following amino-sequences in the N-terminal: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-MetGln-Tyr- Phe-Glu-Trp-Tyr-Leu-Pro-Asm-Asp.

Φ · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ · ·····

A polypeptide is considered to be X% homologous to source amylase if the comparison of the respective amino acid sequences, by an algorithm such as described by Lipman and Person in Science 227, 1985, p. 1435, reveals an X% identity.

(d) α-amylase according to (a to c), wherein α-amylase can be obtained from alkophilic Bacillus species; and in particular any of the strains NCIB 12 289, NCIB 12 512, NCIB 12 513 and DSM 935.

In the context of the present invention, the term "obtainable from" is intended not only to refer to amylase produced by Bacillus, but also to amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in a host organism transformed with said α-amylase DNA sequence (e) positive immunological cross-reactivity with antibodies raised against α-amylase having an amino acid sequence corresponding to the aamylases at (a to d).

(f) Variants of the following source amylases which (i) have one of the amino acid sequences shown in the corresponding α-amylases corresponding to (a to e) or (ii) exhibit at least 80% homology with one or more of said amino acid sequences or exhibit immunological cross-reactivity with an antibody raised against α-amylase having one of said amino acid sequences or is encoded by a DNA sequence that hybridizes to the same probe as the DNA sequence encoding α-amylase having one of said amino acid sequences; in which variants:

1. at least one amino acid residue of said source α-amylase has been deleted; or

2. at least one amino acid residue of said source α-amylase has been replaced by a different amino acid residue; or

3. at least one amino acid residue corresponding to said source aamylase has been inserted;

said variant has α-amylase activity and exhibits at least one of the following properties corresponding to said source α-amylase: increased thermal stability, increased oxidation stability, reduced Ca ion dependence, increased stability or α-amylolytic activity in neutral to relatively high pH values, increased α-amylolytic activity at a relatively high temperature and increased or φ φ φ · · φ φ φ

-63 decreased isoelectric point (pl) to better adjust the pH of the α-amylase variant to the pH of the medium.

Said variants are described in patent application PCT / DK 96/00 056

Other amylases suitable for use in the present invention include, for example, α-amylases as described in British Patent 1296 839 to Novo, RAPIDASE®, Intemational Bio-Synthetics, Inc, and TERMAMYL®, Novo. FUNGAMYL® from Novo is particularly suitable. A technique for improving the stability of enzymes, e.g., oxidative stability, is known. See, for example, J. Biological Chem., Vol. 260, No. 11, 1985-06-11, st. Certain preferred embodiments of compositions of the present invention can be made using amylases having improved detergency stability, for example, in automatic dishwasher types, particularly improved oxidation stability, as measured against a TERMAMYL® reference point that is commercially available. use since 1993. These preferred amylases share a feature of "enhanced stability" of amylases herein, characterized by, at least, measurable improvement in one or more properties: oxidation stability, for example, to hydrogen peroxide / tertraacetylethylenediamine in a buffered solution at pH 9 to 10; thermal stability, e.g. at conventional wash temperatures such as 60 ° C; or alkaline stability, e.g. at a pH of from 8 to 11, measured against the aforementioned reference amylase point. Stability can be measured by any of the tests described in the art. See, for example, the references described in WO 94/02 597. Amylases with increased stability can be obtained from Novo or Genencor Intemational. One class of highly preferred amylases of the invention has in common that it is derived using site-directed mutagenesis from one or more Bacillus amylases, particularly Bacillus α-amylases, regardless of whether the immediate precursors are one or two or multiple amylase strains. Amylases with increased oxidation stability as compared to the above identified amylases in reference are preferred for use in the detergent compositions of the present invention, particularly in bleaching, more preferably oxygen bleaching as opposed to chlorine bleaching. Such preferred amylases include (a) amylases according to WO 94/02 597, Novo, incorporated hereinabove, from 1994-02-03, as further elucidated on a mutant in which the substitution is made using alanine or threonine, preferably threonine a methionine residue located at position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or in a homologous position variation similar to the source amylase, e.g., B. amyloliquefaciens, B. subtilis or B. stearothermophilus; (b) stability-enhanced amylases as described by Genencor Intemational in a paper entitled "Oxidatively Resistant alpha-Amylases - Oxidation resistant alpha-amylase," presented at the Congress 207 ^th American Chemical Society National Meeting, March 13 to 17, 1994 by C. Mitchinson. There it was noted that bleaching agents in automatic dishwashing detergents inactivate alpha.amylases, but that amylases with improved oxidation stability were produced from Genencor from B. licheniformis NCIB8061. Methionine (Met) was found to be the most likely residue for modification. Met was substituted, at the same time, at positions 8, 15,197,256, 304, 366, and 438, which led to specific mutants, of particular importance being M197L and M197T with the M197T variant being most stable. Stability was measured by CASCADE® and SUNLIGHT®; (c) particularly preferred amylases of the invention include amylase variants having additional modification in the immediate source material as described in WO 95/10 603A and available from Novo as DURAMY1®. Other particularly preferred amylases with enhanced oxidation stability include those described in WO94 / 18314 to Genencor Intemational and WO 94/02597 to Novo. Any other amylase with increased oxidative stability, for example, derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant source forms of available amylases, may be used. Other preferred enzyme modifications are available, see WO 95/09 909 to Novo.

Various carbohydrate enzymes that confer antimicrobial activity may also be included in the present invention. Such enzymes include endoglycosidase, type II endoglycosidase, and glucosidase as described in U.S. Pat. U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843, and 5,356,803, the disclosures of which are incorporated herein by reference. Naturally, other enzymes having antimicrobial activity may also be used, including peroxidases, oxidases, and various other enzymes.

If an enzyme is present in the composition, an enzyme stabilization system may also be incorporated into the compositions of the present invention.

Perfumes

Perfumes and perfume ingredients useful in the compositions and methods of the present invention include a wide variety of natural and synthetic chemical ingredients including, but not limited to, aldehydes, ketones, esters, and the like. Also includes various natural extracts and essences, which may include complex admixture mixtures such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, sandalwood oil, pine oil, cedar and the like. Finished perfumes typically comprise from 0.01% to 2% by weight of the detergent compositions of the present invention. and the individual perfume ingredients may comprise from 0.000% to 90% of the finished perfume composition.

· · · .... · · · · · .....

Non-limiting examples of perfume ingredients useful in the present invention include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; jononomethyl; jonon-gamamethyl; methylcedrylon; methyldihydrojasmonate; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl-ketone; 7-acetyl-1,1,3,4,4,6-hexamethyltetralin; 4-acetyl-6-tert-butyl-1,1-dimethylindane; parahydroxyphenylbutanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethylindane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethylindane; 1-dodecanal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyloctanal; 10-undecen-1-al; iso-hexenylcyclohexylcarboxaldehyde; formyltricyclodecane; condensation products of hydroxycitronellal and methylanthranilate, condensation products of hydroxycitronellal and indole, condensation products of phenylacetylaldehyde and indole; 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde; ethylvanillin; heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2- (p-i-propylphenyl) -propionaldehyde; coumarin; gamadekalactone; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopentane-gamma-2-benzopyran; betanaftolmethylether; ambroxan; dodecahydro-3a, 6,6,9atetramethylnaphthol [2,1-b] furan; cedrole, 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethylcyclopenten-1-yl) -2-buten-1-ol; caryophyllene alcohol; tricyclodecenylpropionate; tricyclodecenylacetate; benzylsalicylate; cedrylacetate; and p- (tert-butyl) cyclohexyl acetate.

Particularly preferred perfumery materials are those which provide a more extensive odor enhancement in the finished product compositions containing cellulases. Such perfumes include, but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; benzylsalicylate; Acetyl-1,1,3,4,4,6-hexamethyltetralin; p-tert-butylcyclohexyl acetate; methyldihydrojasmonate; betanaftolmethylether; methyl beta-naphthyl ketone; 2-methyl-2- (p-i-propylphenyl) -propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopentane-gamma-2-benzopyran; dodecahydro-3a, 6,6,9a-tertramethylnaphthol [2,1b] furan; anisaldehyde; coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfumery materials include essential oils, gums, and resins from a variety of sources, including but not limited to: Peruvian balsam, oliban oil, ambronia balsam, labdane resin, nutmeg, cassia oil, benzoin resin, coriander, and lavender. Still other perfumery chemicals include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geranoil, nerol, 2- (1,1-dimethylethyl) cyclohexanol acetate, benzyl acetate and eugenol. Carriers, such as diethyl phthalate, may be used in the finished perfume compositions.

·· ·· ♦ ·

-66Dispersive polymers

The compositions used in the methods of the invention may also optionally contain from 0.1% to 20%, more preferably from 0.5% to 10% by weight of the dispersant polymer composition. Dispersing polymers are compounds that act as soil suspending agents in an aqueous wash solution. That is, they act to suspend the dirt particles in the solution and prevent the dirt from depositing again on the surface of fabrics and dishes. This allows dirt to be removed with the washing solution. Dispersion polymers are known and customary and are available from BASF Corp and Rohm & Haas. Typical examples include polyethoxylated amines and copolymers of acrylic acid and maleic acid.

Dirt-releasing agents

The compositions of the invention may optionally comprise one or more soil release agents. Polymeric soil release agents are characterized by having both hydrophilic segments for hydrophilizing the surface of hydrophobic fabrics, such as polyesters and nylon, and hydrophobic segments for storage on hydrophobic fabrics, and remain on them until the wash cycle is complete, thereby serving as an anchor for hydrophilic segments. This may allow stains that appear after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures.

When used, soil release agents will comprise from 0.01% to 10%, preferably from 0.1% to 5%, more preferably from 0.2% to 3% by weight of the composition.

The following documents, all of which are incorporated herein by reference, describe soil release polymers suitable for use in the present invention. U.S. Pat. No. 5,691,298, Gosselink et al., Issued 1997-11-25; U.S. Pat. 5,599,782, Pan et al., Issued 1997-02-04; U.S. 5,415,407, Gosselink et al., Issued 1995-05-16; U.S. Pat. No. 5,182,043, Morrall et al. from 1993-01-26; U.S. Pat. No. 4,956,447, Gosselink et al., 1990-09-11; U.S. Pat. No. 4,976,879, Maldonado et al., Issued 1990-12-11; U.S. Pat. No. 4,968,451 Scheibel et al., Issued 1990-11-06; U.S. Pat.

925, 577, Borcher, Sr. et al., 1990-05-15; U.S. 4,861,512, Gosselink, issued 1989-08-29; U.S. Pat. No. 4,877,896, Maldonado et al., Issued 1989-10-31; U.S. Pat. No. 4,771,730, Gosselink et al., Issued 1987-10-27; U.S. Pat. 711,730, Gosselink et al., Issued 1987-12-8; U.S. Pat. 4,721,580, Gosselink, issued 1988-01-26; U.S. Pat. 4,000,093, Nicol et al., Issued 1976-12-28; U.S. Pat.

································· «· ·· ···

-673,959,230, Hayes, issued 1976-05-25; U.S. Pat. 3,893,929, Basadur, issued 1975-07-08; and Evr. U.S. Pat. application 0 219 048, Kud et al., published 1987-04-22.

Further suitable soil release agents are described in U.S. Pat. 4,101,824, Voilland et al .; U.S. Pat. 4,240,918, Lagasse et al .; U.S. Pat. 4,525,524, Tung et al .; U.S. Pat. 4,579,681, Ruppert et al .; U.S. Pat. 4,220,918; U.S. Pat. 4,787,989; EP 279,134 A, RhonePoulenc Chemie; 1988; EP 457,205 A, BASF (1991); and DE 2,335,044, Unilever N.V., 1974; all of which are incorporated herein by reference.

Brightening agents

Any optical brightener or other brightener or whitening agent known in the art may be used in the compositions of the invention at levels typically from 0.05% to 1.2% by weight. Commercial optical brighteners that can be used in the present invention can be classified into subgroups including, but not limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinkyanine, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered cyclic heterocyclic chains and other miscellaneous reagents. Examples of such brighteners are described in "Production and Application of Fluorescent Brightening Agents" by M. Zahradnik, edited by John Wikley &amp; Sons, New York, USA (1982).

Specific examples of optical brighteners that can be used in these compositions are those identified in U.S. Pat. No. 4,790,856, Wixon, 1988-12-13. These brighteners include a series of PHORWHITE brighteners from Verona. Other brightening agents described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, supplied by Ciba-Geigy; Artic White CC and Artic White CWD from Hilton-Davis from Italy; 2- (4-ethyl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1,2,3-triazol-2-yl) -stilbenes; 4,4'-bis (stryl) bisphenyls; and aminocoumarins. Specific examples of optical brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis (-benzimidazol-2-yl) ethylene; 1,3-diphenylfrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-stryl-naphth- [1,2-d] oxazole; and 2- (stilben-4-yl) 2H-naphtho- [1,2-d] triazole. See also U.S. Pat. U.S. Patent 3,646,015, Hamilton, issued 1972-02-29. Anionic brighteners are preferred in the present invention.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Other ingredients

The compositions may further comprise one or more cleaning adjuvants selected from the following polysaccharides, abrasives, bacteriocides, matting inhibitors, colorants, buffers, fungicides or antifungal agents, insect repellents, perfumes, thickeners, processing aids, anticorrosive agents, stabilizers and antioxidants. A wide variety of other ingredients useful in detergent compositions can be incorporated into the compositions of this invention, including other active ingredients, carriers, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, etc.

Conventional ingredients may include as part of one or more materials to promote or enhance cleaning performance, treat the material to be cleaned, or modify the aesthetic aspect of the composition. Typical detergent adjuvants for detergent compositions include those disclosed in U.S. Patent 3,936,537 to Baskerville et al. Supplementary agents that can also be used in the compositions utilized in the present invention at their conventional levels of use in the art (generally from 0% to 20% detergent ingredients, preferably from 0.5% to 10%) include additional active ingredients, for example, enzyme stabilizers, stain stain agents, antimicrobial and anticorrosive agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, antioxidants, enzymes stabilize agents, perfumes, dyes, solubilizers, clay dirt remover / anti-redeposition agents, carriers, processing aids, pigments, solvents for liquid preparations, fabric softeners, antistatic agents, etc. Dye transfer inhibiting agents, including polyamine N-oxides such as polyvinylpyridine N-oxide, can be used. Dye transfer inhibiting agents are further elucidated on polyvinylpyrrolidone and copolymers of N-vinylimidazole and N-vinylpyrrolidone. If desired, soluble magnesium salts such as MgCl 2, MgSO ₄ and the like can be added at levels typically 0.1% to 2% to increase the grease removal performance.

The various cleaning ingredients used in the compositions may optionally be further stabilized by absorbing said ingredients on the porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the cleaning additive is mixed with a surfactant before being absorbed into the porous substrate. In use, the cleaning additive is released from the substrate into an aqueous washing solution where it performs the intended cleaning function.

This to this to this to this to this to · ♦ ♦ • • • • • • • • • • toto toto • toto • • toto • • · ·· ·· ···

For a more detailed explanation of this technique, porous hydrophobic silica (trade mark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3% to 5% non-ionic C13.15 ethoxylated alcohol surfactant (EO 7). Typically, the ratio in enzyme solution to surfactant is 2.5 times the weight of silica. The resulting powder is dispersed with stirring into silicone oil (various viscosities of silicone oil ranging from 500 to 12,500 may be used). The resulting silicone oil dispersion is emulsified or otherwise added to the detergent matrix. In this way, additives for use in detergent compositions such as the aforementioned enzymes, bleaching agents, bleach activators, bleach catalysts, photoactivators, dyes, fluorescent agents, fabric conditioners, and hydrolyzable surfactants can be "protected".

Optionally, an antioxidant may be added to the detergent compositions of the present invention. These can be any conventional antioxidants used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine, etc. so that the antioxidant, if present, is present in the composition from 0.001% to 25%, preferably from 0.01% to 10%, more preferably from 0.05% to 5% by weight.

The compositions of the invention may be in any form, including liquid, tablets, paste, gel, microemulsion or three-phase formulation. A highly preferred embodiment is a liquid or gel form. Liquid detergent compositions may contain water and other solvents and carriers. Suitable are low molecular weight primary or secondary alcohols, exemplified by methanol, ethanol, propanol and isopropanol. Monohydroxy alcohols are preferred for solubilizing surfactants, but polyols, for example those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol) may also be used . The compositions may contain from 5% to 90%, typically 10% to 50%, of such carriers.

it «··· • ·

9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 ttt

DETAILED DESCRIPTION OF THE INVENTION

An example of a process for preparing the liquid compositions of the present invention is as follows:

Citrates are added and dissolved into unbound water. To this solution are added amine oxide, betaine, ethanol, hydrotrope and nonionic surfactant. If unbound water is not available, citrates are added to the above mixture and then mixed until dissolved. At this point, acid is added to neutralize the formulation. It is preferred that the acid be selected from organic acids such as malic and citric, but inorganic acids may also be used. In preferred embodiments, these acids are added to the formulation followed by the addition of the diamine. AExS is added last.

The compositions of the invention will have a pH range of from 2 to 13, preferably the pH is basic, more preferably 7 to 12.5, more preferably 8 to 12, and even more preferably from 9 to 11.5.

Claims (32)

PATENT CLAIMS What is claimed is: 1. A hand-held ultrasonic cleaning device comprising a housing forming a gripping device; a scrub head adapted to rest on and move over the surface to be cleaned, wherein the scrub head is adapted to be detachably mounted on the housing, and the minimum surface area of the scrub head that rests on the surface is greater 6.25 cm; a transducer to be mounted in the housing for oscillating the cleaning head at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device. Device according to claim 1, characterized in that the gripping device is at the proximal end of the housing and the cleaning head is at the distal end of the housing. Device according to claim 1 or 2, characterized in that the feeder is mounted in the housing. Device according to any one of claims 1 to 3, characterized in that the feeder is a rechargeable battery. The apparatus of any one of claims 1 to 4, further comprising at least one solution reservoir that is associated with said apparatus and said solution reservoir comprising at least one cleaning agent suitable for surface cleaning; and at least one dispensing device that is mounted in the housing for delivering at least one cleaning agent from the at least one solution reservoir to the surface before or simultaneously when the surface is in contact with the cleaning head. Device according to claim 5, characterized in that the solution reservoir is adapted for removable mounting in a housing. Device according to claim 5, characterized in that the solution reservoir is mounted in a housing. * · · · · · Device according to any one of claims 1 to 7, characterized in that the device comprises at least two of said at least one solution reservoir. Device according to any one of claims 1 to 8, characterized in that the surface is a hard surface. 10. An ultrasonic cleaning device comprising a first housing comprising a gripping device; a scrub head adapted to rest on and move over the surface to be cleaned, and the scrub head adapted to be detachably mounted to the first housing, and the minimum surface area of the scrub head that rests on the surface is greater 6.25 cm; a second housing, wherein the first housing is associated with the second housing and the second housing comprises a second housing mounted transducer for oscillating the cleaning head at an ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device. The apparatus of claim 10, wherein the gripping device is at the proximal end of the first housing and the cleaning head is at the distal end of the first housing. Device according to any one of claims 10 to 11, characterized in that the feeder is mounted in the second housing. Apparatus according to any one of claims 10 to 12, characterized in that the apparatus further comprises at least one solution reservoir which is associated with said apparatus and the at least one solution reservoir comprises at least one cleaning agent suitable for surface cleaning ; and at least one dispensing device that is mounted in the first housing for delivering at least one cleaning agent from the at least one solution reservoir to the surface before or simultaneously when the surface is in contact with the cleaning head. Device according to any one of claims 10 to 13, characterized in that the solution reservoir is adapted for removable mounting in the second housing. 99 9999 · • 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 Device according to any one of claims 10 to 14, characterized in that at least one solution reservoir is adapted for removable mounting in the first housing. Apparatus according to any one of claims 5 to 9 and 13 to 15, wherein the cleaning composition comprises a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants. agents, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Apparatus according to any one of claims 5 to 9 and 13 to 16, characterized in that the cleaning composition further comprises cleaning adjunct ingredients selected from the group consisting of cleaning components, enzymes, bleach activators, bleach catalysts, bleaching agents. enhancers, bleaching agents, alkalinity sources, dyes, perfumes, lime soap dispersants, polymeric dye transfer inhibitors, crystal growth inhibitors, photo-whitening agents, heavy metal ion masking agents, anti-matting agents, antimicrobial agents, antioxidants, re-deposition agents, soil release polymers, electrolytes, pH modifiers, thickeners, grains, metal ion salts, enzyme stabilizers, corrosion inhibitors, diamines, foam stabilizing polymers, solvents, processing aids, antibacterial agents, perfume, fabric softening agents, optical brighteners, hydrotropes, and mixtures thereof. A cleaning device according to any one of claims 5 to 9 and 17 to 17, wherein the cleaning agent is supplied to a surface adjacent the cleaning head. Cleaning device according to any one of claims 1 to 18, characterized in that the cleaning head is in the form of a sponge, scouring pad or brush. A cleaning device according to any one of claims 1 to 19, characterized in that the converter oscillates at an average frequency of from 1,000 Hz to 100 kHz. φ φ φ φ φ φ φ φ • • • • • • • • • φ φ φ φ φ φ φ - 75 - .............. Cleaning device according to any one of claims 1 to 20, characterized in that it provides an output power per unit of surface area of the cleaning head of at least 0.02 W / cm ² . A cleaning device according to any one of claims 1 to 21, characterized in that it is adapted to operate when partially immersed in an aqueous environment. A cleaning device according to any one of claims 1 to 20, adapted to operate when fully immersed in an aqueous environment. 24. A method of removing firmly adhering dirt to food from a hard surface, comprising the steps of: (i) contacting the dirt with the detergent; (ii) contacting the dirt with a cleaning head of a device according to any one of the claims 1 to 23 and by the ultrasonic energy of the dirt. 25. The method of removing food adhering soil dirt according to claim 24, further comprising the step of: (iii) rinsing the hard surface with an aqueous solution. 26. An ultrasonic cleaning product comprising: (a) a cleaning composition comprising a cleaning agent; and (b) a handheld ultrasonic cleaning device comprising a housing forming a gripping device; a cleaning head adapted to rest on and move over the surface to be cleaned, wherein the cleaning head adapts removably to the housing and the minimum surface area of the cleaning head that rests on the surface is greater than 6.25 cm ² ; a transducer to be mounted in the housing for oscillating the cleaning head at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device. «· ·· _» ··· _75- * ’* **” * ” 27. An ultrasonic cleaning product comprising: (a) a cleaning composition comprising a cleaning agent; and (b) an ultrasonic cleaning device comprising a first housing that includes a gripper; a scrub head adapted to rest on and move over the surface to be cleaned, and the scrub head adapted to be detachably mounted to the first housing, and the minimum surface area of the scrub head that rests on the surface is greater than 6.25 cm ² ; a second housing, wherein the first housing is associated with the second housing and the second housing comprises a second housing mounted transducer for oscillating the cleaning head at an ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device. 28. The ultrasonic cleaning product of either claim 26 or claim 27 wherein the cleaning agent is selected from the group consisting of cleaning components, surfactants, enzymes, bleach activators, bleach catalysts, bleach enhancers, bleaching agents. , sources of alkalinity, dyes, perfumes, lime soap dispersants, polymeric dye transfer inhibiting agents, crystal growth inhibitors, photobleaching agents, heavy metal ion masking agents, anti-matting agents, antimicrobial agents, antibacterial agents, antioxidants, re-deposition agents, soil release polymers, electrolytes, pH modifiers, thickeners, abrasives, metal ion salts, enzyme stabilizers, corrosion inhibitors, diamines, foam stabilizing polymers, solvents, processing aids, perfumes, fabric softening agents, optical brighteners, hydrotropes, and mixtures thereof. 29. The ultrasonic cleaning product of any one of claims 26 to 28, further comprising instructions for using said product, comprising the steps of: (i) applying an effective amount of a cleaning composition to the surface; and (ii) imparting ultrasonic waves to the surface using said device. ♦ · ··· · ··· The ultrasonic cleaning product of any one of claims 26 to 28, further comprising instructions for using said product, comprising the steps of: (i) using an apparatus for applying an effective amount of a cleaning agent to the surface simultaneously and adjacent to the cleaning head; and (ii) moving the scrub head over the surface and maintaining contact of the scrub head with the surface. 31. An ultrasonic cleaning device, comprising a housing forming a gripping device, a holding device for detachably holding table utensils; a transducer to be mounted in the housing for oscillating the cleaning head at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device. 32. An ultrasonic cleaning device comprising a housing adapted to be at least partially immersed in an aqueous environment and said housing comprising a gripping device, a holding device for detachably holding tableware; a transducer to be mounted in the housing for oscillating the aquatic environment at ultrasonic frequency; and a feeder for supplying the converter with direct current, wherein the feeder is associated with said device.