Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS20030213500 A1
Publication typeApplication
Application numberUS 10/141,408
Publication dateNov 20, 2003
Filing dateMay 8, 2002
Priority dateMay 8, 2001
Also published asEP1256622A1, WO2002090485A1
Publication number10141408, 141408, US 2003/0213500 A1, US 2003/213500 A1, US 20030213500 A1, US 20030213500A1, US 2003213500 A1, US 2003213500A1, US-A1-20030213500, US-A1-2003213500, US2003/0213500A1, US2003/213500A1, US20030213500 A1, US20030213500A1, US2003213500 A1, US2003213500A1
InventorsRaphael Mangin, Tom Goderis, Eric Espinosa
Original AssigneeThe Procter & Gamble Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Kit for hand dishwashing
US 20030213500 A1
Abstract
The present invention relates to a kit comprising a dishwashing applicator comprising a cavity capable of receiving a unit dose dishwashing composition, and a unit dose dishwashing composition. Preferably the unit dose dishwashing composition is a water-soluble or water-dispersible pouch comprising a hand dishwashing composition.
Images(19)
Previous page
Next page
Claims(19)
What is claimed is:
1. A kit comprising a dishwashing applicator comprising a cavity capable of receiving a unit dose dishwashing composition, and a unit dose dishwashing composition.
2. A kit according to claim 1 wherein the applicator is a cloth, wipe, sheet, sponge, brush or mixtures thereof.
3. A kit according to claim 2 wherein the applicator is a sponge made from a material natural or synthetic material, preferably a synthetic material selected from the group consisting of polyester, polyurethane and mixtures thereof.
4. A kit according to claim 1 wherein the cavity is located in the interior of the sponge and is accessed by a tube leading to an exterior surface of the applicator.
5. A kit according to claim 4, wherein the opening of the tube at the exterior surface is covered or otherwise closed.
6. A kit according to any of claim 1 wherein the cavity is located on one of the exterior surfaces of the applicator.
7. A kit according to claim 6 wherein the cavity is covered with a cap.
8. A kit according to claim 1 wherein the applicator comprises a first section comprising a cavity and a second complimentary section which may be secured to said first section to cap said cavity.
9. A kit according to claim 8 wherein the first and second sections may be fully separable from one another or may be hingedly attached to one another.
10. A kit according to claim 1 wherein the unit dose dishwashing composition is in the form of a water-soluble or water-dispersible pouch, water-soluble or water-dispersible foam, water-soluble or water-dispersible gelatine bead comprising a hand dishwashing composition or a hand dishwashing tablet comprising a disrupting agent.
11. A kit according to claim 10 wherein the unit dose dishwashing composition is in the form of a water-soluble or water-dispersible pouch, water-soluble or water-dispersible foam, water-soluble or water-dispersible gelatine bead comprising a hand dishwashing composition.
12. A kit according to claim 11 wherein the pouch is made from a material selected from the group consisting of polymers, copolymers or derivatives thereof of polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums, more preferably polyvinyl alcohol, xanthum and carragum, and mixtures thereof.
13. A kit according to claim 10 wherein the pouch comprises two sheets of water-soluble, water-dispersible material sealed around the perimeter.
14. A kit according to claim 1 wherein the pouch is heat sealed.
15. A kit according to claim 10 wherein the pouch comprises less than 10 mL of composition.
16. A kit according to claim 1 wherein the unit dose dishwashing composition comprises at least one ingredient selected from surfactant, suds booster, pH adjusting agent, enzyme, solvent and mixtures thereof.
17. A kit according to claim 10 wherein the disrupting agent of the hand dishwashing tablet is either an effervescent or disintegrant system.
18. A process of washing dishware, utilizing a dishwashing applicator, comprising a cavity capable of receiving a unit dose dishwashing composition, and a unit dose dishwashing composition, comprising the sequential steps of:
a) optionally pre-moistening the applicator with water;
b) accessing the cavity of the applicator;
c) positioning a unit dose hand dishwashing composition in the cavity of the applicator;
d) optionally covering the cavity with another section of the applicator or cap;
e) optionally contacting the applicator and/or dishware with water; and
f) contacting the dishware with the applicator.
19. A process according to claim 18 wherein the process further comprises the step of squeezing the applicator comprising the unit dose detergent at least once before contacting the dishware with the applicator.
Description
    TECHNICAL FIELD
  • [0001]
    The present invention relates to a kit comprising a sponge capable of receiving a unit dose hand dishwashing detergent and a unit dose hand dishwashing detergent.
  • BACKGROUND
  • [0002]
    Unit dose detergents, such as detergent tablets and water-soluble or water-dispersible pouches, are known in the prior art. Detergent in the form of a unit dose are generally understood to provide a convenient method of allowing the user to dose the correct amount of detergent, reduces the risk of spillage usually encountered with liquid or powder products and in some cases, eliminates the need for the user to directly handle the detergent product, especially where hazardous or irritable chemicals are concerned.
  • [0003]
    EP 879 874 describes pouches comprising hard surface cleaning compositions, including hand dishwashing compositions. Such pouches are described to provide the benefits described above with respect to convenience and ease of handling.
  • [0004]
    The Applicants have found that whilst unit dose detergents provide the above benefits, they also present some problems which are unique to hand dishwashing applications. Hand dishwashing requires the use of water at no more than 50 to 60° C. Use of water at any greater temperature will be uncomfortable and scold the hands of the dishwasher. This presents the problem that the water is not hot enough to dissolve the unit dose detergent sufficient quickly to release cleaning detergent. The consumer must therefore wait until the unit dose dissolves. In the case of a tablet this may take may take more than a 5 minutes. In addition, there is the problem that dishwashing jobs vary in size ranging from a glass or two to a full load consisting of pots, pans, glassware, crockery, cutlery etc. Whilst the user can use more than one unit dose for each dishwashing job if necessary thereby providing enough detergent for the larger jobs, it is difficult to reduce the size of the dose so as to use only the detergent required for a very small job. The unit dose detergent thus lacks flexibility, especially for the smaller jobs.
  • [0005]
    The Applicants have found a way of dealing with these problems by providing a hand dishwashing applicator, designed to be used in combination with a unit dose hand dishwashing detergent.
  • [0006]
    GB 979 735 described a sponge-like cleaning device having a cavity formed internally therein and an inlet extending to an external surface of the sponge and a removable plug. Said cleaning device is however described for use with scraps of soap. At no point does GB 979 735 describe the use of a unit dose detergents as described hereinafter.
  • [0007]
    A further advantage of the present invention is the increased mileage of the unit dose composition versus the same amount of liquid composition applied directly to dishware or the exterior surface of the applicator itself.
  • [0008]
    It is further envisaged that the kit of the present invention may equally be applied to other hard surface cleaning or laundry applications, for example for hand washing or pre-treatment of fabrics.
  • SUMMARY OF THE INVENTION
  • [0009]
    According to the present invention there is provided a kit comprising a dishwashing applicator comprising a cavity capable of receiving a unit dose dishwashing composition, and a unit dose dishwashing composition.
  • [0010]
    In a preferred embodiment the unit dose dishwashing detergent is a water-soluble or water-dispersible pouch comprising a hand dishwashing composition, or a hand dishwashing tablet.
  • [0011]
    According to the present invention there is also provided a process of washing dishware comprising the sequential steps of: optionally pre-moistening the applicator with water; accessing the cavity of the applicator; positioning a unit dose dishwashing detergent in the cavity; optionally covering the cavity with another section of the applicator or cap; optionally contacting the applicator and/or dishware with water; and contacting the dishware with the applicator. More preferably the unit dose detergent is a water-soluble or water-dispersible pouch or dishwashing tablet. More preferably the applicator is squeezed by the user prior to he step of contacting the dishware with the applicator.
  • DETAILED DESCRIPTION OF THE INVENTION
  • [0012]
    The present invention relates to a kit comprising a dishwashing applicator and a unit dose dishwashing composition, preferably in the form of a water-soluble or water-dispersible pouch or tablet.
  • [0013]
    The applicator may be any suitable implement for applying detergent to a surface and washing dishware, as long as it comprises a cavity suitable for receiving the unit dose dishwashing composition. The applicator may be any such suitable applicator currently available on the market that has been adapted to comprise a cavity. Suitable applicators include a cloth, wipe, sheet, sponge, brush or mixtures thereof. More preferably the applicator is a sponge. By the term ‘cavity’ it is meant a hole, indent or generally carved-out space which provides an area suitable in size to hold the unit dose dishwashing composition. For example the cavity may be found on one exterior surface of the applicator. The cavity may be partially or completely covered by a cap arrangement to protect the composition and keep it within the applicator. Alternatively the cavity may be found inside the applicator. In this latter embodiment the cavity may be accessed by a tube extending from an exterior surface into the cavity of the applicator. In this case, the exterior end of the tube may be partially or completely covered or closed. The exterior surface of the tube may be covered with a cap arrangement. Alternatively opposing sides of the tube may be brought together and secured, closing the tube. The opposing sides may be secured in a closed position using any suitable material, for example a lock, interlocking or Velcro (tradename)-type system, magnets etc. Closing or covering the exterior surface of the cavity of tube in this way protects the unit dose detergent and keeps it within the applicator. The tube may be provided either by cutting away part of the applicator itself to make a tube or a separate tube in suitable material e.g. plastic, may be added to the applicator. Alternatively the applicator may consist of at least two sections which are at least partially separable from one another. The first section comprises the cavity and the second complimentary section may then be secured to the first section. The cavity may then be accessed by separating the at least two sections of the applicator to reveal the cavity. The sections may be partially separable, for example hinged or totally separable. Once the unit dose dishwashing composition has been placed in the cavity, the sections of the applicator can then be replaced and secured together. The sections can be secured by any suitable method known in the art, for example by a lock, interlocking or Velcro (tradename)-type system, magnet.
  • [0014]
    The Applicator may be made from any suitable material. In the case of a cloth, wipe or sheet, the applicator is most commonly made of fabric, other woven or non-woven materials. Non-woven materials are preferably selected from natural or synthetic fibres. Natural fibres include all those which are naturally available without being modified, regenerated or produced by man and are generated from plants, animals, insects or by-products of plants, animals and insects. Preferred examples of natural fibres include cellulosic fibres, including wood pulp, cotton, hemp, jute, fax and combinations thereof. Natural material nonwovens useful in the present invention may be obtained from a wide variety of commercial sources. Nonlimiting examples of suitable commercially available paper useful herein include Airtex®, an embossed airlaid cellulosic having a base weight of about 71 gsy, available from James River, Green Bay, Wis.; and Walkisoft®, an embossed airlaid cellulosic having a base weight of about 75 gsy, available from Walkisoft U.S.A., Mount Holly, N.C.
  • [0015]
    As used herein, “synthetic” means that the materials are obtained primarily from various man-made materials or from natural materials that have been further altered. Nonlimiting examples of synthetic materials useful in the present invention include those selected from the group consisting of acetate fibers, acrylic fibers, cellulose ester fibers, modacrylic fibers, polyamide fibers, polyester fibers, polyolefin fibers, polyvinyl alcohol fibers, rayon fibers and combinations thereof. Examples of suitable synthetic materials include acrylics such as acrilan, creslan, and the acrylonitrile-based fiber, orlon; cellulose ester fibers such as cellulose acetate, arnel, and acele; polyamides such as nylons (e.g., nylon 6, nylon 66, nylon 610, and the like); polyesters such as fortrel, kodel, and the polyethylene terephthalate fiber, polybutylene terephalate fiber, dacron; polyolefins such as polypropylene, polyethylene; polyvinyl acetate fibers and combinations thereof. These and other suitable fibers and the nonwovens prepared therefrom are generally described in Riedel, “Nonwoven Bonding Methods and Materials,” Nonwoven World (1987); The Encyclopedia Americana, vol. 11, pp. 147-153, and vol. 26, pp. 566-581 (1984). Methods of making nonwovens are well known in the art.
  • [0016]
    Where the applicator is a brush it may be made from any suitable material, for example metal, rubbers, but preferably plastics. The brush preferably comprises a plastic handle portion and fibres which provide a scrubbing surface. The cavity will be located in the handle section. Preferably plastics include thermoplastic polymers, such as polyethylene or polypropylene, or thermosetting polymers such as polyurethane. Where the applicator is a sponge, it may be natural or synthetic. Synthetic sponges are most commonly made from polymeric materials, including polyester and polyurethane. The sponge may be made using available methods. The material forming the sponge and the method used to make the sponge will affect the properties of the sponge for example, pore size, pore size distribution, pore shape, strength, compressibility and flexibility. The sponge may comprise an abrasive layer which may be an integral part of the sponge or secured onto the sponge. The abrasive material may be for example, a more abrasive sponge or synthetic fibres e.g. Scotchbrite (tradename).
  • [0017]
    In addition to the above the applicator may comprise perforating, abrasive or otherwise friction-inducing units to aid the disruption and release of composition from the unit dose. The units may be found in the cavity or in the embodiment described above wherein the applicator comprises at least two sections, the units may be found in either the cavity comprising section or the complimentary section.
  • [0018]
    Unit Dose Hand Dishwashing Detergent
  • [0019]
    The unit dose hand dishwashing detergent of the present invention is defined as solid detergent unit which is designed to provide sufficient detergent for one average washing task. A unit dose detergent as used herein is defined as a solid detergent unit, at least 60% of which dissolves/disintegrates or otherwise disperses in demineralised water at 65° C., according to the unit dose dissolution test, in 5 minutes.
  • [0020]
    Preferred unit dose hand dishwashing detergents include hand dishwashing tablets, water-soluble or water-dispersible pouches, foam and gelatine beads comprising dishwashing detergent or mixtures thereof. More preferred unit dose dishwashing detergents include water-soluble or water-dispersible pouches, foam and gelatine beads comprising dishwashing detergent or mixtures thereof. Most preferred dishwashing unit dose detergents include water-soluble or water-dispersible pouches and gelatine beads comprising dishwashing detergent. The unit dose detergent dissolves, disintegrated or disperses on contact with water. Thus when the applicator is moistened with water, water will be conveyed to the unit dose composition, moistening the detergent and starting dissolution, disintegration or dispersion of the unit dose. The unit dose detergent composition is suitably sized to fit within the cavity of the applicator.
  • [0021]
    Unit Dose Dissolution Test
  • [0022]
    An 800 mL glass beaker is filled with 800 mL of demineralised water at 64° C. A cylindrical magnetic stirrer is added to the beaker and set to rotate at a speed of 200 rpm (e.g. cross-shaped magnetic stirrer—length 3.5 cm, diameter 1.5 cm). A unit dose is put into a sieve (mesh hole size is 1.5 mm by 1.5 mm) which is then placed on top of the beaker such that the mesh of the sieve is at least partially submersed in the water and the unit dose is fully submersed in the water. The sieve allows the dissolved/disintegrated material of the unit dose to transfer into the water, whilst the remaining material remains in the sieve. After 5 minutes, the sieve is taken out of the water and placed on a stand to allow the excess water to drip of the sieve. After two minutes, the bottom side of the sieve is gently dried with a paper towel to remove the remaining water. By comparing the weight of the sieve plus the unit dose before and after the test, we can calculate the amount of product that has dissolved, disintegrated or otherwise dispersed into the water.
  • [0023]
    The results of the dissolution test for the gelatin bead, tablet, pouch and foam embodiments of the unit dose detergent are presented in the table below. For comparison, also presented are the results of the test wherein the detergent is a small piece of soap. As can be seen soap, commercially available Camay soap, does not meet the criteria of a unit dose detergent as described herein since it does not dissolve sufficiently quickly in water.
    Gelatine Effervescent
    Soap Bead tablet PVA Pouch PVA Foam
    Initial 4.26 g 4.30 g 10.35 g 5.06 g 4.44 g
    weight
    End 3.00 g 0.62 g  0.66 g   0 g  0.2 g
    Weight
    % material 30% 86% 94% 100% 95%
    dissolved
  • [0024]
    Hand Dishwashing Tablets
  • [0025]
    A preferred unit dose detergent is a hand dishwashing tablets comprising hand dishwashing ingredients including at least a disrupting agent, as discussed below. The majority of ingredients are in particulate form. Liquid components may also form part of the tablet, however they must be sprayed onto or otherwise carried by the particulate ingredients. Hand dishwashing tablets are made according to generally known tabletting processes. The hand dishwashing tablet of the present invention comprise a disrupting agent. The disrupting agent is essential to ensure that the tablet dissolves quickly enough to be useful in hand dishwashing. The disrupting agent may preferably be a disintegrating or effervescing agent. Any known disintegrating or effervescing agent suitable for use in dishwashing applications is envisaged for use herein. Suitable disintegrating agents include agents that swell on contact with water or facilitated water influx and/or efflux by forming channels in compressed and/or non-compressed portions. Suitable disintegrating agent include starch, starch derivatives, alginates, carboxymethylcellulose (CMC), CMC-based polymers, sodium acetate, aluminium oxide. Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervesing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervesing agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic acids, such as citric or maleic acid, and mixtures thereof.
  • [0026]
    Water-Soluble or Water-Dispersible Foam
  • [0027]
    Water-soluble or water-dispersible foam according to the present invention is a foam component comprising a mixture of a polymeric material and an active dishwashing detergent composition, the foam component being stable upon contact with air and unstable upon contact with water.
  • [0028]
    The foam component preferably releases the dishwashing composition or part thereof upon contact with water, the component preferably partially or completely disintegrating, dispersing, denaturing and/or dissolving upon contact with water.
  • [0029]
    The foam component comprises a matrix, formed from or partially formed from at least part of the polymeric material. This means that the matrix may be formed completely by the polymeric material, or the matrix may be formed partially by the polymeric material and partially by the dishwashing composition or part thereof, or by other additional ingredients.
  • [0030]
    The matrix is preferably such that it forms an interconnected network of open and/or closed cells, in particular a network of solid struts or plates which form the edges and faces of open and/or closed cells. Then, the polymeric material or part thereof, forms at least part of the struts or plates, whilst the active ingredient, and optionally other materials, may form part of the struts or plates.
  • [0031]
    Any polymeric material which can be formed into a air-stable, water-unstable foam, can be used in the foam component and can be used to form the matrix or part thereof, of the foam component. Preferred is that the polymeric material comprises a water-dispersible, or more preferably a water-soluble polymer.
  • [0032]
    Preferred water-dispersable polymers herein have a dispersability of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out hereinafter using a glass-filter with a maximum pore size of 50 microns; more preferably the polymer herein is a water-soluble polymer which has a solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out hereinafter using a glass-filter with a maximum pore size of 20 microns, namely:
  • [0033]
    Gravimetric Method for Determining Water-Solubility or Water-Dispersability of Polymers:
  • [0034]
    50 grams±0.1 gram of polymer is added in a 400 ml beaker, whereof the weight has been determined, and 245 ml±1 ml of distilled water is added. This is stirred vigorously on magnetic stirrer set at 600 rpm, for 30 minutes. Then, the water-polymer mixture is filtered through a folded qualitative sintered-glass filter with the pore sizes as defined above (max. 20 or 50 microns). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining polymer is determined (which is the dissolved or dispersed fraction). Then, the % solubility or dispersability can be calculated.
  • [0035]
    Preferred are polymers selected from cationic polymers, such as quaternary polyamines, polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, cellulose, polysaccherides, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, or derivatives or copolymers thereof. More preferably the polymer is selected from polyvinyl alcohols, cellulose ethers and derivatives thereof, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum.
  • [0036]
    Copolymers block polymers and graft polymers of the above can also be used. Mixtures of polymers can also be used. This may in particular be beneficial to control the mechanical and/or dissolution properties of the foam component, depending on the application thereof and the required needs.
  • [0037]
    The polymer can have any average molecular weight, preferably from about 1000 to 1,000,000, or even form 4000 to 250,000 or even form 10,000 to 200,000 or even form 20,000 to 75,000.
  • [0038]
    Preferred polymers in cleaning compositions may be homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine, organic polymeric clay flocculating agents as described in European Patents No.s EP-A-299,575 and EP-A-313,146, more preferred polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, gelatin, guar gum, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, cationic polymers including ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, polyamino compounds such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629, terpolymers containing monomer, non-cotton soil release polymer as described in to U.S. Pat. No. 4,968,451, and U.S. Pat. No. 5,415,807, dispersant/anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines, as described in EP-B-0 11965 and U.S. Pat. No. 4,659,802 and U.S. Pat. No. 4,664,848.
  • [0039]
    The foam component is described in more detail in the Applicants copending applications WO01/25390 and WO01/25322. A preferred process for making the foam component is described in more detail in the Applicants copending Great Britain applications numbers GB0022525.0 and GB0022496.4.
  • [0040]
    Water-Soluble or Water-Dispersible Gelatine Beads
  • [0041]
    Water-soluble or water-dispersible gelatine beads are unit dose detergents comprising a solid, but preferably liquid detergent compositions completely surrounded by a coating made from gelatine. The components of the composition are preferably compatible with gelatine and as such do not cause deterioration of the gelatine coating. The gelatine bead is water-soluble or water dispersible. The gelatine beads are prepared according to any known and suitable process.
  • [0042]
    Water-Soluble or Water-Dispersible Pouch
  • [0043]
    The unit dose compositions of the present invention is preferably a water-soluble or water-dispersible pouch. The pouch is typically a closed structure, made of a water-soluble or water-dispersible film described herein, enclosing a volume space which comprises a composition. Said composition may be in solid, gel or paste form but is preferably a liquid and is described in more detail herein.
  • [0044]
    As with the other embodiments, when the applicator is moistened with water, water will be conveyed to the pouch, moistening the pouch and starting dissolution, disintegration or dispersion of the film. After at least partial dissolution of the film, the enclosed composition will be released. It is often the habit of the user of such applicators to squeeze the applicator before use. Squeezing of the applicator comprising the pouch will cause the pouch to burst, further improving the release of composition into the applicator.
  • [0045]
    The pouch can be of any form, shape and material which is suitable to hold the composition, e.g., without allowing the release of the composition from the pouch prior to contact of the pouch with water. The exact execution will depend on for example, the type and amount of the composition in the pouch, the number of compartments in the pouch, the characteristics required from the pouch to hold, protect and deliver or release the composition.
  • [0046]
    It may be preferred that the water-soluble or water-dispersible film and preferably the pouch as a whole is stretched during formation and/or closing of the pouch, such that the resulting pouch is at least partially stretched. This is to reduce the amount of film required to enclose the volume space of the pouch. When the film is stretched the film thickness decreases. The degree of stretching indicates the amount of stretching of the film by the reduction in the thickness of the film. For example, if by stretching the film, the thickness of the film is exactly halved then the stretch degree of the stretched film is 100%. Also, if the film is stretched so that the film thickness of the stretched film is exactly a quarter of the thickness of the unstretched film then the stretch degree is exactly 200%. Typically and preferably, the thickness and hence the degree of stretching is non-uniform over the pouch, due to the formation and closing process. For example, when a water-soluble or water-dispersible film is positioned in a mould and an open compartment is formed by vacuum forming (and then filled with the components of a composition and then closed), the part of the film in the bottom of the mould, furthest removed from the points of closing will be stretched more than in the top part. Preferably, the film which is furthest away from the opening, e.g. the film in the bottom of the mould, will be stretched more and be thinner than the film closest by the opening, e.g. at the top part of the mould.
  • [0047]
    Another advantage of stretching the pouch, is that the stretching action, when forming the shape of the pouch and/or when closing the pouch, stretches the pouch non-uniformly, which results in a pouch which has a non-uniform thickness. This allows control of the dissolution of water-soluble pouches herein, and for example sequential release of the components of the detergent composition enclosed by the pouch to the water.
  • [0048]
    Preferably, the pouch is stretched such that the thickness variation in the pouch formed of the stretched film is from 10 to 1000%, preferably 20% to 600%, or even 40% to 500% or even 60% to 400%. This can be measured by any method, for example by use of an appropriate micrometer. Preferably the pouch is made from a water-soluble film that is stretched, said film has a stretch degree of from 40% to 500%, preferably from 40% to 200%.
  • [0049]
    The pouch is made from a water-soluble or water-dispersible film. It is preferred that the pouch as a whole comprises material which is water-dispersible or more preferably water-soluble. Preferred water-soluble films are polymeric materials, preferably polymers which are formed into a film or sheet. The material in the form of a film can, for example, be obtained by casting, blow-moulding, extrusion or blow extrusion of the polymer material, as known in the art.
  • [0050]
    Preferred water-dispersible material herein has a dispersability of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out hereinafter using a glass-filter with a maximum pore size of 50 microns.
  • [0051]
    More preferably the material is water-soluble and has a solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out hereinafter using a glass-filter with a maximum pore size of 50 microns, namely:
  • [0052]
    Gravimetric Method for Determining Water-Solubility or Water-Dispersability of the Material of the Compartment and/or Pouch:
  • [0053]
    50 grams±0.1 gram of material is added in a 400 ml beaker, the weight of which has been determined, and 245 ml±1 ml of distilled water is added. This is stirred vigorously with a magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered-glass filter with pore size as defined above (max. 50 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining polymer is determined (which is the dissolved or dispersed fraction). Then, the % solubility or dispersability can be calculated.
  • [0054]
    Preferred polymers, copolymers or derivatives thereof are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferably the polymer is selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, most preferably polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC). Preferably, the level of a type polymer (e.g., commercial mixture) in the film material, for example PVA polymer, is at least 60% by weight of the film.
  • [0055]
    The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, or even from 10,000 to 300,000 or even from 15,000 to 200,000 or even from 20,000 to 150,000. Mixtures of polymers can also be used. This may in particular be beneficial to control the mechanical and/or dissolution properties of the compartment or pouch, depending on the application thereof and the required needs. For example, it may be preferred that a mixture of polymers is present in the material of the compartment, whereby one polymer material has a higher water-solubility than another polymer material, and/or one polymer material has a higher mechanical strength than another polymer material. It may be preferred that a mixture of polymers is used, having different weight average molecular weights, for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of 10,000-40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000.
  • [0056]
    Also useful are polymer blend compositions, for example comprising a hydrolytically degradable and water-soluble polymer blend such as polylactide and polyvinyl alcohol, achieved by the mixing of polylactide and polyvinyl alcohol, typically comprising 1-35% by weight polylactide and approximately from 65% to 99% by weight polyvinyl alcohol, if the material is to be water-dispersible, or water-soluble.
  • [0057]
    It may be preferred that the polymer present in the film is from 60-98% hydrolysed, preferably 80% to 90%, to improve the dissolution of the material.
  • [0058]
    Most preferred are films which are water-soluble and stretchable films, as described above. Highly preferred water-soluble films are films which comprise PVA polymers and that have similar properties to the film known under the trade reference M8630, as sold by Chris-Craft Industrial Products of Gary, Ind., US.
  • [0059]
    The water-soluble film herein may comprise other additive ingredients than the polymer or polymer material. For example, it may be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof, additional water, disintegrating aids. It may be useful that the pouch or water-soluble film itself comprises a detergent additive to be delivered to the wash water.
  • [0060]
    The pouch is made by a process comprising the steps of contacting a composition herein to a water-soluble film in such a way as to partially enclose said composition to obtain a partially formed pouch, optionally contacting said partially formed pouch with a second water-soluble film, and then sealing said partially formed pouch to obtain a pouch.
  • [0061]
    Preferably, the pouch is made using a mould, preferably the mould has rounded inner side walls and rounded inner bottom wall. A water-soluble film may be vacuum pulled into the mould so that said film is flush with the inner walls of the mould. A composition herein may then be poured into the mould, a second water-soluble film may be placed over the mould with the composition and the pouch may then be sealed, preferably the partially formed pouch is heat sealed. The film is preferably stretched during the formation of the pouch.
  • [0062]
    The pouches of the present invention comprises from 1 to 50 mL, more preferably from 1 to 30 mL, even more preferably from 1 to 20 mL, more preferably less than 10 mL and most preferably from 2 to 10 mL of composition.
  • [0063]
    The kit of the present invention may be provided with a number of different pouches, for example at least two pouches, said pouches comprising compositions. The first type of pouch may comprise a first type of composition and a second type of pouch may comprise a second type of composition. In a preferred embodiment the kit comprises a first and second type of pouch and composition and a third, optionally fourth and optionally further types of pouch and composition. Each pouch or composition contained therein providing a different visual effect or comprising at least one different ingredient. By the term ‘visual effect’ it is meant the visual appearance of the pouch or composition noticeable by the human eye. By ‘pouch or compositions comprising at least one different ingredient’ it is meant herein that the pouch and/or composition containing within the pouch, may be substantially identical but differ by the presence of at least one ingredient in the first pouch or composition that is not present in the second pouch or composition or vice versa. In a preferred aspect of the present invention the first and second and optionally third, fourth and further pouches or compositions each comprise at least one ingredient that is not present in each of the other pouches or compositions. More preferably the pouches are all identical and the compositions provide the different visual effect or chemically different composition.
  • [0064]
    The difference in visual effect may be achieved by varying for example, the shape, size, texture of the pouch. Alternatively the difference in visual effect may be achieved by varying the colour, transparency, form of the compositions. The composition may be dyed to any preferred colour depending on the presence of colourant in the composition. The composition may be more or less transparent depending on the formulation, for example the composition may be opaque or transparent or have any degree of transparency in between. The composition may be in solid, liquid, gel, paste form or mixtures thereof. For example the compositions may be liquid and one may comprise suspended solid particles. Said suspended solid particles may be any size, shape or colour as is required. In one embodiment the compositions all comprise suspended solids in a liquid matrix and the compositions differ in the colour of the suspended solids. Alternatively one composition may be in the form of a homogeneous substantially transparent liquid, whilst the other is in the form of a substantially opaque emulsion.
  • [0065]
    The kit preferably comprises sufficient pouches of the first type and second type to provide a months supply of detergent product. More preferably the kit comprises at least 7 to 15 pouches, more preferably a mixture of at least first pouches, comprising the first composition and second pouches comprising the second composition. More preferably the kit comprises first, second, third and fourth pouches and compositions.
  • [0066]
    Dishwashing Composition Ingredients
  • [0067]
    The compositions of the present invention may comprise ingredients selected from the group consisting of hydrotrope, viscosity modifier, diamine, surfactants, polymeric suds stabiliser, enzymes, builder, oxygen bleach, bleach activators, catalysts, perfume, solvent, colourants, chelating agent, soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides and other antimicrobials, tarnish inhibitors, buffers, antifungal or mildew control agents, insect repellents, processing aids, suds boosters, brighteners, anti-corrosive aids, stabilizers, antioxidants and mixtures thereof. More preferably the compositions comprise ingredients selected from the group consisting of perfume, dye and mixtures thereof.
  • [0068]
    All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference.
  • [0069]
    The compositions may be aqueous or non-aqueous. Where the compositions are aqueous they preferably comprise less than 15% water, more preferably less than 12% water, more preferably less than 8% water and most preferably less than 6% water.
  • [0070]
    The composition may be prepared for specific dishwashing tasks. For example a tough food cleaning unit dose detergent may preferably comprise ingredients selected from solvents, builders, chelants, abrasives, enzymes, anionic surfactants and mixtures thereof. Compositions for glass cleaning preferably comprise ingredients selected from builders, chelants, solvents, sheeting nonionic surfactants and mixtures thereof. Compositions conferring a mildness benefit on the user may preferably comprise protease enzymes. Compositions for cleaning specific stains, especially highly coloured stains for example tea, coffee, wine, tomato-based stains, preferably comprise ingredients selected from stabilised oxygen bleach, bleach activator, catalysts and mixtures thereof.
  • [0071]
    Perfumes
  • [0072]
    In a preferred aspect of the present invention the compositions comprise a perfume. In a particularly preferred embodiment the compositions comprise different perfumes such that the user will gain a different olfactory experience with each different type of pouch.
  • [0073]
    In a particularly preferred embodiment the compositions comprise a blooming perfume. A blooming perfume composition is one which comprises blooming perfume ingredients. A blooming perfume ingredient may be characterized by its boiling point (B.P.) and its octanol/water partition coefficient (P). B.P. according to the present invention is measured under normal standard pressure of 760 mmHg. The boiling points of many perfume ingredients, at standard 760 mmHg are given in, e.g., “Perfume and Flavor Chemicals (Aroma Chemicals),” Steffen Arctander, published by the author, 1969, incorporated herein by reference.
  • [0074]
    The octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water. The partition coefficients of the preferred perfume ingredients of the present invention may be more conveniently given in the form of their logarithm to the base 10, logP. The logP values of many perfume ingredients have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, Calif., contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the “CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database. The “calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.
  • [0075]
    In a preferred aspect of the present invention the perfume composition comprising at least two perfume ingredients. The first perfume ingredient is characterised by having boiling point of 250° C. or less and ClogP of 3.0 or less. More preferably the first perfume ingredient has boiling point of 240° C. or less, most preferably 235° C. or less. More preferably the first perfume ingredient has a ClogP value of less than 3.0, more preferably 2.5 or less. The first perfume ingredient is present at a level of at least 7.5% by weight of the composition, more preferably at least 8.5% and most preferably at least 9.5% by weight of the composition.
  • [0076]
    The second perfume ingredient is characterised by having boiling point of 250° C. or less and ClogP of 3.0 or more. More preferably the second perfume ingredient has boiling point of 240° C. or less, most preferably 235° C. or less. More preferably the second perfume ingredient has a ClogP value of greater than 3.0, even more preferably greater than 3.2. The second perfume ingredient is present at a level of at least 35% by weight of the composition, more preferably at least 37.5% and most preferably greater than 40% by weight of the perfume composition.
  • [0077]
    More preferably the perfume composition may comprise a plurality of ingredients chosen from the first group of perfume ingredients and a plurality of ingredients chosen from the second group of perfume ingredients. In addition to the above, it is also preferred that the composition comprise at least one perfume ingredient selected from either first and/or second perfume ingredients which is present in an amount of at least 7% by weight of the perfume composition, preferably at least 8.5% of the perfume composition, and most preferably, at least 10% of the perfume composition.
  • [0078]
    The first and second perfume ingredients are preferably selected from the group consisting of esters, ketones, aldehydes, alcohols, derivatives thereof and mixtures thereof. Preferred examples of the first and second perfume ingredients can be found in PCT application number US00/19078 (Applicants case number CM2396F).
  • [0079]
    In the perfume art, some auxiliary materials having no odor, or a low odor, are used, e.g., as solvents, diluents, extenders or fixatives. Non-limiting examples of these materials are ethyl alcohol, carbitol, diethylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, and benzyl benzoate. These materials are used for, e.g., solubilizing or diluting some solid or viscous perfume ingredients to, e.g., improve handling and/or formulating. These materials are useful in the blooming perfume compositions, but are not counted in the calculation of the limits for the definition/formulation of the blooming perfume compositions of the present invention.
  • [0080]
    It can be desirable to use blooming and delayed blooming perfume ingredients and even other ingredients, preferably in small amounts, in the blooming perfume compositions of the present invention, that have low odor detection threshold values. The odor detection threshold of an odorous material is the lowest vapor concentration of that material which can be detected. The odor detection threshold and some odor detection threshold values are discussed in, e.g., “Standardized Human Olfactory Thresholds”, M. Devos et al, IRL Press at Oxford University Press, 1990, and “Compilation of Odor and Taste Threshold Values Data”, F. A. Fazzalari, editor, ASTM Data Series DS 48A, American Society for Testing and Materials, 1978, both of said publications being incorporated by reference. The use of small amounts of non-blooming perfume ingredients that have low odor detection threshold values can improve perfume odor character, without the potential negatives normally associated with such ingredients, e.g., spotting and/or filming on, e.g., dish surfaces. Non-limiting examples of perfume ingredients that have low odor detection threshold values useful in the present invention include coumarin, vanillin, ethyl vanillin, methyl dihydro isojasmonate, 3-hexenyl salicylate, isoeugenol, lyral, gamma-undecalactone, gamma-dodecalactone, methyl beta naphthyl ketone, and mixtures thereof. These materials are preferably present at low levels in addition to the blooming and optionally delayed blooming ingredients, typically less than 5%, preferably less than 3%, more preferably less than 2%, by weight of the blooming perfume compositions of the present invention.
  • [0081]
    The perfumes suitable for use in the cleaning compositions herein can be formulated from known fragrance ingredients and for purposes of enhancing environmental compatibility, the perfume compositions used herein are preferably substantially free of halogenated fragrance materials and nitromusks.
  • [0082]
    Alternatively the perfume ingredients of the present invention or a portion thereof may be complexed with a complexing agent. Complexing agents may include any compound which encapsulate or bind perfume raw materials in aqueous solution. Binding can result from one or more of strong reversible chemical bonding, reversible weak chemical bonding, weak or strong physical absorption or adsorption and, for example, may take the form of encapsulation, partial encapsulation, or binding. Complexes formed can be 1:1, 1:2, 2:1 complexant:perfume ratios, or can be more complex combinations. It is also possible to bind perfumes via physical encapsulation via coating (e.g. starch coating), or coacervation. Key to effective complexation for controlled perfume release is an effective de-complexation mechanism, driven by use of the product for washing dishes or hard surfaces. Suitable de-complexation mechanisms can include dilution in water, increased or decreased temperature, increased or decreased ionic strength. It is also possible to chemically or physically decompose a coated perfume, e.g., via reaction with enzyme, bleach or alkalinity, or via solubilization by surfactants or solvents. Preferred complexing agents include cyclodextrin, zeolites, coacervates starch coatings, and mixtures thereof.
  • [0083]
    Cyclodextrin molecules are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume carrier. In addition, cyclodextrin molecules also appear to be surprisingly effective at reducing malodors generated by nitrogenous compounds, such as amines.
  • [0084]
    The prior art teaches the use of drier-added fabric softener sheets containing high levels of cyclodextrin/perfume complexes wherein the fabrics treated with this solid cyclodextrin complex release perfume when the fabrics are rewetted and that these cyclodextrin/perfume complexes can be used in aqueous rinse-added fabric softener compositions without being protected. By “protected” it is meant that the cyclodextrin is encapsulated in a hydrophobic wax coating so the cyclodextrin/perfume complexes will not decompose due to the presence of water. See e.g. U.S. Pat. No. 5,578,563, issued Nov. 26, 1996, to Trinh et al., which is hereby incorporated by reference. Thus the cyclodextrin used in the present invention may either be “unprotected”, as discussed above, or “protected” by the hydrophobic-coating protection techniques discussed in the prior art; see e.g. U.S. Pat. No. 5,102,564 to Gardlik et al., issued Apr. 7, 1992; U.S. Pat. No. 5,234,610, to Gardlik et al., issued Aug. 10, 1993.
  • [0085]
    The cavity of a cyclodextrin molecule has a substantially conical shape. It is preferable in the present invention that the cone-shaped cavity of the cyclodextrins have a length (altitude) of 8 Å and a base size of from 5 Åto 8.5 Å. Thus the preferred cavity volume for cyclodextrins of the present invention is from 65 Å3 to 210 Å3.
  • [0086]
    Suitable cyclodextrin species include any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives and/or mixtures thereof. The alpha-cyclodextrin consists of six glucose units, the beta-cyclodextrin consists of seven glucose units, and the gamma-cyclodextrin consists of eight glucose units arranged in a donut-shaped ring. The specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume. The “lining” of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic. The unique shape and physical-chemical property of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many perfume molecules can fit into the cavity.
  • [0087]
    The cyclodextrin molecules are preferably water-soluble. The water-soluble cyclodextrins used herein preferably have a water solubility of at least 10 g in 100 ml water, more preferably at least 25 g in 100 ml of water at standard temperature and pressure. Examples of preferred water-soluble cyclodextrin derivative species suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylareal alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from 1 to 14, more preferably from 1.5 to 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin derivatives typically have a degree of substitution of from 1 to 18, preferably from 3 to 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-.beta.-cyclodextrin, commonly known as DIMEB, in which each glucose unit has 2 methyl groups with a degree of substitution of 14. A preferred, more commercially available methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin having a degree of substitution of 12.6. The preferred cyclodextrins are available, e.g., from American Maize-Products Company and Wacker Chemicals (USA), Inc.
  • [0088]
    Further cyclodexrin species suitable for use in the present invention include alpha-cyclodextrin and derivatives thereof, gamma-cyclodextrin and derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof. Other derivatives of cyclodextrin which are suitable for use in the present invention are discussed in U.S. Pat. No. 5,578,563, incorporated above. It should be noted that two or more different species of cyclodextrin may be used in the same liquid detergent composition.
  • [0089]
    The complexes may be formed in any of the ways known in the art. Typically, the complexes are formed either by bringing the fragrance materials and the cyclodextrin together in a suitable solvent e.g. water and ethanol mixtures, propylene glycol. Additional examples of suitable processes as well as further preferred processing parameters and conditions are disclosed in U.S. Pat. No. 5,234,610, to Gardlik et al., issued Aug. 10, 1993, which is hereby incorporated by reference. After the cyclodextrin and fragrance materials are mixed together, this mixture is added to the liquid detergent composition.
  • [0090]
    Generally, only a portion (not all) of the fragrance materials mixed with the cyclodextrin will be encapsulated by the cyclodextrin and form part of the cyclodextrin/perfume complex; the remaining fragrance materials will be free of the cyclodextrin and when the cyclodextrin/perfume mixture is added to the detergent composition they will enter the detergent composition as free perfume molecules. A portion of free cyclodextrin molecules which are not complexed with the fragrance materials may also be present. In an alternative embodiment of the present invention, the fragrance materials and cyclodextrins are added uncomplexed and separately to the liquid detergent compositions. Consequently, the cyclodextirns and fragrance materials will come into the presence of each other in the composition, and a portion of each will combine to form the desired fragrance materials/cyclodextrin complex.
  • [0091]
    Suitable fragrance materials for use in the present invention are described in greater detail below.
  • [0092]
    In general, perfume/cyclodextrin complexes have a molar ratio of perfume compound to cyclodextrin of 1:1. However, the molar ratio can be either higher or lower, depending on the size of the perfume compound and the identity of the cyclodextrin compound. In the present invention the molar ratio of fragrance materials to cyclodextrin is preferably from 4:1 to 1:4, more preferably from 1.5:1 to 1:2, most preferably from 1:1 to 1:1.5. The molar ratio can be determined easily by forming a saturated solution of the cyclodextrin and adding the perfume to form the complex. In general the complex will precipitate readily. If not, the complex can usually be precipitated by the addition of electrolyte, change of pH, cooling, etc. The complex can then be analyzed to determine the ratio of perfume to cyclodextrin.
  • [0093]
    The actual complexes are determined by the size of the cavity in the cyclodextrin and the size of the perfume molecule. Although the normal complex is one molecule of perfume in one molecule of cyclodextrin, complexes can be formed between one molecule of perfume and two molecules of cyclodextrin when the perfume molecule is large and contains two portions that can fit in the cyclodextrin. Highly desirable complexes can be formed using mixtures of cyclodextrins since perfumes are normally mixtures of materials that vary widely in size. It is usually desirable that at least a majority of the material be beta- and/or gamma-cyclodextrin. It is highly desirable to use the reaction mixtures from the intermediate stages of the manufacture of the pure cyclodextrins as discussed hereinbefore.
  • [0094]
    Perfume Examples
  • [0095]
    The following examples numbered A to H, of the preferred perfume composition are in no way meant to be limiting.
    Perfume
    ingredient A B C D E F G H
    Allyl 2 4 2 3
    Caproate
    Citronellyl 5 8 6 3 5 6 5 3
    Acetate
    Delta 1 0.5 0.9 3 0.8 2 0.6 1
    Damascone
    Ethyl-2-methyl 8 2 1.5 12 1.5 15 1 11
    Butyrate
    Flor Acetate 8 4 4 5
    Frutene 4 8 4 8
    Geranyl Nitrile 1 15 22 1 28 1 32 5
    Ligustral 6 7.5 12 10 8 13 8 10
    Methyl dihydro 27.69 37.36 21.89 25 28.04 30 25.70 25.59
    Jasmonate
    Nectaryl 5 3 4 3
    Neobutanone 0.30 0.09 0.12 0.3 0.1 0.2 0.15 0.4
    Oxane 0.01 0.05 0.09 0.01 0.06 0.01 0.05 0.01
    Tetrahydro 32 26.69 18.79 25
    Linalool
    Methyl nonyl 7 15 10 8.5
    acetaldehyde
    Ethyl-2-methyl 1 1.5 1 1
    pentanoate
    Iso E Super 3 2 3 3
    Ionone beta 1.5 2 1.5 1
    Habanolide 3 3 3 3
    Geraniol 15 12 10 11
  • [0096]
    Hydrotrope
  • [0097]
    The compositions of the present invention may preferably comprise a hydrotrope. Hydrotrope generally means a compound with the ability to increase the solubilities, preferably aqueous solubilities, of certain slightly soluble organic compounds, more preferably “hydrotrope” is defined as follows (see S. E. Friberg and M. Chiu, J. Dispersion Science and Technology, 9(5 & 6), pages 443 to 457, (1988-1989)):
  • [0098]
    1. A solution is prepared comprising 25% by weight of the specific compound and 75% by weight of water.
  • [0099]
    2. Octanoic Acid is thereafter added to the solution in a proportion of 1.6 times the weight of the specific compound in solution, the solution being at a temperature of 20° C. The solution is mixed in a Sotax beaker with a stirrer with a marine propeller, the propeller being situated at about 5 mm above the bottom of the beaker, the mixer being set at a rotation speed of 200 rounds per minute.
  • [0100]
    3. The specific compound is hydrotrope if the the Octanoic Acid is completely solubilised, i.e., if the solution comprises only one phase, the phase being a liquid phase.
  • [0101]
    Preferred hydrotopes include the alkyl aryl sulphonates or alkyl aryl sulphonic acids. Preferred alkyl aryl sulphonates include: sodium, potassium, calcium and ammonium xylene sulphonates; sodium, potassium, calcium and ammonium toluene sulphonates; sodium, potassium, calcium and ammonium cumene sulphonates; sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulphonates; and mixtures thereof. Preferred alkyl aryl sulphonic acids include xylene sulphonic acid, toluene sulphonic acid, cumene sulphonic acid, substituted or unsubstituted naphthalene sulphonic acid and mixtures thereof. More preferably, cumene sulphonate or p-toluene sulphonate or mixtures thereof are used.
  • [0102]
    Viscosity Modifier
  • [0103]
    The present compositions may preferably comprise a viscosity modifier. Suitable viscosity modifiers include lower alkanols, ethylene glycol, propylene glycol, ethers, amines, and the like may be used in the present invention. Particularly preferred are the C1-C4 alkanols.
  • [0104]
    Suitable viscosity modifiers for use herein include ethers and diethers having 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 viscosity modifiers are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
  • [0105]
    Suitable alkoxylated alcohols which can be used herein are according to the formula
  • R-(A)n—R1—OH
  • [0106]
    wherein R is H, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R1 is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2. Suitable alkoxylated alcohols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
  • [0107]
    Suitable aromatic alcohols which can be used herein are according to the formula R—OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10. For example a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • [0108]
    Suitable aliphatic branched alcohols which can be used herein are according to the formula R—OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12. Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
  • [0109]
    Suitable alkoxylated aliphatic branched alcohols which can be used herein are according to the formula R (A)n—OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.
  • [0110]
    Suitable linear C1-C5 alcohols which can be used herein are according to the formula R—OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.
  • [0111]
    Other suitable viscosity modifiers include, but are not limited to, butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and glycerol. Particularly preferred viscosity modifiers which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, propylene glycol, glycerol, ethanol, methanol, isopropanol and mixtures thereof.
  • [0112]
    Other suitable viscosity modifiers for use herein include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, water-soluble CARBITOL R viscosity modifiers or water-soluble CELLOSOLVE R viscosity modifiers; water-soluble CARBITOL R viscosity modifiers are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol. Water-soluble CELLOSOLVE R viscosity modifiers are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being preferred. Other suitable viscosity modifiers 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 viscosity modifiers for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL Ò and mixtures thereof.
  • [0113]
    The viscosity modifiers can also be selected from the group of compounds comprising ether derivatives of mono-, di- and tri-ethylene glycol, butylene glycol ethers, and mixtures thereof. The molecular weights of these viscosity modifiers are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250. Examples of preferred viscosity modifiers include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether, and tri-propylene glycol methyl ether. Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename “Dowanol” and from the Arco Chemical Company under the tradename “Arcosolv”. Other preferred viscosity modifiers including mono- and di-ethylene glycol n-hexyl ether are available from the Union Carbide Company.
  • [0114]
    When present the composition will preferably contain at least 0.01%, more preferably at least 0.5%, even more preferably still, at least 1% by weight of the composition of viscosity modifier. The composition will also preferably contain no more than 20%, more preferably no more than 10%.
  • [0115]
    These viscosity modifiers may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present. Viscosity modifiers are broadly defined as compounds that are liquid at temperatures of 20° C.-25° C. and which are not considered to be surfactants. One of the distinguishing features is that viscosity modifiers tend to exist as discrete entities rather than as broad mixtures of compounds. Examples of particularly preferred viscosity modifiers for the present invention include ethanol, propanol, isopropanol, 2-methyl pyrrolidinone, benzyl alcohol and morpholine n-oxide. Most preferred among these viscosity modifiers are ethanol and isopropanol.
  • [0116]
    Diamines
  • [0117]
    Another optional, although preferred, ingredient of the compositions according to the present invention is a diamine. In the context of a hand dishwashing composition, the “usage levels” of such diamine in the compositions herein can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the length of time the dishware is contacted with the wash water.
  • [0118]
    Since the habits and practices of the users of detergent compositions show considerable variation, the composition will preferably contain at least 0.1%, more preferably at least 0.2%, even more preferably, at least 0.25%, even more preferably still, at least 0.5% by weight of said composition of diamine. The composition will also preferably contain no more than 15%, more preferably no more than 10%, even more preferably, no more than 6%, even more preferably, no more than 5%, even more preferably still, no more than about 1.5% by weight of said composition of diamine.
  • [0119]
    It is preferred that the diamines used in the present invention are substantially free from impurities. That is, by “substantially free” it is meant that the diamines are over 95% pure, i.e., preferably 97%, more preferably 99%, still more preferably 99.5%, free of impurities. Examples of impurities which may be present in commercially supplied diamines include 2-Methyl-1,3-diaminobutane and alkylhydropyrimidine. Further, it is believed that the diamines should be free of oxidation reactants to avoid diamine degradation and ammonia formation.
  • [0120]
    Preferred organic diamines are those 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 from 8.6 to 10.75. Preferred materials for performance and supply considerations are 1,3-bis(methylamine)-cyclohexane (pKa=10 to 10.5), 1,3 propane diamine (pKl=10.5; pK2=8.8), 1,6 hexane diamine (pKl=11; pK2=10), 1,3 pentane diamine (Dytek EP) (pK1=10.5; pK2=8.9), 2-methyl 1,5 pentane diamine (Dytek A) (pK1=11.2; pK2=10.0). Other preferred materials are the primary/primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines.
  • [0121]
    Definition of pK1 and pK2—As used herein, “pKa1” and “pKa2” are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from “Critical Stability Constants: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont, a supplier of diamines.
  • [0122]
    As a working definition herein, the pKa of the diamines is specified in an all-aqueous solution at 25° C. and for an ionic strength between 0.1 to 0.5 M. The pKa is an equilibrium constant which can change with temperature and ionic strength; thus, values reported in the literature are sometimes not in agreement depending on the measurement method and conditions. To eliminate ambiguity, the relevant conditions and/or references used for pKa's of this invention are as defined herein or in “Critical Stability Constants: Volume 2, Amines”. One typical method of measurement is the potentiometric titration of the acid with sodium hydroxide and determination of the pKa by suitable methods as described and referenced in “The Chemist's Ready Reference Handbook” by Shugar and Dean, McGraw Hill, NY, 1990.
  • [0123]
    It has been determined that substituents and structural modifications that lower pK1 and pK2 to below 8.0 are undesirable and cause losses in performance. This can include substitutions that lead to ethoxylated diamines, hydroxy ethyl substituted diamines, diamines with oxygen in the beta (and less so gamma) position to the nitrogen in the spacer group (e.g., Jeffamine EDR 148). In addition, materials based on ethylene diamine are unsuitable.
  • [0124]
    The diamines useful herein can be defined by the following structure:
  • [0125]
    wherein R2-5 are independently selected from H, methyl, —CH3CH2, and ethylene oxides; Cx and Cv are independently selected from methylene groups or branched alkyl groups where x+y is from 3 to 6; and A is optionally present and is selected from electron donating or withdrawing moieties chosen to adjust the diamine pKa's to the desired range. If A is present, then x and y must both be 1 or greater.
  • [0126]
    Examples of preferred diamines can be found in the copending provisional patent application of Phillip Kyle Vinson et al., entitled “Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution”, having P & G Case No. 7167P, application serial No. 60/087,693, and filed on Jun. 2, 1998, which is hereby incorporated by reference.
  • [0127]
    Carboxylic Acid
  • [0128]
    The compositions according to the present invention may comprise a linear or cyclic carboxylic acid or salt thereof. Where the acid or salt thereof is present and is linear, it preferably comprises from 1 to 6 carbon atoms whereas where the acid is cyclic, it preferably comprises greater than 3 carbon atoms. The linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent group selected from the group consisting of hydroxyl, ester, ether, aliphatic groups having from 1 to 6, more preferably 1 to 4 carbon atoms and mixtures thereof
  • [0129]
    The carboxylic acids or salts thereof preferably have a pKa1 of less than 7, more preferably from 1 to 3. The carboxylic acid and salts thereof may comprise one or two or more carboxylic groups.
  • [0130]
    Suitable carboxylic acids or salts thereof are those having the general formula:
  • [0131]
    wherein R1, R2, R3, R4, R5, R6, R7 are selected from the group consisting of alkyl chain having from 1 to 3 carbon atoms, hydroxy group, hydrogen, ester group, carboxylic acid group with the proviso that no more than 3 carboxylic acid groups are present.
  • [0132]
    Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetyl salicylic acid, 3 methyl salicylic acid, 4 hydroxy isophthalic acid, dihydroxyfumaric acid, 1,2,4 benzene tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof. Where the carboxylic acid exists in the salt form, the cation of the salt is preferably selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
  • [0133]
    The carboxylic acid or salt thereof is preferably present at the level of from 0.1% to 5%, more preferably from 0.2% to 1% and most preferably from 0.25% to 0.5%.
  • [0134]
    Carboxylic acids can be used to provide improved rinse feel as defined below. The presence of anionic surfactants, especially when present in higher amounts in the region of 15-35% by weight of the composition, results in the composition imparting a slippery feel to the hands of the user and the dishware. This feeling of slipperiness is reduced when using the carboxylic acids as defined herein i.e., the rinse feel becomes draggy.
  • [0135]
    Surfactant
  • [0136]
    The compositions of the present invention preferably comprise a surfactant. Surfactants may be selected from the group consisting of amphoteric, zwitterionic, nonionic, anionic, cationic surfactants and mixtures thereof.
  • [0137]
    Amphoteric surfactants are preferred additional surfactants. The amphoteric surfactants useful in the present invention are preferably selected from amine oxide surfactants. Amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • [0138]
    Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • [0139]
    wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 3; and each R5 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 R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • [0140]
    Also suitable are amine oxides such as propyl amine oxides, represented by the formula:
  • [0141]
    wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to 10.
  • [0142]
    A further suitable species of amine oxide semi-polar surface active agents comprise compounds and mixtures of compounds having the formula:
  • [0143]
    wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to 10. Particularly preferred are amine oxides of the formula:
  • [0144]
    wherein R1 is a C10-14 alkyl and R2 and R3 are methyl or ethyl. Because they are low-foaming it may also be desirable to use long chain amine oxide surfactants which are more fully described in U.S. Pat. No. 4,316,824 (Pancheri), U.S. Pat. Nos. 5,075,501 and 5,071,594, incorporated herein by reference.
  • [0145]
    Other suitable, non-limiting examples of amphoteric detergent surfactants that are useful in the present invention include amido propyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • [0146]
    Further examples of suitable amphoteric surfactants are given in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch), hereby incorporated by reference.
  • [0147]
    Preferably the amphoteric surfactant where present, is present in the composition in an effective amount, more preferably from 0.1% to 20%, even more preferably 0.1% to 15%, even more preferably still from 0.5% to 10%,by weight.
  • [0148]
    Suitable nonionic detergent surfactants are generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference.
  • [0149]
    The condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from 2 to 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is referred to generally as “alkyl ethoxylates.”
  • [0150]
    The preferred alkylpolyglycosides have the formula
  • R2O(CnH2nO)t(glycosyl)x
  • [0151]
    wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which 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, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
  • [0152]
    Fatty acid amide surfactants having the formula:
  • [0153]
    wherein R6 is an alkyl group containing from 7 to 21 (preferably from 9 to 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and —(C2H4O)XH where x varies from 1 to 3.
  • [0154]
    Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • [0155]
    Preferably the nonionic surfactant, when present in the composition, is present in an effective amount, more preferably from 0.1% to 20%, even more preferably 0.1% to 15%, even more preferably still from 0.5% to 10%, by weight.
  • [0156]
    The detergent compositions hereof may also contain an effective amount of polyhydroxy fatty acid amide surfactant. By “effective amount” is meant that the formulator of the composition can select an amount of polyhydroxy fatty acid amide to be incorporated into the compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of 1%, by weight, polyhydroxy fatty acid amide will enhance cleaning performance.
  • [0157]
    Where present, the detergent compositions may comprise 1% weight basis, polyhydroxy fatty acid amide surfactant, preferably from 3% to 30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula:
  • [0158]
    wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of —CH2—(CHOH)n—CH2OH, —CH(CH2OH)—(CHOH)n-1—CH2OH, —CH2—(CHOH)2(CHOR′)(CHOH)—CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R1 is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly —CH2—(CHOH)4—C2OH.
  • [0159]
    R′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • [0160]
    R2—CO—N<can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • [0161]
    Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • [0162]
    Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO3M wherein R preferably is a C6-C20 linear or branched hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C10-C14 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation or ammonium or substituted ammonium, but preferably sodium.
  • [0163]
    Other suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted linear or branched C6-C20 alkyl or hydroxyalkyl group having a C10-C20 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C14 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 5, more preferably between 0.5 and 2, and M is H or a cation which can be, for example, a metal cation, ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Exemplary surfactants are C10-C14 alkyl polyethoxylate (1.0) sulfate, C10-C14 polyethoxylate (1.0) sulfate, C10-C14 alkyl polyethoxylate (2.25) sulfate, C1-C14 polyethoxylate (2.25) sulfate, C10-C14 alkyl polyethoxylate (3.0) sulfate, C10-C14 polyethoxylate (3.0) sulfate, and C1-C4 alkyl polyethoxylate (4.0) sulfate, C10-C18 polyethoxylate (4.0) sulfate. In a preferred embodiment the anionic surfactant is a mixture of alkoxylated, preferably ethoxylated and non-alkoxylated sulfate surfactants. In such a preferred embodiment the preferred average degree of alkoxylation is from 0.4 to 0.8.
  • [0164]
    Other particularly suitable anionic surfactants for use herein are alkyl sulphonates including water-soluble salts or acids of the formula RSO3M wherein R is a C6-C20 linear or branched, saturated or unsaturated alkyl group, preferably a C10-C20 alkyl group and more preferably a C10-C14 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • [0165]
    Suitable alkyl aryl sulphonates for use herein include water-soluble salts or acids of the formula RSO3M wherein R is an aryl, preferably a benzyl, substituted by a C6-C20 linear or branched saturated or unsaturated alkyl group, preferably a C12-C16 alkyl group and more preferably a C10-C14 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • [0166]
    In a further preferred embodiment the carbon chain of the anionic surfactant comprises alkyl, preferably C1-4 alkyl branching units. The average percentage branching of the anionic surfactant is greater than 30%, more preferably from 35% to 80% and most preferably from 40% to 60%. Such average percentage of branching can be achieved by formulating the composition with one or more anionic surfactants all of which are preferably greater than 30% branched, more preferably from 35% to 80% and most preferably from 40% to 60%. Alternatively and more preferably, the composition may comprise a combination of branched anionic surfactant and linear anionic surfactant such that on average the percentage of branching of the total anionic surfactant combination is greater than 30%, more preferably from 35% to 80% and most preferably from 40% to 60%.
  • [0167]
    The anionic surfactant is preferably present at a level of at least 10%, more preferably from 15% to 40% and most preferably from 20% to 35% by weight of the total composition.
  • [0168]
    Other additional anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, sulphobetaines, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • [0169]
    Other particularly suitable anionic surfactants for use herein are alkyl carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20, preferably from 5 to 15. Preferred alkylalkoxycarboxylate for use herein is sodium laureth 11 carboxylate (i.e., RO(C2H4O)10—CH2COONa, with R═C12-C14) commercially available under the name Akyposoft® 100NV from Kao Chemical Gbmh. The particular surfactants used can therefore vary widely depending upon the particular end-use envisioned. Suitable additional surfactants are described in detail in the copending provisional patent application of Chandrika Kasturi et al., entitled “Liquid Detergent Compositions Comprising Polymeric Suds Enhancers”, having P & G Case No. 6938P, application serial No. 60/066,344, incorporated above.
  • [0170]
    In a preferred aspect of the present invention, the composition comprises at least 30% surfactant, preferably selected from the group consisting of anionic, foaming nonionic, amphoteric and zwitterionic surfactants.
  • [0171]
    Polymeric Suds Stabilizer
  • [0172]
    The compositions of the present invention may optionally contain a polymeric suds stabilizer. These polymeric suds stabilizers provide extended suds volume and suds duration without sacrificing the grease cutting ability of the liquid detergent compositions. These polymeric suds stabilizers are selected from:
  • [0173]
    i) homopolymers of (N,N-dialkylamino)alkyl acrylate esters having the formula:
  • [0174]
    wherein each R is independently hydrogen, C1-C18 alkyl, and mixtures thereof, R1 is hydrogen, C1-C6 alkyl, and mixtures thereof, n is from 2 to 6; and
  • [0175]
    ii) copolymers of (i) and
  • [0176]
    wherein R1 is hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from 2 to 1 to 1 to 2; The molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from 1,000 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, even more preferably from 35,000 to 200,000. The polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • [0177]
    One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely
  • [0178]
    When present in the compositions, the polymeric suds booster may be present in the composition from 0.01% to 15%, preferably from 0.05% to 10%, more preferably from 0.1% to 5%, by weight.
  • [0179]
    Enzymes
  • [0180]
    Detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, 13-glucanases, arabinosidases or mixtures thereof. A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase. Enzymes when present in the compositions, at from 0.0001% to 5% of active enzyme by weight of the detergent composition. Preferred proteolytic enzymes, then, 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. Preferred amylase enzymes include TERMAMYL®, DURAMYL® and the amylase enzymes those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • [0181]
    Further non-limiting examples of suitable and preferred enzymes are disclosed in the copending application: “Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low temperature stability and Dissolution”, having P & G Case No. 7167P and application serial No. 60/087,693, which is hereby incorporated by reference.
  • [0182]
    Because hydrogen peroxide and builders such as citric acid and citrates impair the stability of enzymes in LDL compositions, it is desirable to reduce or eliminate the levels of these compounds in compositions which contain enzymes. Hydrogen peroxide is often found as an impurity in surfactants and surfactant pastes. As such, the preferred level of hydrogen peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm. Amine impurities in amine oxide and betaines, if present, should be minimized to the levels referred above for hydrogen peroxide.
  • [0183]
    Magnesium Ions
  • [0184]
    While it is preferred that divalent ions be omitted from LDL compositions prepared according to the present invention, alternate embodiments of the present invention may include magnesium ions.
  • [0185]
    It is desirable to exclude all divalent ions from the present LDL compositions, because such ions may lead to slower dissolution as well as poor rinsing, and poor low temperature stability properties. Moreover, formulating such divalent ion-containing compositions in alkaline pH matrices may be difficult due to the incompatibility of the divalent ions, particularly magnesium, with hydroxide ions.
  • [0186]
    Nonetheless, the presence of magnesium ions offers several benefits. Notably, the inclusion of such divalent ions improves the cleaning of greasy soils for various LDL compositions, in particular compositions containing alkyl ethoxy carboxylates and/or polyhydroxy fatty acid amide. This is especially true when the compositions are used in softened water that contains few divalent ions.
  • [0187]
    But in the present invention, these benefits can be obtained without the inclusion of divalent ions. In particular, improved grease cleaning can be achieved without divalent ions by the inclusion of organic diamines in combination with amphoteric and anionic surfactants in the specific ratios discussed above while enzymes have been shown to improve the skin mildness performance of the present LDL compositions.
  • [0188]
    If they are to be included in an alternate embodiment of the present LDL compositions, then the magnesium ions are present at an active level of from 0.01% to 1.5%, preferably from 0.015% to 1%, more preferably from 0.025% to 0.5%, by weight. The amount of magnesium ions present in compositions of the invention will be also dependent upon the amount of total surfactant present therein.
  • [0189]
    Preferably, the magnesium ions are added as a hydroxide, chloride, acetate, sulfate, formate, oxide or nitrate salt to the compositions of the present invention. Because during storage, the stability of these compositions becomes poor due to the formation of hydroxide precipitates in the presence of compositions containing moderate concentrations of hydroxide ions, it may be necessary to add certain chelating agents. Suitable chelating agents are discussed further below and in U.S. Pat. No. 5,739,092, issued Apr. 14, 1998, to Ofosu-Asante, incorporated herein by reference.
  • [0190]
    Chelating Agents
  • [0191]
    The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • [0192]
    Amino carboxylates useful as optional chelating agents include ethylene diamine tetracetates, N-hydroxy ethyl ethylene diamine triacetates, nitrilo-tri-acetates, ethylenediamine tetraproprionates, triethylene tetraamine hexacetates, diethylene triamine pentaacetates, and ethanol diglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • [0193]
    Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • [0194]
    Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • [0195]
    A preferred biodegradable chelator for use herein is ethylenediamine disuccinate (“EDDS”), especially the [S,S] isomer as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.
  • [0196]
    The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder. Similarly, the so called “weak” builders such as citrate can also be used as chelating agents.
  • [0197]
    If utilized, these chelating agents will generally comprise from 0.00015% to 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.0003% to 3.0% by weight of such compositions.
  • [0198]
    A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • [0199]
    An antioxidant can be optionally added to the detergent compositions of the present invention. They can be any conventional antioxidant used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine(MEA), diethanolamine, triethanolamine, etc. It is preferred that the antioxidant, when present, be present in the composition from 0.001% to 5% by weight.
  • [0200]
    Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • [0201]
    To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5× the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be “protected” for use in detergents, including liquid laundry detergent compositions.
  • [0202]
    Non-Aqueous Liquid Detergents
  • [0203]
    The manufacture of liquid detergent compositions which comprise a non-aqueous carrier medium can be prepared according to the disclosures of U.S. Pat. Nos. 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. Pat. No. 4,988,462; U.S. Pat. No. 5,266,233; EP-A-225,654 (Jun. 16, 1987); EP-A-510,762 (Oct. 28, 1992); EP-A-540,089 (May 5, 1993); EP-A-540,090 (May 5, 1993); U.S. Pat. No. 4,615,820; EP-A-565,017 (Oct. 13, 1993); EP-A-030,096 (Jun. 10, 1981), incorporated herein by reference. Such compositions can contain various particulate detersive ingredients stably suspended therein. Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • [0204]
    Process of Cleaning Dishware
  • [0205]
    The present invention also relates to a process for cleaning dishware using an applicator. The applicator may be any of those described above. The detergent is enclosed within a pouch as described above. In a preferred embodiment herein the dishwashing process involves the use of a specially modified dishwashing sponge. The sponge comprises a cavity designed to hold the pouch. The applicator is optionally pre-moistening with water. The user must then access the cavity of the applicator and position a water-soluble or water-dispersible pouch in the cavity. The cavity is then optionally covered with another section of the applicator or cap as described above. The applicator is then optionally contacting with water, however at least one of either the applicator or dishware to be washed must be moistened with water. Finally the dishware is contacted with the applicator comprising the pouch.
  • [0206]
    To assess the time taken for the pouch to at least partially dissolve, the pouch is subjected to the below test. The PVA unit dose dishwashing detergent pouches, is placed in a 600 mL glass beaker filled with 500 mL of demineralised water at 48° C. A cylindrical magnetic stirrer (length 50 mm, diameter 8 mm) was added to the water and set to rotate at 200 rpm. The time is measured between placing the pouch into the water and the first moment of release of dishwashing composition. The above experiment is repeated 4 times. The pouch of the present invention should preferably at least partially dissolve in water, according to the above test method, in less than 60 seconds, more preferably less than 30 seconds, more preferably less than 20 seconds. In a preferred embodiment the applicator is squeezed at least once before contacting the dishware with the applicator. Squeezing the applicator comprising the unit dose detergent, more preferably the pouch, breaks or bursts the unit dose and improves the rate of release of the detergent into the applicator.
  • EXAMPLES
  • [0207]
    The examples provided below are in no way meant to be limiting. The pouches are made by placing one layer of polyvinyl alcohol (PVA) film, Monosol M8630 film of 76 micron, into a mould with preferably rounded corners (24 mm×24 mm). A vacuum is applied to deform the PVA film so that it takes the shape of the cavities. Heat is applied to the film to facilitate the deformation of the film. Whilst the vacuum is maintained, each cavity is filled with 5 ml of composition A-D listed below. A second layer of PVA film is then put on the mould and both PVA films are sealed onto each other to form the pouches. The average sealing conditions are 150° C. for 2 seconds. Finally, after releasing the vacuum, each pouch is individually cut by hand out of the net of 90 pouches. The perfumes listed below are selected form the perfume examples described earlier.
    A B C D
    INGREDIENT BLUE GREEN YELLOW RED
    NaAE0.6 30.15 30.15 30.15 30.15
    Amine Oxide 7.24 7.24 7.24 7.24
    Nonionic C10E8 3.36 3.36 3.36 3.36
    Bis(aminomethyl)cyclohexane 0.55 0.55 0.55 0.55
    Polydimethylaminoethyl 0.22 0.22 0.22 0.22
    methacrylate
    NaCl 0.10 0.10 0.10 0.10
    Water 14.76 14.76 14.76 14.76
    Propylene glycol 43.11 42.87 42.90 43.00
    Duasin Acid Blue AE liquid #9 0.008 0.001
    from Clariant
    Perfume A 0.5
    Duasin Acid Yellow 0.05 0.025 0.001
    SF liquid #23 From Clariant
    Perfume C 0.7
    Perfume B 0.7
    D&C Red liquid #23 0.015
    from Warner & Jenkinson
    Perfume H 0.6
  • [0208]
    The 5 ml PVA unit dose dishwashing detergent pouches, above, were placed in a 600 mL glass beaker filled with 500 mL of demineralised water at 48° C. A cylindrical magnetic stirrer (length 50 mm, diameter 8 mm) was added to the water and set to rotate at 200 rpm. The time is measured between placing the pouch into the water and the first moment of release of dishwashing composition. The above experiment was repeated 4 times with each pouch A-D. The average time taken for the release of detergent was 22 seconds.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1975451 *Aug 29, 1932Oct 2, 1934Expello CorpCleaning implement
US2032762 *Feb 28, 1931Mar 3, 1936Mitchell Patents CorpCleaning device
US3066347 *May 2, 1961Dec 4, 1962Vosbikian Peter SCleaning devices
US3086241 *Apr 30, 1962Apr 23, 1963Bohn Frank WGlass washer
US3114928 *Nov 20, 1961Dec 24, 1963Electr O Mech IncSponge for containing soap
US3198478 *May 11, 1962Aug 3, 1965Johnston Donald NGate valve operating mechanism
US3428405 *Dec 3, 1965Feb 18, 1969Posner Howard LarryCleansing structure
US4254530 *Nov 13, 1979Mar 10, 1981Drutan Products, Inc.Cleaning and washing pad
US4291697 *Apr 18, 1980Sep 29, 1981Stephen GeorgevichCleaning and application device for medical purposes
US4776445 *Sep 24, 1986Oct 11, 1988Voest-Alpine AktiengesselschaftDevice for transferring the cup heap of debris onto a drift conveying means
US4789262 *Jun 1, 1983Dec 6, 1988Theolinde SanchezSoap holding cleaning pad
US4886388 *Jul 28, 1988Dec 12, 1989Gulker Stuart PCleanser dispensing sponge system
US5638236 *Apr 25, 1994Jun 10, 1997Sony CorporationTape cartridge having a single use cleaning leader which utilizes rupturable pouches of cleaning solvent
US5802655 *Jul 18, 1996Sep 8, 1998Denton; Thomas W.Cleaner-wiper package
US6037319 *Apr 1, 1997Mar 14, 2000Dickler Chemical Laboratories, Inc.Water-soluble packets containing liquid cleaning concentrates
US6086278 *Apr 19, 1994Jul 11, 2000Keller; James McneelFoam dispensing bottle brush
US6303553 *May 7, 2001Oct 16, 2001Colgate-Palmolive CompanyPowdered automatic dishwashing cleaning system
US6624130 *Dec 28, 2000Sep 23, 2003Unilever Home & Personal Care Usa Division Of Conopco, Inc.Laundry product
US6685376 *Feb 21, 2001Feb 3, 2004Coronet-Werke GmbhCleaning or application device comprising a sponge body, and method for producing the same
US20020137648 *Nov 27, 2001Sep 26, 2002Sanjeev SharmaDishwashing method
US20020169092 *Nov 27, 2001Nov 14, 2002Alexandre Catlin Tanguy Marie LouiseDetergent products, methods and manufacture
US20030050210 *Oct 23, 2002Mar 13, 2003The Procter & Gamble CompanyPouched compositions
US20030077106 *Feb 21, 2001Apr 24, 2003Georg WeihrauchCleaning or application device comprising a sponge body, and method for producing the same
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6911059 *Nov 26, 2003Jun 28, 2005Infineon Technologies AgAbrasive pad and process for the wet-chemical grinding of a substrate surface
US8283305Jan 22, 2007Oct 9, 2012The Procter & Gamble CompanyCleaning implement with erodible foam substrate and controlled release system of active agent
US20040116054 *Nov 26, 2003Jun 17, 2004Stefan GeyerAbrasive pad and process for the wet-chemical grinding of a substrate surface
US20070161533 *Jan 22, 2007Jul 12, 2007The Procter & Gamble CompanyCleaning implement with erodible foam substrate and controlled release system of active agent
WO2007127045A1 *Apr 11, 2007Nov 8, 2007Ecolab Inc.A packaged cleaning composition concentrate and a method and system for forming a cleaning composition
WO2013165725A1Apr 22, 2013Nov 7, 2013Danisco Us Inc.Unit-dose format perhydolase systems
Classifications
U.S. Classification134/6, 134/29, 134/25.2
International ClassificationA47L13/17, A47L17/00, C11D17/00, A47L15/44, C11D17/04
Cooperative ClassificationC11D17/042, C11D17/041, A47L17/00, C11D17/0091
European ClassificationC11D17/00H8T8, A47L17/00, C11D17/04B2, C11D17/04B
Legal Events
DateCodeEventDescription
Apr 6, 2005ASAssignment
Owner name: PROCTER & GAMBLE COMPANY,THE, OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MANGIN, RAPHAEL LOUIS;GODERIS, TOM JOZEF PIETER;ESPINOSA, ERIC HENRI;REEL/FRAME:016058/0470;SIGNING DATES FROM 20010720 TO 20010723