GB1587783A - Detergent-scrubber articles - Google Patents

Description

(54) DETERGENT-SCRUBBER ARTICLES (71) We, COLGATE-PALMOLIVE COMPANY, a Corporation organised under the laws of the State of Delaware, United States of America, of 300 Park Avenue, New York, New York 10022, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to detergent-scrubber articles, and to methods of manufacturing such articles.

According to one aspect of the invention a detergent scrubber article comprises an exposed solid detergent-composition body affixed to an exterior surface of a body of a low density closed cell material functional as a scrubbing means for scrubbing soiled or stained surfaces of the items to be cleaned after application of the detergent composition thereto and functional as a handle by means of which the solid detergent composition can be held while applying the composition to the items to be cleaned.

Preferably the body of low density closed cell material is thicker than the solid detergent composition body.

The body of low density closed cell material, e.g. a closed cell foam of polymeric material such as polystyrene or polyethylene, acts as a handle, allowing the use of the detergent composition without requiring the user to touch the detergent composition itself.

This is advantageous in cases where the detergent composition is a built synthetic organic detergent composition which may be drying to the skin or irritating to it. The body of low density closed cell material, functional as a handle, facilitates holding of the detergent composition body by means of the handle to assist in applying detergent to surfaces to be cleaned; it furnishes a backing for the solid detergent composition body to limit tensile stresses being imposed on it which could otherwise result in its disintegration; it furnishes a platform on which the solid detergent composition body may rest after use, which platform facilitates draining of water from the detergent composition body and thereby prevents excessive gel formation, conserving the detergent; and it helps one to hold on to and apply detergent from a thin or small detergent body which might otherwise be wasted.

Additionally, the handle portion functions as a scrubbing means (which term includes mildly abrading and wiping means) for working the detergent into or promoting contact of it with the surface to be cleaned and for removing loosened soils and stains from such surface. Because the handle and scrubbing means is made of low density material it decreases the overall density of the article and normally makes it capable of floating in water, thereby preventing accidental permanent or temporary loss of the article in a body of water with which it is being used. This feature allows the making of the usually comparatively high density solid built detergent compositions into products of weights and densities with which the consumer is more familiar. This factor, with the handle feature, makes the articles much easier to utilize.

A binder may be employed between the scrubber-handle body portion and the detergent composition body portion to fix the bodies together, and as the scrubber-handle portion is made of a closed cell material this prevents the transmission of moisture through the scrubber-handle to the binding agent and thereby improves its stability and binding effect.

Thus, there is no need to provide a protective film of water-insoluble material between the closed cell material and the binding agent, nor is it necessary to utilize a binder which is so insoluble in water as to leave an objectionable residue along the contacting surface of the scrubber portion of the article as detergent is consumed and that surface is exposed.

According to another aspect of the invention a method of manufacturing a detergentscrubber article comprises continuously producing a bar or slab of low density closed cell synthetic organic polymeric material, continuously producing a solid bar or slab of detergent composition, continuously bringing major surfaces of the bars or slabs together as they are produced so that a bar or slab of low density closed cell material is brought into contact with a bar or slab, respectively, of detergent composition, pressing the contacting bars or slabs together to affix the detergent composition to the closed cell polymeric material and cutting the product into individual detergent-scrubber articles.

The invention may be performed in various ways, and by way of example an article embodying the invention and a method for manufacturing such articles will be described with reference to the accompanying drawings, in which: Figure I is a perspective view of an article embodying the invention, of flat rectangular shape, with a handle-scrubber portion of closed cell foam polymer cemented to a similarly sized but thinner bar of a milled and plodded built laundry detergent composition; Figure 2 is a side elevation of the bar of Figure 1; Figure 3 is an enlarged view of the circled portion of Figure 2; and Figure 4 is a schematic representation of the arrangement of equipment and the processing steps employed in the manufacture of such articles.

In Figures 1 and 2 the detergent-scrubber article 11 includes a scrubbing and handle body 13 and a solid detergent composition body 15 held together by cement, glue or other adhesive layer 17 between major surfaces of the two bodies. The scrubber-handle body 13 is made of a closed cell foam of a polymeric plastics material (a polyethylene foam is used in this embodiment but a polystyrene or other acceptable closed cell foam can also be used).

As illustrated, the foam has been cut at the surfaces thereof, or at least at some of such surfaces, so that many cells at such surface are cut through or open. The structure of such cells is better shown in Figure 3.

In Figure 3, opened cells of the polymeric foam are shown at 19 and the unaltered closed cells are shown at 21. The adhesive 17 penetrates into the interiors of the cut surface cells to hold to the foam better.

Similarly, if desired, the surface of the detergent bar to be cemented to the polymer foam may be roughened, grooved, perforated or otherwise treated to promote bonding to the foam material.

In Figure 4 a method for manufacturing a preferred article of this invention is illustrated.

A milled detergent composition is plodded to continuous bar form 23 in a plodder 25, and a polymeric closed cell foam is produced in bar form 27 by an extruder 29. The detergent bar and the extruded foam bar are brought together, preferably after application by applicator 31 of cement or adhesive 33 to one of the major surfaces to be held together to make a coated bar 32. A roller press 36 presses the bars together at a location 34 where the foam has become substantially rigid. The joined bodies, with the parts thereof not yet firmly fastened together, are cut to length by a cutter 35 to form the desired articles. These are wrapped at a wrapping machine 37 to make the wrapped products 39, the wrappings holding the articles tightly and pressing the foam and detergent bodies together, facilitating good cementing while the cement is hardening.

The detergent compositions utilized preferably comprise a synthetic organic detergent or a mixture of synthetic organic detergents as the active detersive component, but fatty acid soaps may also be utilized, either as the only active detersive component or in mixture with synthetic organic detergent(s).

Cationic detergents are generally unsatisfactory and their use should be avoided. Usually they do not have the desired cleaning powers, nor do they possess other desirable physical characteristics of the preferred normally solid anionic and nonionic detergents. While amphoteric detergents may be employed, preferably in combination with normally solid nonionic detergents, these too are generally less acceptable than the anionic and nonionic detergents. Soaps are useful but they do have the disadvantage of forming insoluble curd in hard waters, which is often objectionable. Also, they may not clean as well as the anionic and nonionic synthetic organic detergents in hard water.

Among the useful anionic synthetic organic detergents there may be mentioned the alkyl aryl sulphonates, preferably those wherein the alkyl group is linear and the aryl is benzene; olefin sulphonates; paraffin sulphonates; fatty alcohol sulphates; fatty acid monoglyceride sulphates; sulphated oxyethylated fatty alcohols; fatty esters of isethionic acid; fatty amides of taurine and N-methyl taurine; fatty amides of sarcosine; fatty sulphoacetates; and sulphated fatty alkylolamides. Also useful are various sulphated derivatives of nonionic detergents, such as those which will be mentioned below. In addition to the sulphonates and sulphates (the so-called sulphuric reaction products) one may also employ phosphates and phosphonates and other suitable anionic groups in making the detergents. The alkyl and acyl groups of the anionic detergents are usually of 8 to 20 carbon atoms, preferably of 12 to 18 carbon atoms and generally preferably being linear in configuration. All the anionic synthetic organic detergents are employed as water-soluble salts, preferably as alkali metal salts and most preferably as sodium salts. However, alkaline earth metal salts, ammonium salts, triethanolamine salts and other salts may also be employed, but the sodium salts are usually preferred because of their desirable level of water solubility and their sufficient physical hardness to be converted to a satisfactory bar product. The fatty acid soaps that are useful are the water-soluble and normally solid soaps. The fatty acids of such soaps are normally of 8 to 20 carbon atoms and are obtained by saponification of usual soap making fats and oils, such as tallow, hydrogenated tallow, lard, grease, coconut oil, palm oil, palm kernel oil and other well-known materials of similar types. The soaps are usually alkali metal soaps, preferably sodium soaps, but potassium soaps have also been found satisfactory in some applications. Triethanolamine soaps or soaps of other organic bases can be used but usually are not as efficient as those of sodium. Alkaline earth metal soaps and magnesium soaps are not generally employed as detersive components but in some instances they may be added to the bar composition as fillers or lubricants or for other proposes, and sometimes magnesium salts may be added to form magnesium detergents from the synthetic anionic detergents.

The normally solid water-soluble nonionic detergents that may be included in the detergent bar usually contain chains of lower alkylene oxide, most frequently ethylene oxide, to increase their hydrophilic properties. Examples are fatty alcohol ethers of polyoxyethylene alcohols; ethylene oxide-propylene oxide block copolymers of high molecular weight, e.g. 5,000 to 20,000; ethylene oxide aducts of di-alkyl phenols; fatty acid esters of polyoxyethylene alcohols; and fatty acid esters of multihydroxy compounds, such as sugars, hexitans and polyglycols. The molecular weights of such materials will be chosen so as to result in their being of satisfactory water solubility and of sufficient hardness to be useful in the present compositions. Thus, a preferred class of such compounds includes fatty condensation products which are the monoethers of a fatty alcohol or a mixture of such alcohols and terminally bi-alcoholic polyethylene oxide wherein the fatty alcohol is of 12 to 15 carbon atoms and the number of ethylene oxide units per mol is from 5 to 20, preferably 7 to 15 and most preferably 12 to 15. Although it is important that the synthetic organic detergent be sufficiently solid to allow the production of a satisfactory solid bar product, a small proportion of a normally liquid synthetic organic detergent, usually a nonionic detergent, may be employed in the compositions providing that it is sufficiently absorbed or held to the other components of the composition, such as the detergents, builders, fillers and other solid components present. Thus, up to as much as 10% of a normally liquid detergent component may be present but usually such percentage will be less than 5% and most preferably is less than 2%. These and all other proportions, ratios and parts used throughout this specification, are by weight unless otherwise indicated.

Specific examples of preferred anionic synthetic organic detergents are sodium linear tridecyl benzene sulphonate; sodium linear dodecyl benzene sulphonate; sodium dodecyl sulphate; sodium C16-18 paraffin sulphonate; sodium C14.15 olefin sulphonate; sodium polyoxyethylene ethylene sulphonate wherein the oxyethylene group is of 3 to 15 ethylene oxides; and sodium N-lauroyl sarcoside. Preferred nonionic detergents include condensation products of a mixture of C12 to C15 fatty alcohols with ethylene oxide (11 mols of ethylene oxide per mol. of fatty alcohol) condensation products of polypropylene glycol with ethylene oxide of molecular weight of about 10,000 (PLURONIC trade mark, made by BASF-Wyandotte, U.S.A.); and polyoxyethylene sorbitan and hexitan fatty acid esters (TWEEN trade mark, made by Atlas Chemical Inudstries, U.S.A.). Instead of the anionic detergents there may be employed an anionic hydrotrope such as a soluble benzene sulphonic acid or substituted benzene sulphonic acid alkali metal salt, e.g. sodium toluene sulphonate and sodium cumene sulphonate. Usually a hydrotrope will be present, if at all, in a lower proportion than the anionic detergent, e.g. from 2 to 20%, preferably 5 to 15%, the proportion of hydrotropic material being limited to about 1/20 to 1/4 of the synthetic detergent present. Among the preferred soaps are the sodium soaps of tallow and hydrogenated tallow and of mixtures of either or both of such tallows with coconut oil, palm oil or palm kernel oil, wherein, for example, the ratio of tallow to coconut oil is in the range from 90:10 to 70:30, preferably from 85:15 to 80:20.

Builder salts for the detergents may be inorganic and/or organic, the former usually being preferred. Among these are included alkali metal phosphates, polyphosphates, borates, carbonates, silicates and bicarbonates, such as pentasodium tripolyphosphate, tetrasodium pyrophosphate, tripotassium polyphosphate sodium carbonate, sodium silicate (usually of Na2O:SiO2 ratio in the range from 1:1.6 to 1:3, e.g. 1:2.0 and 1:2.4), borax and sodium bicarbonate. Mixtures of such materials may also be utilized. Among the organic builders for synthetic organic detergents (and also for soaps) are sodium citrate, sodium gluconate, various sequestrants including trisodium nitrilotriacetate and tetrasodium ethylene diamine tetraacetate, and trisodium 2-oxa-1,1,3-propane tricarboxylate. In addition to watersoluble builders, many of which hydrate so as to tie up moisture and thereby prevent access of such moisture to the bonding surface between the detergent composition body and the cellular polymeric foam material, also useful are water-insoluble builders of the molecular sieve or synthetic zeolite type, such as types 4A and 3A molecular sieves and various other such sieves, e.g. type x and y sieves. Such materials are sodium aluminium silicates, usually hydrated, and also are capable of absorbing large quantitites of moisture without liquefying. These and various other such compounds that are useful are described in the text book Zeolite Molecular Sieves by Donald W. Breck, published in 1973 by John Wiley & Co., Inc., New York. Such zeolites may also function as mild abrasives or scrubbing components in the detergent bar.

Filler materials may also be utilized in the detergent compositions to improve the body thereof and often these (and other component) materials also perform other desirable functions. Among the desirable fillers are hydratable sodium sulphates, including sodium bisulphate. Sodium chloride may also be employed but is not a sorbent for moisture. Clays, wood flour, finely divided silica (silex), pumice powder and similar materials may perform a filler function but usually will be primarily considered as abrasives or scrubbing agents, intended to improve rubbing contact with the surfaces to be cleaned. The particle sizes of such materials and others employed in the solid detergent composition body will usually be kept small enough not to be destructive of or harmful to the materials being cleaned. Thus, in detergent-scrubber articles intended for use in washing laundry, particularly for helping to remove dirt from shirt collars and cuffs, the particle sizes will be less than one millimetre, preferably less than 500 microns and most preferably less than 100 microns. Similarly, with respect to other insoluble materials which may be present in the compositions, limitation to such particle sizes is also desirable. Normally the particles will be larger than 5 microns and generally most of them will be larger than 10 microns, equivalent diameters.

In addition to the previously mentioned desirable components of the solid detergent composition body there may also be present small proportions of water and various adjuvants. The proportion of water will usually be in the range from 1 to 20%, preferably from 3 to 15% and often most preferably from 5 to 10%. The total amount of adjuvants will generally not exceed 20% and preferably will not exceed 10% of the composition, often being less than 5% thereof. Amounts of individual adjuvants will usually be small, e.g. from 0.05 to 8%, preferably from 0.05 to 2%. The adjuvants which may be employed include inorganic pigments, e.g. Indanthrene Blue RS; dyes, e.g. Color Index Direct Blue 1; fluorescent dyes, known as optical brighteners, such as coumarin, triazolyl stilbene, stilbene cyanuric, acylamino stilbene and other types; organic gum anti-redeposition agents, e.g.

sodium carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylamide; perfumes; fungicides or preservatives, e.g. polyhalosalicylanilides; sanitizers, e.g.

trichlorocarbanilide; foam supressors, e.g. N,N-dilauryl amine; enzymes, e.g. subtilisin protease; bleaching agents, e.g. di- and tri-chloro (or bromo) cyanuric acid and water-soluble salts thereof, and sodium perborate; fabric softeners, e.g. 1,2-alkane diols of 15-18 carbon atoms; plasticizers, e.g. cetyl alcohol, glycerine and propylene glycol; and bodying agents, e.g. wood flour.

The proportions of the various components of the solid detergent composition body will normally be in the range from 5 to 35% of water-soluble detergent component, from 20 to 95% of builder and 0 to 60% of filler. If water is present the proportion thereof will usually be in the range from 1 to 25% (including water of hydration). The total proportion of adjuvants will generally be limited to 20%, as previously mentioned. Preferably, the detergent will be water-soluble synthetic anionic organic detergent, the builder will be water-soluble inorganic builder salt and the filler will be water-soluble filler salt, sometimes in conjunction with a water-soluble inorganic powder material which may function as a scrubbing agent to improve cleaning power of the product. The ranges of water-soluble filler salt and water-insoluble inorganic powder will usually be 0 to 60% of the former and 0 to 50% of the latter, preferably from 5 to 40% of filler, when employed, and from 10 to 35% of abrasive or scrubbing agent, when employed.

Although it is possible to utilize a settable detergent composition which is deposited on the surface of the foamed polymeric material and allowed to harden and set there to produce an article resembling that shown in Figures 1-3, in which setting will preferably be promoted by hydration of the content of hydratable builder or filler present, it is highly preferred to utilize a plodded detergent composition in bar form, the manufacture of which is illustrated in Figure 4. For the manufacture of such a bar the various components of the composition are mixed together and the mix is plodded, utilizing a conventional soap or detergent plodder, which compresses the mix and converts it to form retaining bar shape.

Preferably, before plodding the mixture is amalgamated so that the components thereof are evenly distributed and then is milled, using a soap mill, preferably of 3 or 5 rolls or more, to disperse the various components even better. Mill opening settings may vary but for best mixing and size reduction of oversize particles they are usually in the range from 0.1 mm to 0.4 mm, preferably 0.1 to 0.3 mm. If desired, before milling and plodding, the moisture and volatile materials content of the detergent composition may be decreased by a drying operation, such as one wherein chips or flakes of the composition are made and are dried on a belt dryer by means of warm air.

The handle-scrubber body of the articles may be one which is substantially rigid and of low density, in addition to being optionally of a thickness greater than that of the solid detergent composition body. While various materials may be employed for the handlescrubber body an important consideration is that the material selected should be sufficiently rigid so that even when wet it will not become so pliable as to make it unsuited for holding and for use as a scrubbing surface. Thus, opened cell foams such as cellulosic foams and open celled polyurethane foams are not useful for making the articles of the present invention. Some essentially closed cell materials, such as low density woods, e.g. balsa wood, which satisfy the density requirements of the present invention, may be employed but far superior to any such other materials are the closed cell synthetic organic polymeric material foams, such as those of polystyrene and polyethylene. Other such foams may also be used, including those made from polypropylene and polyurethane and various other foamed plastics providing they have the desired characteristics of low density, waterinsolubility, rigidity (resistance to excessive distortion) and surface and cell strength to make them suitable for employment as scrubbing surfaces. Thus, among such materials from which suitable foams may be made are acrylics, cellulose acetates, epoxies, polybenzimidazoles, polycarbonates, polyethylenes (both cross-linked and non-crosslinked), ionomers, phenolics, polypropylenes (preferably cross-linked), polystyrenes, polyurethanes, polyvinyl chlorides, silicones, styrene acrylonitriles and urea formaldehydes. Additionally, various reinforced foams may be employed, such as those of nylons, polycarbonates, polypropylenes and polystyrenes (but preferably these are of lower densities than those normally utilized for such reinforced foams).

The closed cell polymer foams employed will preferably be extrudable to quickly solidifiable form, such as by the equipment and method illustrated in Figure 4. However, such foams may be cast in place or may be made into rods, slabs or bars which are subsequently cut to desired shape. Also, they may be moulded to shapes, in which case it is easier to form rounded corners, curved surfaces and various other shapes and indicia. The synthetic organic polymeric foam will normally be of a density in the range from 0.01 to 0.7 g/cc, preferably from 0.01 to 0.2 g/cc and more preferably from 0.01 to 0.07 g/cc most preferably being from 0.01 to 0.04 g/cc for polystyrene and from 0.02 to 0.07 g/cc for polyethylene and similar materials. The compression strength of the foam at a 10% deflection, as measured by ASTM Test D 1621, will usually be in the range from 0.1 to 20 kg/sq. cm and preferably from 0.1 to 10 kg/sq. cm, most preferably being from 0.2 to 2 kg/sq. cm. Compressive strengths in such ranges allow the successful utilization of the foam as a scrubbing implement and furnish sufficient rigidity for use as a handle. Thus, while holding the foam handle at the sides thereof with a force of about 5 kg exerted by the thumb on one side and the four fingers on the other side at room temperature (20"C), a suitable polyethylene or polystyrene foam will deflect about 0.5 to 5 mm and is resilient enough to return to the original form when the pressure is released. Tensile strengths should be greater than 1 kg/sq. cm, preferably being from 1 to 10 kg/sq. cm so as to avoid fragmentation of the product during subjection to the stresses of ordinary scrubbing and handle uses.

Of the various foams that are usable polystyrene and polyethylene foams are most preferred. The former foam is inexpensive, the various cells are filled with polystyrene material and it acts satisfactorily as a handle and scrubbing material. However polyethylene foams often appear to be easier to hold, have surfaces of more desirable tactile properties and often are of more attractive appearance, especially after use. They also appear to be more resistant to separations of minor portions of cells, which appear to be more firmly interconnected than those of polystyrene.

To fasten the milled and plodded detergent bar and extruded closed cell plastic body together the employment of cement, glue or other adhesive is not always necessary. Thus, when the closed cell foam is still somewhat soft, either before total curing or before cooling to rigidity, pressing a surface thereof against the detergent bar, especially if such bar is extruded in striated or grooved shape on the joining major surface or has perforations made at such surface, can result in the two portions of the article being satisfactorily held together so as to resist any stresses which might tend to separate them during normal use. Also, the detergent composition may be solidified, as by hydration of hydratable salts thereof, while in contact with a surface of the cellular foam, especially if such surface has been cut or roughened beforehand; the detergent composition, filling such openings, may make a firm bond. However, often it will be more desirable to utilize an appropriate cement, glue or other adhesive, which is preferably a synthetic organic resinous material, such as polyvinyl acetate, epoxy resin, melamine formaldehyde, phenolic resins, urea formaldehyde, nylon, cyanoacrylate, silicone elastomer, polyethylene, polyvinyl butyral, polyisobutylene, polyisoprene, neoprene and nitrile rubber. However, other bonding agents may also be used, such as casein, hide and bone glues and other protein-based glues and any other suitable materials known to be effective cements. Alternatively, a solvent may be employed to soften the material of the foam polymer so that such surface itself may be bonded to the detergent bar. Generally, it will be desirable for the bonding agent employed to hold tightly to both the detergent composition and the foam polymer, resist loosening when contacted by water, yet not leave an objectionable surface in contact with the foam at locations where the detergent composition has been dissolved away. Polyvinyl acetate and casein glues are inexpensive products which satisfactorily and effectively function as binding agents and have the described desirable properties. However, pressure-sensitive rubber-based or similar adhesives are also suitable, as are various others of the bonding agents of the types mentioned above.

The ratio of the volume of the solid detergent composition body to that of the low density synthetic polymeric material body will normally be in the range from 1:1.5 to 1:10, preferably being from 1:1.5 to 1:3 and most preferably being from 1:2 to 1:3. The thicknesses of the usually substantially flat bodies will normally be from 5 mm to 5 cm for the foam body and from 2 mm to 2 cm for the detergent composition body, preferably from 1.5 cm to 3.5 cm for the foam body and from 8 mm to 1.5 cm for the detergent composition body. At such thicknesses and volumes and in such ratios of volumes (and thicknesses) satisfactory handles and scrubbing surfaces are provided, and over the density ranges of the detergent composition bodies and those of the polymeric foam the total article will float in water. Weights of the articles will usually range from 25 to 150 g, preferably 30 to 130 g, with volumes of.from 75 to 250 cc preferably 90 to 240 cc and overall densities of from 0.4 to 0.9 g/cc, preferably from 0.4 to 0.7 g/cc.

The cement layer, when employed, will normally not be of a greater thickness than 1 mm and preferably is less, e.g. about 0.2 mm. Such thickness does not include penetration into the opened cells of the foam and such penetration may be equal to the cell's equivalent diameter. Of course, when no cement, glue or other adhesive is utilized, in some cases the polymeric material may be fused for the top cell thickness or the fused layer may be up to twice such thickness. Normally the layer of adhesive or fused material will be at least 0.1 mm thick. While it is possible to spot adhesive or distribute it in lines or other patterns across the surfaces to be joined together, normally evenly spreading over the entire surfaces, as by a doctor roll, is preferable.

The articles of this invention possess many significant advantages over prior art products.

The substantially rigid closed cell foam acts as both a handle and a scrubbing surface and at the same time supports a thin detergent composition body to prevent cracking during shipment, storage and use. The handle may be em consumption of the detergent composition.

The following Examples further illustrate the invention.

Example 1 A dodecylbenzene sulphonic acid of light colour, having been bleached with hydrogen peroxide, is mixed with water, sodium carbonate, kaolin, impalpable calcium carbonate, titanium dioxide, magnesium sulphate, perfume and sufficient moisture to compensate approximately for that expected to be lost in processing. The mix formula is as follows: Parts *Bleached dodecylbenzene sulphonic acid 24.8 Sodium carbonate, dense 36.8 Kaolin 12.0 Calcium carbonate, impalpable 22.1 Titanium dioxide, rutile 0.3 Magnesium sulphate 2.0 Perfume (citronellol) 0.3 Water 1.7 100.0 *85 % dodecylbenzene sulphonic acid, 2% sulphuric acid, 3.2% free organic acid and 9.8% water.

In the above product the sizes of particulate materials utilized are in the 5 micron to one millimetre equivalent diameter range, mostly being between 0.1 mm and 1 mm in equivalent diameter. After mixing in a sigma blade mixer is completed the detergent composition resulting is milled in a three-roll soap mill set at an opening in the 0.1 mm to 0.3 mm range and is continuously plodded as a flat bar having a thickness of 1.1 cm and a width of 5.9 cm. During manufacture of the bar there is a moisture loss of about 1.6 parts so that 98.4 parts of detergent composition bar product result. The bar contains 22.8% of sodium dodecylbenzene sulphonate, 30.7% of sodium carbonate, 5.0% of sodium bicarbonate, plus the calculable proportions of the other components. The bar is cut to rectangular shaped pieces each 9.2 cm long.

A closed cell polyethylene foam, "Ethafoam 220" (ETHAFOAM is a trade mark) made by The Dow Chemical Company, U.S.A., having closed cells of equivalant diameters of from about 0.5 mm to about 2 mm, most of which are of diameters in the 0.8 to 1.5 mm range, and having a density of about 0.035 g/cc, is cut to size to match the length and width of the detergent composition body, with a thickness of 3.2 cm. A major surface of each such body has had cells thereof cut or otherwise divided so that the opened cells at such surface may serve as anchors for a bonding agent. Thin layers (e.g. 0.2 mm thick) of polyvinyl acetate resin glue ("Elmer's Glue-All", manufactured by Borden Chemical Co. U.S.A.) are spread on the major surfaces of both the detergent composition body and the foam body and the glued surfaces are pressed together with a nominal force, e.g. 0.3 kg/sq. cm until sealed. The combination article, after application of the cement and pressing of the parts together, is packaged and the packaging holds the article together until the cement is set.

Alternatively, holding means, such as rubber bands, are utilized to hold the two bodies of the article together during setting of the cement. If desired the bands may be retained thereon to assist in such holding during use. However, although such additional holding means may be useful, they are not essential.

The detergent-scrubber articles made are tested for use in washing clothing, such as heavily soiled shirts and trousers, some of which are oily and greasy denims, also having clay and other dirt thereon. Application of the detergent composition by contacting the soiled surfaces with the detergent composition body portion of the article while holding the article by the handle portion and subsequent application of the foam surface to the soiled surfaces with a rubbing motion, significantly facilitate removal of the oil, grease, clay and other dirt and staining materials also present. Similarly, shirt cuffs and collars are treated and it is found that direct thereon is readily and conveniently removed. The detergentscrubber article floats in wash water so it is not readily lost and does not require immersing of one's arm in a tub or dishpan to retrieve such an article that has slipped from one's hand.

Also, because of its low density and effective handle portion it is easier to hold so that dropping it is a less frequent occurrence. When use of the bar is temporarily suspended it is stored with the foam side down and it is found that it drains and rehardens fast, without the formation of objectionable gel on the bar and on the sink or other surface on which it is placed. Despite repeated uses the detergent composition body portion is satisfactorily held to the closed cell foam portion, and even if it is accidentally removed therefrom it is still possible to reassemble the parts easily, utilizing cement as originally applied or using mechanical means for refastening. During continued use, wherein several loads of laundry, up to 10 kg, are washed with the article, the detergent composition body wears down evenly and does not crack or disintegrate into smaller pieces and thus the article helps to prevent waste of detergent composition. For any composition that might dry poorly, single use tablets may be preferred.

Test results indicate that the articles are superior to ordinary laundry detergent bars in removing dirt, in economy, in being kind to the hands, in not causing fading of clothing, for washing rough fabrics such as denim, for washing delicate fabrics, for removing dirt with minimum scrubbing effort, for being capable of scrubbing a large area, for being easy to rinse, for being easy to rub on clothes and for remaining dry and hard when not in use. The articles were also found to be capable of many other uses than just for washing heavily soiled laundry.

When the detergent composition is completely consumed the cellular foam body is still of approximately its original size and shape. It may be recoated with another slab of detergent composition, may be used as an art material or a plaything, or may be employed in various other ways for functional and aesthetic purposes.

In variations of the described embodiments different detergent compositions may be utilized, such as those having sodium lauryl sulphate; sodium tridecylbenzene sulphonate; sodium dodecylbenzene sulphonate plus 1/10 such proportion of nonionic detergent (Neodol 45-11, manufactured by Shell Chemical Co. U.S.A.); and a mixture of sodium soaps of hydrogenated tallow and hydrogenated coconut oil (85:15) weight proportion) and sodium tridecylbenzene sulphonate; (in 50:50 prop6rtion) replacing the sodium dodecylbenzene sulphonate; pentasodium tripolyphosphate or equal parts of sodium carbonate and sodium silicate (Na2O:SiO2 = 1:2.4) replacing the sodium carbonate and sodium bicarbonate; and sodium sulphate replacing the kaolin and magnesium sulphate.

Alternatively, the magnesium sulphate may be omitted from the formula and the moisture content of the finished production may be adjusted to about 9%. The products resulting are also useful detergent-scrubber articles. Similarly, the closed cell polyethylene foam may be replaced by a "Styrofoam" (Trade Mark) of similar size and structure, such as Dow "Styrofoam 1B", which is of about the same density as the polyethylene foam. Also, the polyvinyl acetate emulsion glue may be replaced with casein, epoxy, cyanoacrylate or sodium silicate solution (water glass). Such articles have the physical characteristics previously mentioned and the polystyrene foam performs in similar fashion. In further modifications the thicknesses of the component parts are diminished to 3/4 and (for both parts) of the original thicknesses and further to 1/4 for the detergent composition body while retaining l/2 the original thickness for the foam. The different articles so described are also useful in the same manner as the others heretofore mentioned with the exception that the detergent composition will be consumed more quickly and so such articles are more suited for fewer wash loads, some being useful for only a single washing. To increase the useful life of the article it may be employed only for rubbing dirt deposits and/or stains that are otherwise difficult to remove, the major proportion of detergent composition for washing of the entire garment or laundry article being supplied by a commercial liquid or powdered heavy duty laundry detergent composition, which may be used in a washing machine.

In addition to employing the article for washing laundry, it may also be used for washing walls, floors, bathtubs, sinks, dishes and various other materials and surfaces and performs satisfactorily, with the advantages previously recited for it. Thus, by "scrubbing article" it is intended also to cover wiping, applying and abrading articles.

Various additional modifications to the article are possible and may be advantageous.

For example, the detergent body and the foam body may be coloured the same, by dyes or pigments, or may be made in contrasting colours. They may be physically interfitted, as by mortise-tenon joints, to promote holding together during use. The density of the detergent composition body may be reduced by having low density cellular polymeric material, such as expanded polystyrene beads (from which the closed cell polystyrene body may be made, although that described in this Example was not so made), dispersed in the detergent composition mix before plodding (care should be taken not to crush the beads during the milling operation). In addition to or instead of perfuming the detergent composition bar, the foam may be perfumed; this may allow the use of perfumes which would not be stable in the normally alkaline detergent composition. As previously mentioned, both the detergent composition body and the cellular foam body may be shaped as desired for example to elliptical, circular or square shapes, viewing the major surface, and may be rounded or have indentations herein for easier holding.

Example 2 Parts Linear dodecylbenzene sulphonic acid 1,000 (85% active ingredient, 10% water, 5% impurities) Pentasodium tripolyphosphate (slow hydrating) 1,732 Sodium hydroxide 132 Water 400 Sodium silicate (50% aqueous solution) 600 Sodium toluene sulphonate (powder) 80 Sodium carboxymethyl cellulose 40 Optical brightener 4 Blue pigment 8 "Polyox WSR 301" (solid polyoxyethylene glycol) 4 (Polyox is a Trade Mark) ~~~~~~ 4,000 The detergent composition is made of the above ingredients by neutralization of the sulphonic acid with the sodium hydroxide in the presence of water and subsequent combination of the reaction product and the other constituents. After completion of mixing the thick pasty product is quickly applied to a major surface of a cellular polystyrene body made from expandable polystyrene particles, which polystyrene body measures 7 cm by 7 cm by 2.3 cm and weighs 2.5 grams. Thirty two g. of the detergent composition are played on the described slab of expanded polystyrene (of a density of about 0.02 g/cc) to form a layer about 0.9 cm thick thereon. The detergent composition body is allowed to set, which occurs when the pentasodium tirpolyphosphate is completely hydrated and the product is ready for use. It has substantially the same utilities as the product of Example 1 and is found to be an excellent detergent-scrubber article which is easy to use and affords advantages over prior art detergent composition bars.

In variations of this Example, water glass (sodium silicate solution) is applied to the polystyrene foam before contacting the latter with the detergent composition. This assists in sealing the detergent composition and foam portions of the article together. As in Example 1, the constitution of the composition body may be varied, and to secure a smoother texture the composition may be milled and extruded as a form-retaining paste before being applied to the foam. Instead of employing the polystyrene foam, the cells of which are about 1.5 mm to 3 mm in equivalent diameter, compared to 0.7 mm to 3 mm for polyethylene, cross-linked or non-cross-linked polyethylene and the other cellular materials previously described may be substituted. Also, by utilizing expanded polystyrene beads and/or air in the detergent composition mix, the density thereof may be changed within the 0.8 to 2.3 g/cc range, which is preferably 1.4 to 2 g/cc, for the compositions of these Examples and of the other articles described in the specification. Similarly, the thicknesses of the detergent composition body and of the foam body may be varied within the 1:1.5 to 1:10 thickness ratio range. Preferably, when substituting different cellular materials of the closed cell type care should be taken so that the physical characteristics thereof previously mentioned in the specification, compression strength and tensile strength, in addition to density, are within the specified ranges, as are those of the present Examples.

Example 3 The products of Examples 1 and 2 are made by extruding the detergent and foam compositions thereof through a plodder and plastic extruder, respectively, applying adhesive or cement of the type described to either or both of the surfaces to be joined, joining the products together, pressing them with a roll press or other suitable device, cutting and packing. Instead of using a cutter, a hot wire may be employed and instead of applying cement or other adhesive reliance may be placed on the hardening of the detergent composition body portion holding it to the surface of the foam, or on the foam being fused and pressed against the detergent composition body. Alternatively, other means of holding the two parts together during and/or after setting may be employed, such as mechanical fasteners, previously mentioned.

The manufacturing method described provides for quick and efficient production of the articles automatically. It helps to conserve perfume and other volatiles which might otherwise be lost during open air setting or curing processes which might be accompanied by drying. The articles of this Example have the same utilities as described for the articles of Examples 1 and 2 and the mentioned variations thereof.

WHAT WE CLAIM IS: 1. A detergent-scrubber article which comprises an exposed solid detergent composition body affixed to an exterior surface of a body of a low density closed cell material functional as a scrubbing means for scrubbing soiled or stained surfaces of the items to be cleaned after application of the detergent composition thereto and functional as a handle by means of which the solid detergent composition can be held while applying the composition to the items to be cleaned.

2. An article according to Claim 1 wherein the body of low density closed cell material is thicker than the solid detergent composition body.

3. An article according to Claim 1 or Claim 2 wherein the solid detergent composition body comprises soap and/or synthetic organic detergent, and builder and/or filler salt.

4. An article according to Claim 3 wherein the solid detergent composition is a built synthetic organic detergent composition comprising from 5 to 350/0 of water-soluble synthetic anionic organic detergent, from 20 to 95% of water-soluble inorganic builder salt, 0 to 60% of water-soluble filler salt and 0 to 50% of water-insoluble inorganic powder.

5. An article according to any of the preceding Claims wherein the solid detergent composition body and the body of low density closed cell material are flat and are joined together at major surfaces thereof.

6. An article according to Claim 5 wherein the solid detergent composition body and the body of low density closed cell material are joined together by a binder.

7. An article according to any of the preceding Claims wherein the low density closed cell material is a closed cell foam of synthetic organic polymeric material.

8. An article according to Claim 7 wherein the density of the closed cell foam is in the range from 0.01 to 0.7 g/cc, the cells of the foam are of sizes in the range from 0.3 mm to 5 mm equivalent diameter, the solid detergent composition body is of a density in the range from 0.8 to 2.3 g/cc and the ratio by volume of the solid detergent composition body to the body of low density material is in the range from 1:1.5 to 1:10.

9. An article according to Claim 8 wherein the density of the closed cell foam is in the range from 0.01 to 0.2 g/cc, the density of the solid detergent composition body is in the range from 1.4 to 2 g/cc, the compression strength of the foam at 10% deflection is in the range from 0.1 to 20 kg/sq. cm and the tensile strength thereof is at least 1 kg/sq. cm.

10. An article according to any of Claims 7 to 9 wherein the synthetic organic polymeric material is polystyrene.

11. An article according to any of Claims 7 to 9 wherein the synthetic organic polymeric material is polyethylene.

12. An article according to Claim 10 wherein the polystyrene foam has a density in the range from 0.01 to 0.04 g/cc, the body of polystyrene foam and the body of solid detergent composition are flat and are held together at major surfaces thereof by a binding material, the ratio of thicknesses of the foam and detergent composition bodies is in the range from 1:1.5 to 1:3 and the thicknesses are in the ranges from 5 mm to 5 cm for the polystyrene foam body and from 2 mm to 2 cm for the detergent composition body.

13. An article according to Claim 12 wherein the density of the foam is about 0.02 g/cc, the cells of the foam are of equivalent diameters in the range from 1.5 mm to 3 mm and the foam body is bound to the detergent composition body by a silicate cement.

14. An article according to Claim 11 wherein the polyethylene foam has a density in the range from 0.02 to 0.07 g/cc, the body of polyethylene foam and the body of solid detergent composition are flat and are held together at major surfaces thereof by an organic resinous

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (23)

**WARNING** start of CLMS field may overlap end of DESC **. the specified ranges, as are those of the present Examples. Example 3 The products of Examples 1 and 2 are made by extruding the detergent and foam compositions thereof through a plodder and plastic extruder, respectively, applying adhesive or cement of the type described to either or both of the surfaces to be joined, joining the products together, pressing them with a roll press or other suitable device, cutting and packing. Instead of using a cutter, a hot wire may be employed and instead of applying cement or other adhesive reliance may be placed on the hardening of the detergent composition body portion holding it to the surface of the foam, or on the foam being fused and pressed against the detergent composition body. Alternatively, other means of holding the two parts together during and/or after setting may be employed, such as mechanical fasteners, previously mentioned. The manufacturing method described provides for quick and efficient production of the articles automatically. It helps to conserve perfume and other volatiles which might otherwise be lost during open air setting or curing processes which might be accompanied by drying. The articles of this Example have the same utilities as described for the articles of Examples 1 and 2 and the mentioned variations thereof. WHAT WE CLAIM IS:

1. A detergent-scrubber article which comprises an exposed solid detergent composition body affixed to an exterior surface of a body of a low density closed cell material functional as a scrubbing means for scrubbing soiled or stained surfaces of the items to be cleaned after application of the detergent composition thereto and functional as a handle by means of which the solid detergent composition can be held while applying the composition to the items to be cleaned.

2. An article according to Claim 1 wherein the body of low density closed cell material is thicker than the solid detergent composition body.

3. An article according to Claim 1 or Claim 2 wherein the solid detergent composition body comprises soap and/or synthetic organic detergent, and builder and/or filler salt.

4. An article according to Claim 3 wherein the solid detergent composition is a built synthetic organic detergent composition comprising from 5 to 350/0 of water-soluble synthetic anionic organic detergent, from 20 to 95% of water-soluble inorganic builder salt, 0 to 60% of water-soluble filler salt and 0 to 50% of water-insoluble inorganic powder.

5. An article according to any of the preceding Claims wherein the solid detergent composition body and the body of low density closed cell material are flat and are joined together at major surfaces thereof.

6. An article according to Claim 5 wherein the solid detergent composition body and the body of low density closed cell material are joined together by a binder.

7. An article according to any of the preceding Claims wherein the low density closed cell material is a closed cell foam of synthetic organic polymeric material.

8. An article according to Claim 7 wherein the density of the closed cell foam is in the range from 0.01 to 0.7 g/cc, the cells of the foam are of sizes in the range from 0.3 mm to 5 mm equivalent diameter, the solid detergent composition body is of a density in the range from 0.8 to 2.3 g/cc and the ratio by volume of the solid detergent composition body to the body of low density material is in the range from 1:1.5 to 1:10.

9. An article according to Claim 8 wherein the density of the closed cell foam is in the range from 0.01 to 0.2 g/cc, the density of the solid detergent composition body is in the range from 1.4 to 2 g/cc, the compression strength of the foam at 10% deflection is in the range from 0.1 to 20 kg/sq. cm and the tensile strength thereof is at least 1 kg/sq. cm.

10. An article according to any of Claims 7 to 9 wherein the synthetic organic polymeric material is polystyrene.

11. An article according to any of Claims 7 to 9 wherein the synthetic organic polymeric material is polyethylene.

12. An article according to Claim 10 wherein the polystyrene foam has a density in the range from 0.01 to 0.04 g/cc, the body of polystyrene foam and the body of solid detergent composition are flat and are held together at major surfaces thereof by a binding material, the ratio of thicknesses of the foam and detergent composition bodies is in the range from 1:1.5 to 1:3 and the thicknesses are in the ranges from 5 mm to 5 cm for the polystyrene foam body and from 2 mm to 2 cm for the detergent composition body.

13. An article according to Claim 12 wherein the density of the foam is about 0.02 g/cc, the cells of the foam are of equivalent diameters in the range from 1.5 mm to 3 mm and the foam body is bound to the detergent composition body by a silicate cement.

14. An article according to Claim 11 wherein the polyethylene foam has a density in the range from 0.02 to 0.07 g/cc, the body of polyethylene foam and the body of solid detergent composition are flat and are held together at major surfaces thereof by an organic resinous

binding material, the ratio of thicknesses of the foam and detergent composition bodies is in the range from 1:1.5 to 1:3 and the thicknesses are in the ranges from 5 mm to 5 cm for the polyethylene foam body and from 2 mm to 2 cm for the detergent composition body.

15. An article according to Claim 14 wherein the density of the foam is about 0.03 g/cc, the cells of the foam are of equivalent diameters in the range from 0.7 mm to 3 mm, the cells are open at the surface affixed to the body of detergent composition and the cell openings containing polyvinyl acetate binder which binds the foam body to the detergent composition body before, during and after use of the article.

16. An article according to any of the preceding Claims of substantially rectangular parallelepiped shape, the solid detergent composition body and the substantially rigid body of low density closed cell material both being of rectangular parallelepiped shape and joined together at major surfaces thereof.

17. A detergent-scrubber article substantially as described with reference to Figures 1 to 3 of the accompanying drawings.

18. A detergent-scrubber article substantially as described in any of the Examples.

19. A method of manufacturing detergent-scrubber articles which comprises continuously producing a bar of slab of low density closed cell synthetic organic polymeric material, continuously producing a solid bar or slab of detergent composition, continuously bringing major surfaces of the bars or slabs together as they are produced so that a bar or slab of low density closed cell material is brought into contact with a bar or slab, respectively, or detergent composition, pressing the contacting bars or slabs together to affix the detergent composition to the closed cell polymeric material and cutting the product into individual detergent-scrubber articles according to Claim 1.

20. A method according to Claim 19 for manufacturing detergent-scrubber articles according to any of Claims 6 or 8 to 17, wherein prior to contacting the solid detergent composition with the closed cell foam a binder is applied to at least one of the surfaces to be brought into contact.

21. A method according to Claim 20 wherein after pressing the solid detergent composition bar or slab against the closed cell synthetic organic polymeric foam bar or slab, with binder between the major surfaces thereof which are being affixed together, and after cutting of the bars or slabs into individual articles, the said surfaces are held together by wrapping material to facilitate permanent affixation together of the solid detergent composition body and the closed cell polymeric foam body.

22. A method of manufacturing detergent-scrubber article substantially as described with reference to Figure 4 of the accompanying drawings.

23. A detergent-scrubber article which has been manufactured by a method according to any of Claims 19 to 22.