CN1309816C - Shaped solid detergent compositions - Google Patents

Abstract

A shaped detergent composition comprises: 0.5-60% detergent active; 0-90% inorganic particulates; and other conventional ingredients, wherein the external surface of the said shaped detergent composition comprises one or more materials that are substantially water insoluble, said material having melting point greater than 30 DEG C, being adherent to the external surface and capable of being abraded during use.

Description

Shaped solid detergent composition

technical field

The present invention relates to shaped solid detergent compositions for cleaning hard surfaces or fabrics. More particularly, the compositions of the present invention are suitable for use in hand laundering.

Background technique

Detergent compositions generally used for fabric or hard surface cleaning typically contain a surfactant system which acts to aid in soil removal. The surfactant system may be predominantly non-soap surfactants. Various abrasives, fillers, builders, and other ingredients such as colors, fragrances, preservatives, etc. may also be incorporated as appropriate.

Cleaning compositions in solid form are much cheaper than liquids due to their low cost packaging and these are very popular forms in developing countries. Among solid forms, bar soap is gaining popularity and growing rapidly in developing country markets owing to better value delivery. Dosing of product in solid form is easier, it avoids spillage, and product application can be better controlled. Cleansing compositions in bar form are economically superior to other product forms and the dosage per bar is highly controlled. Detergent bars require acceptable physical strength so that they retain their structural integrity during handling, shipping and use. However, detergent bars for fabric and hard surface cleaning are always in contact with water during use and subsequent storage and thus gradually soften and generally gradually disintegrate into a pasty form. The shape and contour of the bar soap was not maintained satisfactorily.

This problem is generally sought to be resolved by making appropriate changes to the bar soap formulation. Any attempt to harden the bar, if not properly controlled by the formulation, will result in a hard product which will not release enough product to clean satisfactorily in use. Therefore, a major challenge is to ensure that the product does not disintegrate during use, that the product is not wasted by creating a mush, and that the product is soft enough that the user has access to the correct amount of product for cleaning.

IN 166806 discloses a process for making detergent bar soaps with good strength and handling properties during shipping and use by incorporating various desiccants during neutralization.

WO 9518215 (Ecolab Corporation, 1995) discloses an environmentally stable detergent article. The hygroscopic detergent material is rendered resistant to absorption of ambient humidity or water by introducing a barrier coating onto the detergent. The object of this invention is to obtain a concentrated aqueous detergent for washing machines, but also to control overdosing. The hydrophobic coating is split, creviced, peeled off or partially removed so that the coating dissolves or melts in a controlled manner.

WO 9955823 (Procter & Gamble, 1999) discloses a non-granular detergent product having a core formed by compressing a granular material comprising detersive surfactants and builders, and an essentially water An insoluble coating that substantially covers the surface relief core in order to provide mechanical strength, impact and chipping resistance to the compressed tablet. It is also crucial that this coating dissolves under alkaline conditions or is readily emulsified by surfactants.

Contents of the invention

It has now been found that it is possible to formulate strong shaped detergent compositions which are soft enough to allow the user to obtain just the right amount of product when cleaning dishes or fabrics without losing shape or gradually spreading due to water uptake during use. soft.

The present invention provides a shaped detergent product comprising a water resistant coating which is capable of being abraded away from the detergent product during use. Preferably, the shaped detergent product is an extruded bar soap. Preferably, the bar soap contains an abrasive.

The water-resistant film provided on the product reduces disintegration and deformation of the product during use and also reduces product waste by reducing undesirable lump formation. The water-resistant film is inherent on the surface of the product, and although it abrades with the product during use, it maintains the shape and integrity of the product. The water-resistant coating is preferably substantially insoluble in water, even under alkaline conditions.

Description of drawings

Figures 1a-1c show the characteristics of the bar soap before and during use.

Figure 1a refers to an unused sample.

Figure 1b refers to Example 5, ie according to the invention.

Figure 1c refers to Example 1, the control sample.

Detailed ways

Accordingly, according to the present invention there is provided a shaped detergent composition comprising

-0.5~60% detergent active ingredients,

-0 to 90% inorganic particulate matter, and

- other customary components,

Wherein, the outer surface of the shaped detergent article is covered with one or more substantially water-insoluble materials having a melting point above 30°C and which adhere to the outer surface but abrade away during use.

said material covering the outer surface of the shaped article is selected from natural or modified natural or synthetic polymeric materials or waxes or mixtures thereof, which are substantially water-insoluble and have a melting point higher than 30°C, They can adhere to the outer surface but can wear away during use. More specifically, said material may be one or more polymers and synthetic compounds selected from natural and synthetic waxes, polysaccharides, water-insoluble fatty acid salts, all of which have a melting point above 30°C. Mixture of film thinners. Preferably, said material comprises 5 to 25% by weight of one or more atactic α-olefin copolymers and 75 to 95% by weight of one or more natural and synthetic waxes having a melting point higher than 30°C Selected film-forming diluent.

It is especially preferred that the atactic alpha-olefin copolymer is enriched in propylene or butene monomers.

Synthetic or (modified) natural polymeric materials used for the purposes of the present invention preferably have a molecular weight above 1600 Daltons.

When natural or modified natural polymers are used, the water vapor permeability coefficient of said natural or modified polymers is preferably lower than

$\mathrm{<span\; class="notranslate">\; 5000</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 13</span>}}\frac{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; cm</span>}<span\; class="notranslate">\; ]</span>}{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; Pa</span>}<span\; class="notranslate">\; ]</span>}<span\; class="notranslate">\; .</span>$

When a synthetic polymer is used, the water vapor permeability coefficient of said synthetic polymer is preferably lower than

$\mathrm{<span\; class="notranslate">\; 1000</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 13</span>}}\frac{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; cm</span>}<span\; class="notranslate">\; ]</span>}{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; Pa</span>}<span\; class="notranslate">\; ]</span>}<span\; class="notranslate">\; ,</span>$

In the formula, [Cm ³ ]=Cm ³ (273.15K; 1.013×10 ⁵ Pa), such as "Polymer Handbook, 1989, Third edition, Eds.J.Brandrup and EH Immergut, (Wiley-Interscience Publication), page VI/436 " described in.

The material covering the outer surface of detergent articles according to the invention preferably has a percent elongation at break greater than 2%. The material covering the outer surface of the detergent article is preferably in the form of a film, the thickness of which is kept in the range of 5-1000 μm, preferably 10-100 μm, especially 30-60 μm.

Detergent compositions useful for fabric or hard surface cleaning may be suitably formulated in the form of bars including tablets, compacts or cakes. The bar soap essentially has some outer surface on which is one or more water-resistant materials, preferably having a melting point above 30°C. Preferably, the material on the outer surface is in the form of a film having a thickness of not less than 5 μm, inherently adhered to the outer surface of the profile of the product. The water-resistant film is preferably substantially insoluble in water even under alkaline conditions. Preferably, the bar soap is extruded.

Therefore, a further aspect of the present invention relates to a process for the manufacture of detergent bar soap comprising the steps of:

(a) extruding a detergent composition to form a detergent bar, and

(b) providing on the outer surface of the bar one or more materials which are substantially water insoluble, have a melting point above 30°C and which together form a water resistant film.

Particularly preferably, the material is a polymerizable, photocurable polymer material.

Water-resistant film

The film is made of suitable material capable of forming a water barrier and is made to inherently adhere to the exterior surface of the detergent product. The film is preferably at least 5 μm thick, and may be up to 1000 μm thick, preferably 10-100 μm, more preferably 30-60 μm thick. The water resistant film is preferably substantially insoluble in water, even under alkaline conditions.

The material used for the film has a melting point higher than 30°C, preferably higher than 45°C. At least the surfaces of the bar that are most likely to be in prolonged contact with water during use will be coated with the water resistant film material. Preferably, all surfaces where such contact is likely to occur are coated. Obviously, the top side or working surface of the bar used to remove or apply the detergent material to items to be cleaned does not necessarily need to be coated, but preferably the remaining non-working surfaces of the bar are all coated.

Film forming material

Suitable film-forming materials may include water-insoluble materials capable of forming an inherent film on the outer surface of the detergent composition, such as polymers and combinations thereof, natural and synthetic waxes, polysaccharides and water-insoluble fatty acid salts kind. The film may also contain any of the organic materials together with inorganic materials as diluents/fillers to modify the mechanical properties of the film.

Materials can be selected that do not themselves form an adhesive film on the surface of the detergent product but can be made adherent by using another material capable of bonding the detergent product and the water resistant material.

The film can be formulated as a liquid solution or dispersion in a solvent, or as a hot melt consisting of single or multiple polymer/organic materials.

The film composition can be prepared using a combination of polymers, various waxes and additives known as tackifiers to improve the adhesive properties of the composition. A suitable combination of these may be achieved in order to provide the desired workability and mechanical strength. Depending on the desired properties of the coating, the film can be prepared from a base polymer alone. The base polymer may be selected from the following list: polyacrylates, polymethyl methacrylates, polystyrenes, poly(ethylene co-vinyl acetate), poly(ethylene co-acrylate), poly(ethylene co-methacrylic acid ester), poly(styrene coacrylate), polyolefin, atactic polyalphaolefin, polyethylene, polypropylene, amorphous polyalphaolefin, polyimide, nylon, polyvinyl chloride, polypara Ethylene phthalate, polyurethane, epoxy resin.

Natural and synthetic waxes are optionally added to the composition to provide molten state application viscosity control and to aid in less dry tack and erodibility. Such waxes may be selected from polyethylene waxes, waxes obtained during Fischer-Tropsch synthesis, microcrystalline waxes, paraffin waxes.

Tackifiers and adhesion promoters can optionally be added to the composition to enhance the adhesive and cohesive characteristics of the film. These materials may be selected from the following list: hydrocarbon resins, petroleum _C5 - _C9 resins, hydrogenated petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, coumarin petroleum resins, terpene-based resins, styrene resins , phenolic resins, ester gums, rosins such as rosin and gums.

Antioxidants are optionally added to the composition to prevent degradation in the molten state. These antioxidants may be selected from the following list: phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol, 2,2'-methylene bis(4-methyl-6-tert-butylphenol) , 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-sulfur Bis(4-methyl-6-tert-butylphenol), stearyl propionate-β-(3,5-di-tert-butyl-4-hydroxyphenol ester), tetrakis(3-(3,5-di tert-butyl-4-hydroxyphenyl)propionate (methylene)methane, triethylene glycol, bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate), 1,3,5-triethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and 1,1,3-tris(2-methyl-5- tert-butylphenol)butane; amine antioxidants such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, N-phenyl-N′-cyclohexyl-p-phenylenediamine and N-iso Propyl-N'-phenylphenylenediamine; phosphorus antioxidants such as triisodecyl phosphite and 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite ; sulfur-based antioxidants such as 2,2'-thiobis(4-methyl-6-tert-butylphenol); and hydroquinone-based antioxidants such as 2,5-di-tert-amylhydroquinone.

The film compositions can also be prepared with ultraviolet (UV) curing formulations involving acrylate oligomers, monomers, and photoinitiators. Typical oligomers may be selected from the group consisting of urethane acrylates, polyester acrylates, polyether acrylates, polybutadiene acrylates, and epoxy acrylates, as well as their desired film properties. combination. Such oligomers are described in detail in "N.S.Allen, M.A.Johnson, P.Oldring (ed.) and M.S.Salim, Chemistry & Technology of UV & EB-Curing Formulations for Coatings, Inks & Paints, Vol.2, SITA Technology, London 1991". Monomers can be selected from monofunctional, difunctional, trifunctional, tetrafunctional and pentafunctional acrylates with various aliphatic or aromatic backbones. Typical examples of monomers include triethylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), propoxylated glycerol triacrylate (GPTA), isobornyl acrylate, 2- Phenoxyethyl ester (2-PEA), tridecyl acrylate (TDA), ethoxylated nonylphenol acrylate (EONPA), ethoxylated pentaerythritol tetraacrylate (EOPETA), ethoxylated bis Phenol A diacrylate (EOBPADA), tri(hydroxymethyl)propane trimethacrylate (TMPTA) and triacrylate, allyl methacrylate, stearyl acrylate and methacrylate, 1,3-butyl Glycol dimethacrylate, Ethylene glycol dimethacrylate, Cyclohexyl methacrylate, Glycidyl methacrylate, Isodecyl acrylate, Isooctyl acrylate, Polyvinyl acrylate. Common photoinitiators include aromatic ketone compounds such as benzophenones, alkylbenzophenones, Michler's ketones, anthrone, halogenated benzophenones, 2,4,6-trimethylbenzoyl Diphenylphosphine oxides, phenylglyoxylates, anthraquinones and their derivatives, dibenzoyl ketals, hydroxyalkyl phenones, etc. can be used for polymerization initiation. Mixtures of these compounds may also be employed.

The film-forming material may also include the following substances as additives: inorganic materials such as talc, silica, clay, oxides, carbonates and chlorides of alkali or alkaline earth metals or transition metals, preferably they are calcium or magnesium or zinc of salt.

Film forming method

The detergent composition is provided with a water-resistant material by any of the following methods. Shaped detergent articles may be prepared and then surface coated with the water resistant material using any conventional process. Such processes include applying the coating material in a molten state, for example by dipping the detergent item in the coating melt or spraying the coating melt onto the item, followed by cooling to allow the coating material to solidify. Such processes also include the application of the coating material as a solution in a suitable solvent, again for example by dipping or spraying, followed by evaporation of the solvent in a known manner. It is also possible to apply certain types of film-forming coating materials in monomeric or oligomeric form, which are then further reacted on the surface of the laundry item to form the water-resistant film. Such processes are known as thermal curing, UV curing or electron beam curing. An intermediate can also be used to apply the coating when the water resistant material does not adhere to the product. Furthermore, the coating can be coextruded with the detergent article.

active ingredient in detergent

The detergent composition according to the present invention preferably comprises a detergent active ingredient, which may be a soap or non-soap surfactant, and is generally selected from the group consisting of anionic, nonionic, cationic, zwitterionic detergents Active ingredients or mixtures thereof. Suitable examples of detergent-active compounds are those given in well-known textbooks, commonly used as surfactants: "Surface Active Agents", Vol. 1. by Schwartz & Perry, Interscience 1949; Vol. 2, Schwartz , Perry & Berch, Interscience Published 1958; "McCutcheon's Emulsifiers and Detergents" Current Edition, Manufacturing Confectioners Company Published; "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.

The total amount of detergent-effective compounds to be employed in the detergent compositions of the present invention is preferably from 5 to 30% by weight of the composition.

abrasive

Detergent compositions according to the invention preferably comprise solid insoluble abrasives. Suitable abrasives may be selected from granular zeolites, calcites, dolomites, feldspars, silicas, silicates, other carbonates, aluminas, bicarbonates, borates, sulfates and polymeric materials such as poly vinyl. Abrasive systems with more than one abrasive type can be present to achieve a balanced abrasive performance. Combinations of different hardness abrasives in formulations have been shown to provide some significant benefits in user performance. Abrasives may also be included in the coating to aid in its initial removal on the side of the detergent composition that is applied to the item to be cleaned.

builder

Builders/alkaline buffer salts are preferably used in the detergent compositions. They are preferably inorganic and suitable builders include, for example, alkali metal aluminosilicates (zeolites), sodium carbonate, sodium tripolyphosphate (STPP), tetrasodium pyrophosphate (TSPP), and combinations of these. Builders/alkaline buffer salts are suitably used in amounts ranging from 2 to 15 wt%, preferably 5 to 10 wt%.

other components

Other components, such as fillers, solvents, amines, fragrances, colourants, optical brighteners, enzymes, may also be used in the formulation, for example in amounts which may be as high as 10% by weight.

The invention will now be illustrated by the following non-limiting examples.

Example

A dishwashing detergent composition having a formulation as described in Table 1 was used for demonstration of the present invention. In Example 1 the bar soap was not covered with any water resistant material; whereas in Example 2 the bar soap was covered with a 40 μm thick film made of poly(methacrylonitrile co-styrene) (~50/50 ratio) , whose permeability coefficient is greater than

$\mathrm{<span\; class="notranslate">\; 1000</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 13</span>}}\frac{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; cm</span>}<span\; class="notranslate">\; ]</span>}{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; Pa</span>}<span\; class="notranslate">\; ]</span>}<span\; class="notranslate">\; ,</span>$

That is, it is better than that of the present invention. In Examples 3-5, the composition of the film was a mixture comprising 25 wt% of amorphous poly-alpha-olefin and 75 wt% of microcrystalline wax melted together at 150°C, and its permeability coefficient was lower than that according to the present invention. invented

$\mathrm{<span\; class="notranslate">\; 1000</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 13</span>}}\frac{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; cm</span>}<span\; class="notranslate">\; ]</span>}{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; Pa</span>}<span\; class="notranslate">\; ]</span>}<span\; class="notranslate">\; .</span>$

The thickness of the film is respectively less than 5 μm (Example 3), greater than 1000 μm (Example 4) and equal to 40 μm (Example 5). In Examples 2-5, the bar soap was covered with a film on all sides except the one used to obtain the product for use.

Determination of Bar Soap Integrity

Bar soaps according to Examples 1-5 were tested by a panel of trained personnel for dishwashing over a period of one week under controlled simulated consumer use conditions. Testers give points on a scale of 0 to 10, where 0 means very low disintegration and deformation and 10 means very high disintegration and deformation. Similarly, testers give points on a scale of 0 to 10, where 0 means very high economy of use and 10 means very low economy of use.

The bar soap was also tested by submerging the film covered portion in water for 2 hours and measuring the amount of bar soap lost into solution after 2 hours. The data are listed in Table 2.

Table 1 components composition(%) Sodium linear alkylbenzene sulfonate 14 Sodium carbonate 12 sodium tripolyphosphate 2 Inorganic particulates such as calcite/dolomite/clay 59 magnesium sulfate 0.5 Alkaline silicate 3 water to 100

Table 2 product features Example 1 Example 2 Example 3 Example 4 Example 5 deformation 9 8 7 1 ^* 1 Economical use 9 9 8 1 ^* 1 Bar soap loss (g) 10 9 8 0.001 0.001

^* The shell is too thick to be abraded, resulting in poor economics.

These data show that the bar soap according to the present invention is economical because the loss of the bar bar into solution is very low, as rated by the testers. The control bars and bars with films less than 5 μm thick gradually deformed significantly, while when the film was greater than 1000 μm thick, the film did not abrade and leave a shell during use. This also leads to poor economics and is not favored by users due to inconvenient product availability and for aesthetic reasons.

Coating with Microcrystalline Wax

Bar soaps were prepared by extrusion of the detergent formulations given in Table 1 . Bar soap coating of the hot melt coating composition was carried out by immersing the bar soap in a bath containing the composition at 150°C for 3-5 seconds. Allow excess coating material to drip into the bath and allow the coated bar to cool to room temperature. Details of the coating material composition are described in Table 3.

Various properties of the bar soap were analyzed by the following methods.

1. Coating adhesion: Coating adhesion is measured by evaluating the ease with which the coating film can be peeled off the surface of the detergent bar soap. A scale of 1 to 5 is given. A rating of 1 represents excellent adhesion of the coating to the surface of the bar, in which case the film cannot be peeled off the surface of the bar, while a rating of 5 indicates poor adhesion and the film can be easily removed from the bar. Peel off on soap surface.

2. Bar soap integrity: Bar soap integrity was determined using the procedure described previously.

table 3 Example Coating material composition Observations during coating Example 1 uncoated control none Example 6 Microcrystalline Wax Gives a good coating that adheres to the bar soap Example 7 Crystalline butene-rich atactic α-olefin copolymer + microcrystalline wax (12:88) Good coating, adheres to the bar soap Example 8 Amorphous poly-α-olefin + microcrystalline wax (12:88) Good coating, adheres to the bar soap

Table 4 Example Coating Adhesion bar soap integrity Example 1 uncoated 9 Example 6 1. Strong adhesion 6 Example 7 1. Strong adhesion 1 Example 8 1. Strong adhesion 1

The data presented in Table 4 shows that detergent bars having an outer surface of microcrystalline wax, either alone or in combination with polyolefin, resulted in excellent adhesion to the bar, also maintaining bar integrity.

Coating with modified natural polymers

Bar soaps were prepared by extrusion of the detergent formulations given in Table 1. The bar soap is coated with a cellulose derivative solution. The cellulose acetate of Example 9, the nitrocellulose of Example 10, and the ethylcellulose of Example 11 were compared with Example 1, the uncoated bar soap.

table 5 Example Permeability Coefficient[Cm ³ ][Cm] bar soap integrity [Cm ² ][s][Pa] Example 1 - 9 Embodiment 9 cellulose acetate 4100 3 Example 10 Cellulose Nitrate 4700 3 Embodiment 11 ethyl cellulose 6700 9

The data presented in Table 5 show that modified natural polymers with a permeability coefficient of less than 5000 can be used to maintain bar integrity.

Claims (12)

1. A shaped detergent composition comprising: 0.5 to 60% detergent active ingredients; 0 to 90% inorganic particles; and other usual components, the composition maintains integrity in use, and wherein said shaped detergent The outer surface of the forming composition is covered with a coating, wherein the coating is a film having a thickness in the range of 5 to 1000 μm, provided that at least one side of the forming composition is uncoated, the coating consists of one or more A substantially water-insoluble and water-resistant material having a melting point above 30° C., adhered to the outer surface of the composition, and capable of abrasion during use, and selected from the group consisting of: (a) Natural or modified natural polymers having a water vapor permeability coefficient less than $\mathrm{<span\; class="notranslate">\; 5000</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 13</span>}}\frac{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; cm</span>}<span\; class="notranslate">\; ]</span>}{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; Pa</span>}<span\; class="notranslate">\; ]</span>}<span\; class="notranslate">\; ,</span>$ or (b) Synthetic polymers having a water vapor permeability coefficient less than $\mathrm{<span\; class="notranslate">\; 1000</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 13</span>}}\frac{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; cm</span>}<span\; class="notranslate">\; ]</span>}{<span\; class="notranslate">\; [</span>{\mathrm{<span\; class="notranslate">\; cm</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; ]</span><span\; class="notranslate">\; [</span>\mathrm{<span\; class="notranslate">\; Pa</span>}<span\; class="notranslate">\; ]</span>}<span\; class="notranslate">\; ,</span>$ In formulas (a) and (b), [Cm ³ ]=Cm ³ (273.15K; 1.013×10 ⁵ Pa). 2. A shaped detergent composition as claimed in claim 1, wherein said polymeric material has a molecular weight of 1600 Daltons or more. 3. A shaped detergent composition as claimed in claim 1, wherein said material is one or more polymers and one or more natural and synthetic waxes, polysaccharides, polysaccharides, Mixture with selected film-forming diluents in water-insoluble fatty acid salts. 4. A shaped detergent composition according to claim 3, wherein said material comprises 5 to 25% by weight of one or more atactic α-olefin polymers and 75 to 95% by weight of A film-forming diluent selected from one or more natural and synthetic waxes. 5. The shaped detergent composition according to claim 4, wherein the atactic α-olefin polymer is enriched in propylene or butene monomers. 6. A shaped detergent composition as claimed in claim 1, wherein the coating is a film having a percent elongation at break greater than 2%. 7. The shaped detergent composition according to claim 1, wherein the film has a thickness of 10 to 100 [mu]m. 8. The shaped detergent composition according to claim 7, wherein the film has a thickness of 30 to 60 [mu]m. 9. A shaped detergent composition as claimed in claim 1, wherein the coating is also insoluble in water under alkaline conditions. 10. A shaped detergent composition as claimed in claim 1, wherein the coating material is a heat, ultraviolet light or electron beam polymerizable or curable polymer material. 11. A method for producing a shaped detergent composition according to any one of claims 1 to 10, comprising the steps of: (a) extruding a detergent composition into a shaped form; and (b) providing on the outer surface of the composition a coating of one or more substantially water-insoluble materials having a melting point above 30°C. 12. A method as claimed in claim 11, wherein the shaped detergent composition is in the form of a soap bar or a tablet or a powder extrusion or cake.