Multi-coloured cleaning article

The present invention relates to the field of multi-coloured cleaning articles, particularly soaps and extrudable non-soap cleaning articles, and methods for production of such multi-coloured cleaning articles. The present invention is also applicable to extrudable articles such as laundry bars (also known as non-soap detergent bars).

Multi-coloured soaps and extrudable cleaning articles have been described by various terms including variageted, marbled, striated and striped. Multi-coloured soaps within the ambit of the invention comprise a soap base and one or more coloured regions, achieving the appearance of spacial colour variation. The soap base can be opaque or translucent, and may or may not be coloured itself.

In the art, there are two basic systems for producing multi-coloured soaps. In one system, a coloured liquid is added to a soap mass during plodding of the mass to get a soap bar with marbleized appearance. In the second system, non-liquid materials are added to the soap during plodding, again to obtain a soap bar with marbleized or multi-coloured appearance. Examples of known processes for soap production and/or respective soap production apparatuses are: U. S. Patent 6,805,820, which documents the use of a structurally modified plodder whereby a secondary soap feed apparatus will feed soap pellets of a different colour into the primary soap base prior to extrusion to form multicoloured or marbleised soap bars.

U.S. Patent 6,730,642, which describes a process whereby the secondary soap pellets being introduced into the continuous phase has twice the hardness of the primary soap mass.

U.S. Patent 4,474,545, which describes the equipment to introduce pressurized coloured liquids into the soap mass prior to extrusion to form multicoloured marbled soaps.

U.S. Patent 4,096,221 , which describes the equipment and process to introduce the colour dye in the extruded column of the soap plodder to form striated soaps.

U.S. Patent 4,077,754, which documents the use of an apparatus that allow co-plodding of different coloured soap noodles with different diameters to form variegated soap bars.

U.S. Patent 4,077,753, which describes a soap plodder with a multi-thread extruding screw for different coloured soap material.

U.S. Patent 4,017,574, which describes a process to introduce coloured liquids previously melted into the vacuum chamber of a double-barrel soap plodder prior to extrusion to form multicoloured soap bars.

U.S. Patent 4,017,573, which describes a process to introduce colour dyes dispersed in liquid oil into the base soap material prior to extrusion.

U.S. Patent 4,011 ,170, which describes a process to introduce liquid dye material into the vacuum chamber of a double-barrel soap plodder to form marbled detergent bars.

U.S. Patent 3,947,200, which documents the use of a dye injection assembly to inject dye into the soap mass to produce striated soap bars.

With existing techniques of soap manufacture, a number of problems regularly occur that influence the economic value and thus the usefulness of the soaps such produced. It is desirable that the multi-coloured soap can be easily manufactured using inexpensive materials. The manufacturing process should allow production of a multi-coloured soap with distinctive contras between different colours, particularly at the bar surface. The addition of colour should not interfere with processes of forming the soap, e.g. pressing an extruded bar of soap to achieve a pre-defined texture or three-dimensional picture. Also, colouration of soap should not result in multi-coloured soaps tending to colour migration ("bleeding"), cracking for fissuring during storage or use.

In the past, solid pigments have been added to soap to achieve colouration. However, as only few pigments are approved for cosmetic use, the choice of colours for producing multi-coloured soaps based on pigments had been severely limited. It is therefore re- quired to provide novel methods of producing multi-coloured soaps, wherein said methods and the soaps thus produced should exhibit the desirable qualities mentioned above.

According to the invention, there is thus provided a process for preparing a multi-coloured cleaning article, comprising the steps of:

a) preparing a base mass of a first colour,

b) adding a coloured particle to the cleaning mass, the coloured particle comprising

i) a water-soluble component,

ii) a water-insoluble component, and

iii) a dye for imparting a second colour to the cleaning article, and

c) forming the cleaning article.

The cleaning article is preferably a soap, such that the base mass is a soap mass, or generally a extrudable cleaning article and preferably a non-soap detergent article, such that the base mass is a non-soap detergent mass. The invention is hereinafter described mainly for soaps, but is equally applicable to general extrudable cleaning articles and particularly to non-soap detergent articles such as, for example, non-soap cleaning bars, by substituting references to the soap or base mass by the respective extrudable base mass, e.g. a non-soap extrudable base mass. - A -

It has been found that a combination of water-soluble and water-insoluble components can act as a carrier for both water-soluble and oil-soluble colour dyes. Appropriately coloured particles can thus beneficially be used to impart spatially variated colouration to soaps. Also, such particles allow by appropriately choosing the water-soluble and oil- soluble (water-insoluble) material to influence parameters of soap manufacture particularly melting point of the particles and size of the particles after soap manufacture.

The coloured particles according to the invention can be introduced to the soap mass at an initial mixing stage, after the milling process, prior to extrusion in a refining plodder and combinations thereof. The temperatures of plodding and extrusion can vary and may be chosen appropriately in view of the melting point of the coloured particles. Likewise, the materials for forming the coloured particles may be chosen appropriately to conform to the extrusion and/or plodding temperatures. Since the coloured particles according to the invention can release their dye through conventional plodding and extrusion processes, no specialized equipment such as dye-injection modules, co-plodding soap appa- ratuses etc. are required. Particularly the multi-coloured soaps according to the present invention can be produced in conventional double-barrel soap plodders as well as in single barrel soap plodders without vacuum chambers. The invention thus allows to produce multi-coloured soaps without a high capital investment into specialized equipment.

The coloured particle according to the present invention preferably has a melting temperature, measured for the component with the highest melting temperature, of at least 45 ⁰ C, preferably at least 55 ⁰ C and most preferably at least 6O ⁰ C. In any case, the upper limit for the melting temperature is preferably 7O ⁰ C.

As stated above, the cleaning article is preferably formed using an extrusion or plodding step during which the base mass with added particle(s) is extruded or plodded at a temperature of at least 5 ⁰ C lower than the melting temperature of the coloured particle(s). This way, "bleeding" of the dye into the soap mass can be reduced or avoided, allowing for a high contrast between the coloured particle(s) and adjacent soap regions. In case a mixture of coloured particle with different melting temperatures is used, the extrusion and/or plodding temperature is preferably at least 5 ⁰ C below the lowest melting temperature of a particle "bleeding" of which is to be reduced or avoided. The plodding or extrusion temperature generally is in the range of 30 to 6O ⁰ C, commonly in the range of 40 to 6O ⁰ C, preferably 45 to 5O ⁰ C.

The water-soluble component of a coloured particle preferably is or comprises a polyethylene glycol with an average molecular weight range of at least 1800, preferably at least 4000 and most preferably 5000 to 9000 g/mol, or a mixture of two or more such polyethylene glycols. The water-soluble component preferably is a mixture of two or more of such polyethylene glycols, such that the melting temperature of the highest melting poylethylene glycol is between 45 ⁰ C and 65 ⁰ C. Therefore, the water soluble component preferably comprises a polyethylene glycol with an average molecular weight of at most 9000 g/mol. Furthermore, polyethylene glycols with average molecular weights lower than 1800 g/mol tend to allow a fast release of the dye during forming of the soap - which is according to the invention generally done by plodding -, resulting in a nearly uniformly coloured soap if given enough time to release the dye. It is therefore preferred that the water-soluble component does not comprise a polyethylene glycol with an average molecular weight of less than 1800 g/mol.

Such high molecular weight polyethylene glycols have melting temperatures from 4O ⁰ C to 65 ⁰ C. As it is preferable to limit the release of dye from the particle into the soap mass, the polyethylene glycols with higher molecular mass such as at least 4000 to 9000 or even 5000 to 9000 are particularly preferred. This allows to use in the process of the present invention coloured particles with melting temperatures above the extrusion and/or plodding temperatures of the soap forming step.

Polyethylene glycols (PG), preferably solid at room temperature (2O ⁰ C) with a weight average molecular weight (MW) of 1500 and above, can be obtained from BASF (Pluriol®), Clariant (Polyglykol®), Dow (CarbowaxTM) and various other suppliers. Preferred Polyethylene Glycols for use according to the invention are selected from the following (e.g. Polyglykol ^® from Clariant and Pluriol ^® E from BASF)

Polyglykol Flakes 7,000 - 9,000 55-60 max.0.5 12- 16 8000S ^* ) / ^** )

Polyglykol Wax/ 7,000 - 9,000 55-60 max.0.1 12- 16 8000 FL Melt

*) These products are also available in form of a powder. **) These products are also available in form of a fine powder.

I PJurioi E 8000 E Solid approx. 8000 approx. 1500 approx. 63

I Plurioi E 8000 Flakes approx. 8000 approx. 1500 approx. 63

I Flakes

I Plurioi E ^' 9000 Powder approx. 9000 approx. 2500 approx. 65

I Powder fTfur1orE ^~ 9bW ^~" Flakes approx. 9000 ^™ approx. 2500 approx. ^~ 65 i Flakes

Viscosity: measured using an Ubbelohde viscosity meter according to DIN 51562 [mm ² /s]

Molar mass calculated from hydroxyl number according to DIN 53240 or PSA method

The water-insoluble component of the coloured particle preferably is or comprises a fatty alcohol, a fatty acid or a fatty acid ester, each with a carbon chain length of at least 12, preferably 12 to 18, or mixtures thereof. The use of fatty substances particularly allows to harness their super fatting properties as are known in the field of soap manufacturing. Use of substances with a carbon chain length of more than 18 may introduce some grittiness into the soaps during washing and be perceived as rough to the skin. Preferably, the water-insoluble component comprises a mixture of two or more of such fatty acids, and most preferably is or comprises a mixture of C16+C18 fatty acids.

Another example of preferred water-insoluble component is glycol stearate and fatty alcohols with 12 to 18 carbon atoms in the carbon chain such as cetyl, cetearyl or stearyl alcohol.

Preferred C12-C18 fatty acids are saturated, i.e. "hardened", and can be obtained by hydrogenation of unsaturated C12-C18 fatty acids. Most preferred fatty acids are selected from myristic, palmitic and stearic acids. Corresponding fatty alcohol and fatty acid esters, particularly ethylene glycol ester, are likewise preferred. Also, mixtures of two or more of the respective fatty acids, fatty alcohols and fatty acid esters are preferred.

Both water-soluble and water-insoluble (i.e. oil-soluble) dyes can be used in the coloured particle according to the present invention. Particularly preferred dyes are: Dyes suitable for use in the coloured particle of the present invention can preferably be selected from the Symrise Dragocolor product range

(www.symrise.com/en/fragrances/pdf/dictionary_of_colors.p df). Particularly suitable dyes are water-soluble or water dispersible dyes which include Hansa Yellow G (C.I. 11680), Red (C.I. 12490), Orange Il (C.I. 15510), Pyranine (C.I. 59040), Acid Green (C.I. 61570), Blue (C.I. 61585) and combinations thereof. Particularly suitable pigments are derma- tologically acceptable metal oxides, e.g. titanium dioxide.

Further suitable dyes are given hereinafter as non-limiting examples. Suitable grades would be for use in personal care products and include FD&C grades such as FD&C Blue No.1 and FD&C Yellow 10.

Water-soluble dyes including water-dispersible dyes for personal care can be selected from Clariant under the Sandolin and Viscofil range, Ciba under the Puricolor and Vibra- color range etc. Oil-soluble dyes are also available from Clariant & Ciba. Both water- soluble dyes and oil-soluble dyes are also available from Symrise.

Further preferred dyes are:

a) Water-soluble dyes

FD&C Yellow 5, 6 & 10, 656839 Blue, 5/076834 Violet, Ponceau C.I 16255, Patent Blue V C.I. 42051 , FD&C Red 40, Vanilla Yellow C.I 47005 etc.

b) Oil-soluble dyes

5/002470 Turquoise, 5/002406 Blue, Green C.I. 19140, Dragocolor Red C.I.

12150, 656870 Dragocolor Light Yellow, 5/068016 Light Green etc.

According to the present invention, the soap mass preferably comprises one or more metal C8-C24 fatty acid soap(s), preferably one or more alkali fatty acid soap(s), and most preferably one or more sodium fatty acid soap(s), said fatty acid soap(s) preferably having a carbon chain length of 8 to 18 carbon atoms. Soap masses preferred herein are generally based upon mixtures of fatty acids obtained from various natural sources. Commercial soaps preferred herein are generally based upon mixtures of fatty acids obtained from various natural sources. Coconut oil, for example, is a material, which has found considerable use in high-quality soap compositions. Similarly, tallow is a useful source of high-quality soaps. Other suitable sources include palm kernel oil and babassu kernel oil, olive oil and synthetic fatty acids simulating, for example, tallow. Particularly useful herein are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil, palm oil, palm kernel oil and tallow, e.g. sodium or potassium tallow and coconut soap. These soaps and soap mixtures are preferred from the standpoint of ready availability and ease of processing, and in view of their desirably optimum physical and performance characteristics.

Suitable commercially available fatty acids soaps are available from Uniqema and include Prisavon 9220 (Soap from Palm/Palm Kernel fatty acids), Prisavon 9240 (Soap from Palm/Coconut fatty acids), and Prisavon 9250 (Soap from Tallow/Coconut fatty acids).

Optionally the soap and/or the coloured particle comprise one or more further ingredients. All ingredients that are not either soap mass (i.e. metal fatty acids), water-soluble and water-insoluble material and dye of the coloured particle, are considered further ingredients. For example, water may be a further ingredient of a soap mass according to the present invention, up to a concentration of 10 wt% of the soap mass.

Also according to the invention, the base mass preferably comprises one or more non- soap detergent ingredients selected from the group consisting of surfactants, builders and commonly used auxiliary ingredients for non-soap detergent bars:

a) Surfactants

As surfactants, anionic and nonionic surfactants are preferred. For anionic surfactants, commonly linear alkylbenzene sulfonic acid can be neutralized in-situ with sodium carbo- nate. Alternatively, the neutralized form, sodium linear alkylbenzene sulfonate can be used. Preferred anionic surfactants are sodium linear alkylbenzene sulfonate and sodium coco-sulfate. Preferred nonionic surfactants as co-surfactants can be selected from alkoxylates, for example Lutensol, and ethoxylates, for example Neodol. Also, sodium lauryl sulfate is a preferred surfactant. Builders aid at the detergency of a system. Preferred builders according to the invention are selected from sodium carbonates, sodium tripolyphosphates, zeolites, bentonites, layered silicates and chelating agents, particularly edta and tetrasodium etidronate.

Commonly used auxiliary ingredients, given herein as non-limiting examples, are:

i) bleaches, preferably sodium perborate, sodium hypochlorite,

ii) bleach activators, preferably taed

iii) enzymes, preferably lipolases, proteinases and cellulases

iv) optical brighteners or fluorescent whitening agents (fwa) , preferably stilbenes and pyrazolines, for example Tinopal cbs-x (Ciba).

v) soil-suspending or anti-redeposition agents, preferably sodium carboxymethylcellu- lose, polyacrylates, soil-releasing polymers, for example Srp-4(Rhodia)

vi) anti-dye transfer agents, preferably polyvinylpyrrolidones, polyvinylimidazoles, for example any of the Sokalan series (Basf)

vii) corrosion inhibitors, preferably sodium silicate

viii) foam regulators, preferably fatty amides, non-ionics, silicones

ix) fillers, preferably sodium sulfate, aluminium sulfate, calcium carbonate, kaolin

x) dyes, preferably phthalocyanine blue

xi) water.

Further ingredients which can be present in a soap or non-soap based cleaning article according to the invention can give rise to additional effects. Examples which may be mentioned are: preservatives, abrasives, anti-acne agents, agents against skin aging, antibacterial agents, anticellulitis agents, antidandruff agents, anti-inflammatory agents, anti-irritants, irritation suppressants, antimicrobial agents, antioxidants, astringents, perspiration suppressants, antiseptics, antistatics, binders, buffers, carrier materials, chelating agents, cell stimulants, cleaning agents, treatment preparations, depiliatories, deodorisers, antiperspirants, softeners, emollients, emulsifiers, enzymes, fibres, film- forming agents, fixatives, foaming agents, foam stabilisers, antifoams, foam boosters, fungicides, gelling agents, gel-forming agents, haircare agents, hair-shaping agents, hair- smoothing agents, moisture donors, humectants, moisturisers, bleaching agents, strengthening agents, stain removers, optical brighteners, impregnating agents, soil repellents, friction-reducing agents, lubricants, opacifiers, plasticisers, polish, brighteners, polymers, powders, proteins, fat restorers, abrasive agents, silicones, skin-calming agents, skin-cleansing agents, skin care agents, skin-healing agents, skin-lightening agents, skin-protecting agents, skin-softening agents, cooling agents, skin-cooling agents, warming agents, skin-warming agents, stabilisers, UV-absorbers, UV-filters, detergents, soft rinses, suspending agents, skin-tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyes, color-protection agents, pigments, anti- corrosives, aromas, flavorings, fragrances, perfumes, or essential oils other customary constituents of a cosmetic or dermatological formulation, such as alcohols, polyols, electrolytes, organic solvents or silicone derivatives.

The fragrance compounds or perfumes for use in this invention may be any fragrance compounds or perfumes known to the art, in particular those described in S. Arctander, Perfume and Flavor Chemicals, private publishing house, Montclair, N.J., 1969 and Surburg, Panten, Common Fragrance and Flavor Materials, 5th Edition, Wiley-VCH, Weinheim 2006, preferably those explicitly mentioned in US 2008/0070825. It is a charac- teristic of this invention that an unusually broad range of fragrance compounds or perfumes may be used. Examples include digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl lau- rate, di(citronellyl) maleate, dinonanyl maleate, diphenoxyethyl maleate, di(3,7-dimethyl- 1-octanyl) succinate, di(cyclohexylethyl) maleate, di(phenylethyl) adipate, 7-acetyl- 1 ,2,3,4,5,6,7,8-octahydro-1 ,1 ,6,7-tetramethyl naphthalene, ionone methyl, ionone gamma methyl, methyl cedrylone, methyl dihydrojasmonate, methyl 1 ,6,10-trimethyl-2,5,9- cyclododecatrien-1-yl ketone, 7-acetyl-1 ,1 , 3,4,4, 6-hexamethyl tetralin, 4-acetyl-6-tert- butyl-1 ,1 -dimethyl indane, para-hydroxy-phenyl-butanone, benzophenone, methyl beta- naphthyl ketone, 6-acetyl-1 ,1 ,2,3,3,5 hexamethyl indane, 5-acetyl-3-isopropyl-1 , 1 ,2,6- tetramethyl indane, 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1- carboxaldehyde, 7-hydroxy-3,7-dimethyl octanal, 10-undecen-1-al, isohexenyl cyclohexyl carboxaldehyde, formyl tricyclodecane, condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol, 2-methyl-3-(para-tert-butylphenyl)- propionaldehyde, ethyl vanillin, vanillin, heliotropin, hexyl cinnamic aldehyde, amyl cin- namic aldehyde, 2-methyl-2-(para-iso-propylphenyl)propionaldehyde, coumarin, decalac- tone gamma, cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone, cyclo- hexadecanone, 8-cyclohexadecenone, 1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8- hexamethylcy- clo-penta-gamma-2-benzopyrane, beta-naphthol methyl ether, ambroxane, dodecahydro- 3a,6,6,9a-tetramethyinaphtho[2,1 b]furan, cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3- methylpentan-2-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, caryo- phyllene alcohol, tricyclodecenyl propionate, tricyclodecenyl acetate, benzyl salicylate, cedryl acetate, para-(tert-butyl) cyclohexyl acetate, essential oils, resinoids, and resins from a variety of sources including but not limited to orange oil, lemon oil, patchouli, Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander, lavandin, and lavender, phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(1 ,1-dimethylethyl)cyclohexanol acetate, benzyl acetate, orange ter- penes, eugenol, diethylphthalate, and combinations thereof.

The fragrance compounds or perfumes are generally present in a total amount of 0.05 to 5 wt.%, preferably of 0.1 to 2.5 wt.%, and particularly preferentially of 0.2 to 1.5 wt.%, based on the total weight of the soap.

The fragrance compounds or perfumes can be added in liquid form, undiluted or diluted with a solvent. Suitable solvents for this purpose are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol (glycerine), propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.

Furthermore, the fragrance compounds or perfumes according to the invention can be adsorbed on a carrier which serves both for fine dispersion of the fragrance compounds or perfumes in the product and also for controlled release during use. Such carriers can be porous inorganic materials, such as light sulphate, silica gels, zeolites, gypsums, clays, clay granules, etc. or organic materials such as woods and cellulose-based substances. The soap and coloured particles according to the invention can contain plant parts and plant extracts. Examples which may be mentioned are arnica, aloe, usnea, stinging nettle, ginseng, henna, camomile, marigold, rosemary, sage, horsetail or thyme.

Furthermore, cosmetic oils which can be applied dermally can be incorporated into ac- cording to the present invention, such as, for example, neutral oils of the Miglyol 812 type, apricot kernel oil, avocado oil, babussu oil, cottonseed oil, borage oil, thistle oil, peanut oil, gamma-oryzanol, rosehip kernel oil, hemp oil, hazelnut oil, currant seed oil, jojoba oil, cherry stone oil, salmon oil, linseed oil, maize germ oil, macadamia nut oil, almond oil, evening primrose oil, mink oil, olive oil, pecan nut oil, peach kernel oil, pista- chio kernel oil, rapeseed oil, rice germ oil, casyor oil, safflower oil, sesame oil, soybean oil, sunflower oil, tea tree oil, grapeseed oil or wheatgerm oil.

The soap mass and coloured particles the present invention can contain UV-absorbers (UV-filters), such as, for example, Neo Heliopane® (Symrise) to protect against discoloration of the soap or protect against solar irradiation on the skin. The UV-absorbers can be UV-A and/or UV-B-absorbers.

Suitable UV-absorbers are, for example, organic UV-absorbers from the class of A- aminobenzoic acid and derivatives, salicylic acid derivatives, benzophenone derivatives, dibenzoylmethane derivatives, diphenyl acrylates, 3-imidazol-4-yl-acrylic acid and esters thereof, benzofuran derivatives, benzylidene malonate derivatives, polymeric UV- absorbers, containing one or more silicoorganic radicals, cinnamic acid derivatives, camphor derivatives, trianilino-s-triazine derivatives, 2-hydroxyphenylbenzotriazole derivatives, 2-phenylbenzimidazole-5-sulphonic acid and salts thereof, methyl anthranilate, benzotriazole derivatives.

Preferred UV-absorbers are: 4-aminobenzoic acid, 2-ethylhexyl A- dimethylaminobenzoate, 4-aminobenzoic acid ethyl ester, homomenthyl salicylat, , 2- ethylhexyl salicylate, 5-methyl-2-(1-methylethyl)cyclohexyl 2-aminobenzoate, ethylhexyl

4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl-2-cyano-3,3- diphenylacrylate, 2-phenylbenzimidazole-5-sulfonic acid and salts thereof , 3-(4'- trimethylammonium)benzylidenbornan-2-one methyl sulfate, 3-(4'- sulfo)benzylidenebornan-2-one and the salts thereof, terephthalylidene-dibornansulfonic acid and salts thereof, 4-t-butyl-4'-methoxydibenzoylmethane, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxybenzophenon-5-sulfonic acid and its so- dium salt, 3-(4'-methylbenzylidene) camphor, 3-benzylidenecamphor, 2,4,6-trianilino-(p- carbo-2'-ethylhexyl-1 '-oxy)-1 ,3,5-triazine, phenylene-1 ,4-bis-(2-benzimidazyl)3,3'-5,5'- tetrasulfonic acid and the salts thereof, 2,2'-(1 ,4-phenylene)bis-(1 H-benzimidazole-4,6- disulfonic acid, mono sodium salt), N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]- acrylamide-polymer, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(2-methyl-3-(1 ,3,3,3- tetramethyl-1-(trimethylsilyl)-oxy)-disiloxyanyl)propyl)-phe nol, 4,4'-[(6-[4-(1 ,1-

DdimethyOaminocarbonyOphenylaminol-I .S.S-triazine^^-diyOdiiminol-bis^benzoic acid- 2-ethylhexylester), 2,2'-methylene-bis-(6-(2H-benztriazole-2-yl)-4-(1 ,1 ,3,3- tetramethylbutyl)-phenol, 2,4-bis-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1 ,3,5-triazine, benzylidenemalonate-polysiloxane, 4,4',4-(1 ,3,5-triazine-2,4,6-triyl-triimino)-tris-benzoic acid tris(2-ethylhexyl ester), 2,4-bis-[{(4-(2-ethyl-hexyloxy)-2-hydroxy}phenyl]-6-(4- methoxyphenyl)-1 ,3,5-triazine.

The total amount of UV-absorbers, if at all present, preferably is in the range of 0.1 to 6 wt.%, based on the total weight of the coloured particle or soap mass, respectively.

Moreover, it is possible to use particulate UV-filters or inorganic pigments, which optionally can be rendered hydrophobic, such as the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (e.g. MnO), aluminium (AI ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ) and/or mixtures thereof.

The incorporation of cooling agents according to the present invention is also advanta- geous. Examples of suitable cooling agents are: 1-menthol, menthone-glycerol acetal, menthyl lactate, substituted menthyl-3-carboxamides (e.g. menthyl-3-carboxylic acid N- ethylamide), 2-isopropyl-N,2,3-trimethylbutanamide, substituted cyclohexanecarbox- amides, 3-menthoxypropane-1 ,2-diol, 2-hydroxyethyl menthylcarbonate, 2-hydroxypropyl menthylcarbonate, N-acetylglycine menthyl ester, menthyl hydroxycarboxylates (e.g. menthyl 3-hydroxybutyrate), monomenthyl succinate, 2-mercaptocyclodecanone, men- thyl-2-pyrrolidin-5-one carboxylate.

Substances with a warming effect can advantageously be incorporated according to the invention. Examples are: capsaicin; dihydrocapsaicin; gingerol; paradol; shogaol; piperin; paprika powder, chilli pepper powder, extracts of paprika, extracts of pepper; extracts of chilli pepper; extracts of root ginger; extracts of Aframomum melgueta, extracts of spilan- thesacmella; extracts from Kaempferia galanga; extracts of Alpinia galanga, carboxylic acid N-vanillylamides, in particular nonanoic acid N-vanillylamide; 2-nonenoic acid am- ides, in particular 2-nonenoic acid N-isobutylamide; 2-nonenoic acid N-4-hydroxy-3- methoxyphenylamide; alkyl ethers of 4-hydroxy-3-methoxybenzyl alcohol, in particular A- hydroxy-3-methoxybenzyl n-butyl ether; alkyl ethers of 3-hydroxy-4-methoxybenzyl alcohol; alkyl ethers of 3,4-dimethoxybenzyl alcohol; alkyl ethers of 3-ethoxy-4-hydroxybenzyl alcohol; alkyl ethers of 3,4-methylenedioxybenzyl alcohol; (4-hydroxy-3- methoxyphenyl)acetannides, in particular (4-hydroxy-3-methoxyphenyl)acetic acid N-n- octylamide; nicotinaldehyde; methyl nicotinate; propyl nicotinate, 2-butoxyethyl nicotinate, benzyl nicotinate and 1-acetoxychavicol.

The soap mass and coloured particle according to the invention can contain antimicrobi- ally active ingredients or preservatives. These can be quaternary monoammonium salts, such as cocoalkylbenzyldimethylammonium chloride,

(C-i ₂ -C ₁₄ )alkylbenzyldimethylammonium chloride, 1-(3-chloroallyl)-3,5,7-triaza-1- azoniaadamantane chloride (Dowicil®), cocoalkyldichlorobenzyldimethylammonium chloride, tetradecylbenzyldimethylammonium chloride, didecyldimethylammonium chlo- ride, dioctyldimethylammonium chloride, myristyltrimethylammonium bromide, cetyl- trimethylammonium bromide, monoquaternary heterocyclic amine salts, such as, for example, laurylpyridinium chloride cetylpyridinium chloride, (C-i ₂ -C ₁₄ )alkyl- benzylimidazolium chloride, triphenylphosphonium salts, such as, for example, myristyl- triphenylphosphonium bromide, halogenated biocides, for example hypochlorites or sodium dichloroisocyanurates, phenolic biocides, such as, for example, phenol and its derivatives, phenol ethers, monoalkylphenols, polyalkylphenols, arylphenols, o- phenylphenol, p-tert-butylphenol, 6-n-amyl-m-cresol, 4,4'-diamidino-α,ω diphenoxypropane diisethionate (propamidine isethionate), 4,4'-diamidino-α,ω- diphenoxyhexane diisethionate (hexamidine isethionate), alkyl- and/or aryl-chloro- or - bromophenols, such as, for example, o-benzyl-p-chlorophenol, resorcinol and its derivatives, such as, for example, resorcinol monoacetate, cresols, p-chloro-m-xylene, dichloro- m-xylene, 4-chloro-m-cresol, halogenated diphenyl ethers, such as, for example, 2',4,4'- trichloro-2-hydroxydiphenyl ether (Triclosan) or 2,2'-dihydroxy-5,5'-dibromodiphenyl ether, chlorophenesine (p-chlorophenyl glycerol ether), bisphenol compounds, bis(2-hydroxy- 3,5-dichlorophenyl) sulphide, bis(2-hydroxy-5-chlorobenzyl) sulphide, halogenated car- banilides, such as, for example, 3,4,4'-trichlorocarbanilide, pyrithione, in particular the sodium and zinc compounds, Octopirox®, Nuosept ^® , Nuosept C ^® , dimethyldimethylolhy- dantoin (DMDM, Glydant ^® ), 3-butyl-2-iodopropinyl carbamate, Glydant Plus ^® , 3- isothiazolone compounds, isothiazolinones ("Kathon"), methylisothiazolinone, methyl- chloroisothiazolinone, diazolidinylurea (Germall II ^® ), imidazolidinylurea (Abiol ^® , Unicide U- 13 ^® , Germall 115 ^® ), benzyl alcohol, bicyclic polymethoxyoxazolidinones (e.g. Nu- osept ^® C), 2-bromo-2-nitropropane-1 ,3-diol (Bronopol ^® ), iodopropenylbutyl carbamate (Polyphase P100 ^® ), chloroacetamide, methanamine, 1 ,2-dibromo-2,4-dicyanobutane (Tektamer ^® ), 5-bromo-5-nitro-1 ,3-dioxane (Bronidox ^® ), phenethyl alcohol, o- phenylphenol, sodium o-phenylphenol, sodium hydroxymethylglycinate (Suttocide A ^® ), dimethoxane, thimerosal, dichlorobenzyl alcohol, captan, chlorophenesine, dichloro- phene, chlorobutanol and glyceryl laurate, glutardialdehyde, parabens (e.g. methylpara- ben, ethylparaben, propylparaben and butylparaben), phenoxyethanol, sorbitol, dibro- modicyanobutane, imidazolidinylureas ("Germall"), organic acids (e.g. benzoic acid, sorbic acid, salicylic acid), and esters thereof, glycols, e.g. propylene glycol, 1 ,2-di- hydroxyalkanes), ethoxylated, propoxylated or mixed ethoxylated/propoxylated fatty alcohols, fatty acids and fatty acid esters of chain lengths C ₈ to C ₂₂ with 1 to 250 ethylene glycol ether (EO) and/or propylene glycol ether (PO) units and combinations thereof.

In the soap mass and coloured particle according to the present invention it is also possi- ble to use so-called "natural" antibacterial active compounds; these are mostly essential oils. Typical assential oils having an antibacterial action are, for example, oils obtained from aniseed, lemon, orange, rosemary, wintergreen, thyme, lavender, hops, citronella, wheat, lemongrass, cedarwood, cinnamon, geranium, sandalwood, violet, eucalyptus, peppermint, gum benzoin, basil, fennel, menthol and Ocmea origanum, Hydastis car- radensis, Berberidaceae, Ratanhiae or Curcuma longa.

Important antimicrobially active substances that can be found in essential oils and can be integrated according to the present invention are, for example, anethole, catechol, cam- phene, carvacrol, eugenol, eucalyptol, ferulic acid, farnesol, hinokitiol (sic), tropolone, limonene, menthol, methyl salicylate, thymol, terpineol, verbenone, berberine, curcumin, caryophyllene oxide, nerolidol and geraniol.

The soap mass and coloured particle according to the present invention can contain insect repellents, i.e. compounds active against insects ("repellents"): repellents are agents which are intended to prevent insects coming into contact with the skin and becoming active thereon. They drive away the insects and evaporate slowly. The most frequently used repellent is diethyl toluamide (DEET). Natural repellents, such as aniseed oil, bergamot oil, cedarwood oil, citronella oil, citrus peel oils, eucalyptus oil, spruce needle oil, lavandin oil, lavender oil, Leptospermum petersonii oil, bay leaf oil, massoi oil, Mentha arvensis oil, nutmeg oil, clove leaf oil, clove flower oil, neroli oil, origanum oil, peppermint oil, pennyroyal oil, spike lavender oil, tagetes oil, tea tree oil, thyme oil, vetiver oil, cinnamon leaf oil and cinnamon bark oil or mixtures thereof; fragrances such as δ-decalactone, γ-decalactone, δ-dodecalactone, γ- dodecalactone, (E,Z)-2,6-nonadienal, δ-nonalactone, γ-nonalactone, δ-octalactone, γ- octalactone, α-phellandrene, δ-undecalactone, γ-undecalactone, 1 ,8-cineol, 1-phenyl-1 ,3- propanediol, 2-nonenal, 3,4-dihydrocoumarin, 3,8-p-menthanediol, 4a, 5, 6, 7, 8,8a- hexahydrocoumarin, 8-acetoxy-2-menthanone, benzyl benzoate, camphor, citronellol, coumarin, geraniol, linalool, octahydrocoumarin, piperitone, pulegone, hexylcinnamalde- hyde (3-hexyl-3-phenyl-2-propenal), cinnamaldehyde, coniferyl aldehyde or mixtures thereof; synthetic repellents, such as N,N-diethyltoluamide (N,N-diethyl-3- methylbenzamide, DEET), bis-(dimethylthiocarbamoyl) disulphide (thiram), ethylene- bis(dithiocarbamic acid) disodium salt (nabam), butoxypoly(propylene glycol), N- butylacetanilide, 2,3,4,5-bis(butyl-2-ene)tetrahydrofurfural, butyl 3,4-dihydro-2,2-dimethyl- 4-oxo-2H-pyran-6-carboxylate, dibutyl adiptate, di-n-butyl succinate, 2-butyl-2-ethyl-1 ,3- propanediol, di-n-propylpyridine 2,5-dicarboxylate, isobutyl 2-(2-hydroxyethyl)piperidine- 1-carboxylate, dibutyl phthalate, dimethyl phthalate, indalone and 2-ethyl-1 ,3-hexanediol or mixtures thereof can be used. Isobutyl 2-(2-hydroxyethyl)piperidine-1-carboxylate and N,N-diethyltoluamide or insect repellent mixtures containing these compounds are particularly preferred.

The soap mass and coloured particle according to the present invention can contain deodorants and/or antiperspirants, i.e. active compounds or compounds mixtures having a deodorant and/or antiperspirant action. These include antiperspirants based on aluminium, zirconium or zinc salts, deodorants, bactericides or bacteriostatic deodorising substances, such as, for example, triclosan, hexachlorophene, triclocarban, contain alcohols and cationic substances, such as, for example, quaternary ammonium salts and odour absorbers, such as, for example, ^® Grillocin (combination of zinc ricinoleate and various additives) or triethyl citrate, optionally in combination with an antioxidant, such as, for example, butylhydroxytoluene or ion exchange resins. In so-called antiperspirants, the formation of perspiration can be suppressed by astringents - predominantly aluminium salts, such as aluminium hydroxychloride (aluminium chlorohydrate). The soap mass and coloured particle according to the present invention can contain antioxidants suitable or customary for cosmetic and/or dermatological applications.

The antioxidants are advantageously chosen from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L- carnosine and derivatives thereof (e.g. anserine), carotenoids, carotenes (e.g. α- carotene, β-carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl, glyceryl and oligoglyceryl esters thereof) and salts thereof, dilauryl thiodipropionate, distearyl thio- dipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulphoximine compounds (e.g. buthionine sulphoximines, homocysteine sulphoximine, buthionine sulphones, penta-, hexa- and heptathionine sulphoximine) in very low tolerated doses (e.g. pmol to μmol/kg), also (metal) chelating agents (e.g. α-hydroxy fatty acids, phytic acid, lactoferrin, α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, tannins, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, ferulic acid and derivatives thereof, caffeic acid and derivatives thereof, sinapic acid and derivatives thereof, curcuminoids and derivatives thereof, retinoids, ursolic acid, levulinic acid, butyl- hydroxytoluene, butyl hydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof, (e.g. ZnO, ZnSO ₄ ), selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans- stilbene oxide), and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleo- sides, peptides and lipids) of said active compounds. Natural extracts, e.g. from green tea, algae, grape seeds, wheatgerms, rosemary, flavonoids, quercetin, phenolic ben- zylamines. Coenzymes, such as, for example, coenzyme Q10, plastoquinone, menaquinone, ubiquinols 1-10, ubiquinones 1-10 or derivatives of these substances are also suitable. The soap mass and coloured particle according to the present invention can contain moisture regulators. The moisture regulators ("moisturisers") used are, for example, the following substances: sodium lactate, urea, alcohols, sorbitol, glycerol, propylene glycol, 1 ,2-pentane deiol, collagen, elastin or hyaluronic acid, diacyl adipates, petrolatum, ectoin, urocanic acid, lecithin, pantheol, phytantriol, lycopene, algae extract, ceramides, cholesterol, glycolipids, chitosan, chondroitin sulphate, polyamino acids and sugars, lanolin, lanolin esters, amino acids, alpha-hydroxy acids (e.g. citric acid, lactic acid, malic acid) and derivatives thereof, sugars (e.g. inositol), alpha-hydroxy fatty acids, phytosterols, triterpene acids, such as betulinic acid or ursolic acid, algae extracts.

The mixtures soap mass and coloured particle according to the present invention can contain skin-lightening substances, such as, for example, 2,7-dinitroindazole, thiocitrul- line, lactoferrin, humic acid, bile acid, bile extracts, bilirubin, biliverdin, arbutin, kojic acid, hydroquinone, resorcinol, flavonoids, retinoids, soya milk, serine protease inhibitors or lipoic acid.

The soap mass and coloured particle according to the present invention can also contain skin-regenerating complexes (skin repair complexes), which are obtainable, for example, from inactivated and disintegrated cultures of bacteria of the Bifidus group.

The soap mass and coloured particle according to the present invention can also contain self-tanning agents, such as dihydroxyacetone, glyceraldehyde, indole and derivatives thereof.

The soap mass and coloured particle according to the present invention can contain hair- smoothing agents. Hair-smoothing agent as understood herein are substances which lead to the human or animal hair being smoothed. Suitable hair-smoothing agents are, for example, ammonium hydroxide, ammonium thioglycolate, calcium hydroxide and sodium hydroxide.

The soap mass and coloured particle according to the present invention can contain depilatory agents. Depilatory agents as understood herein are substances which lead to hair being removed from the skin.

Suitable depilatory agents are, for example, barium sulphide, magnesium thioglycolate, strontium sulphide, calcium sulphide, thiopropionic acid, strontium thioglycolate, calcium thioglycolate, potassium sulphide, thioglycerol, ethanolamine thioglycolate, potassium thioglycolate, thioglycolic acid, lithium sulphide, sodium sulphide, thiolactic acid, magnesium sulphide, ammonium thioglycolate and sodium thioglycolate.

The soap mass and coloured particle according to the present invention can also contain antidandruff active compounds, such as, for example, climbazole, ketoconazole or zinc pyrithione.

The soap mass and coloured particle according to the present invention can also contain active compounds selected from the following group, oily or oil-soluble active compounds being preferred: acetylsalicylic acid, atropine, azulene, hydrocortisone and derivatives thereof, e.g. hydrocortisone 17-valerate, vitamins, e.g. vitamin A and derivatives, ascorbic acid and derivatives thereof, vitamins of the B and D series, very beneficially vitamin B ₁ , vitamin B ₁₂ , niacinamide (nicotinamide), vitamin D ₁ , vitamin E (tocopherol) and derivatives thereof, vitamin F, panthenol, pantothenic acid, folic acid, and combinations thereof, but also bisabolol, unsaturated fatty acids, specifically the essential fatty acids (often also called vitamin F), in particular γ-linolenic acid, oleic acid, eicosapentaenoic acid, docosa- hexaenoic acid and derivatives thereof, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of vegetable and animal origin, e.g. evening primrose oil, borage oil or currant seed oil, fish oils, cod-liver oil or also ceramides and ceramide-like compounds and so on, vitamin-based extracts: active compound composi- tions primarily with vitamin A, C, E, B ₁ , B ₁₂ , folic acid and biotin, amino acids and ferments, and compounds of the trace elements magnesium, silicon, phosphorus, calcium, manganese, iron or copper. Vitamins, such as, for example, vitamins A and E, can be incorporated to vitalise the skin.

The soap mass according to the present invention can also comprise colorants, particu- larly dyes like those used in the coloured particle. Colorants suitable for use in the present invention can preferably be selected from the Symrise Dragocolor product range (www.symrise.com/en/fragrances/pdf/dictionary_of_colors.pdf) . Particularly suitable colorants are water-soluble or water dispersible dyes which include Hansa Yellow G (C.I. 11680), Red (C.I. 12490), Orange Il (C.I. 15510), Pyranine (C.I. 59040), Acid Green (C.I. 61570), Blue (C.I. 61585) and combinations thereof. Particularly suitable pigments are dermatologically acceptable metal oxides, e.g. titanium dioxide. The soap mass and coloured particle according to the present invention may also comprise electrolytes, minerals or salts such as sodium chloride (typically up to 0.5 wt.%) and chelating agents such as EDTA or citric acid.

The soap mass and coloured particle according to the present invention may also com- prise agents for adjusting a pH value or the ionic strength. Examples which may be mentioned are phosphoric acid and salts thereof, sodium acetate, acetic acid, citric acid and salts thereof, EDTA, disodium EDTA and tetrasodium EDTA.

In addition, the following ingredients and materials, for example, are possibly incorporated according to the present invention: vegetable waxes and oils, such as, for example, cocoa butter, almond oil, avocado oil or jojoba oil for improving the feel of the skin.

Soap mass and coloured particle according to the present invention may comprise abrasives customary in cosmetic and dermatological preparations. Natural or synthetic minerals which can have an abrading or abrasive action are, for example, dolomite, calcium carbonate, aragonite, feldspars, aluminium oxide, silicon dioxide, quartz, quarzite, gyp- sum, pumice, calcite, limestone, lime, artificial marble, marble, zirconium oxide, titanium dioxide, talc, sand, quartz sand, zirconium silicate, bentonites, precipitated chalk, magnesium carbonate, almond, peach and apricot kernel flour, wheatgerm flour, rice cornflour, olive kernel flour and walnut kernel flour. Pumice, calcite, limestone, lime, chalk, artificial or natural marble are particularly suitable. The hardness of the abrasive is preferably in the range from 1 to 4 on the Mohs' scale. The particle size is advantageously in the range 1 to 70, preferably in the range 1 to 60 and particularly preferentially in the range 1 to 50 micrometres. The total amount of abrasives (one or more) is preferably 0.5 to 10 wt.%, based on the total weight of the soap.

Soap mass and coloured particle according to the present invention may comprise skin conditioners, emollients, moisturizers, preservatives which are preferably selected form the group consisting of Dragoxat EH (Ethylhexyl Ethylhexanoate), Dragoderm (Glycerin,

Wheat Gliadins), Hydrolite-5 (1 ,2-pentane diol), Symdiol 68 (a 1 : 1 (m/m) mixture of 1 ,2- hexane diol and 1 ,2-octane diol), 1 ,2-decane diol, PCL-Liquid (Cetearyl Ethylhexanoate, lsopropyl Myristate), alpha-bisabolol (Dragosantol 100), Dragocid Liquid (a mixture of phenoxyethanol, methylparaben, ethylparaben, butylparaben, propylparaben and isobu- tylparaben) and combinations thereof. The listed ingredients can be obtained from Sym- rise. The present invention can also be used on transparent/translucent extruded soap bases. Suitable commercially available transparent/translucent extruded fatty acid soaps are available from Uniqema and include Prisavon 1983 (Sodium Tallowate, Sodium Palm Kernelate, Water, Glycerin, Sorbitol, Tallow Acid, Palm Kernel Acid, Tetrasodium EDTA, Tetrasodium Etidronate) and Prisavon 1984 (Sodium Palmate, Sodium Palm Kernelate, Water, Glycerin, Sorbitol, Palm Acid, Palm Kenel Acid, Tetrasodium EDTA, Tetrasodium Etidronate). Transparent/translucent extruded fatty acid soaps are also available from other regional soap manufacturers such as PT. Megasuryamas (Indonesia).

Transparent/translucent soap can also be converted from opaque soap of vegetable or tallow origin. The process of converting opaque soap to transparent/translucent soap is well-documented in literature and involves extensive shearing of the soap base with adequate amounts of soap crystal retardant materials such as glycerine, sorbitol, polyethylene glycol, propylene glycol, alcohol etc.

The present invention is also applicable to combi-bars extruded from conventional soap plodders. Combi-bars are hereby defined as a mixture of soap and surfactants. Combi- bars produced on conventional sigma mixers and soap plodders are carefully formulated to address the stickiness of the mixture due to the presence of surfactants that would otherwise pose problems in production. It is common to use dry, absorbent materials such as talc, kaolin, starch etc to address the stickiness in high-surfactants combi-bars. Alternatively, the combi-bar can have a higher soap to surfactant ratio for reasonable processing in conventional equipment.

Preferably the coloured particle according to the present invention comprises:

i) a total of 9.5 to 90 wt%, preferably 30 to 80 wt%, of the water-soluble component(s)

ii) a total of 9.5 to 90 wt%, preferably 10 to 50 wt%, of the water-insoluble component(s)

iii) a total of up to 0.5 wt%, preferably 0.0001 to 0.05 wt%, of the dye(s), and

iv) optionally a total of up to 30 wt%, preferably up to 15 wt%, of further ingredients selected from the group consisting of solvents, skin- and/or soap fabric conditioning agents, perfumes, perfumery raw materials, coloured or uncoloured minerals, surfactants, and combinations thereof,

based on the total weight of the coloured particle.

Also preferably, the soap according to the present invention comprises a total of 0,1 to 5 wt% of the coloured particles, preferably 0,5 to 2 wt%, based on the total of the soap.

The coloured particles according to the present invention can be added to the soap mass at any convenient stage. Thus, the present invention allows for the production of transparent, translucent and opaque soaps as well as combi-bars.

The invention is further described by the accompanying figures and examples, without limiting ambit and scope of the claims. Unless stated otherwise, all percentages relate to weight.

Example 1, 2 and 3

This example studies the effect of the extrusion temperature against the different melting points of individual high-molecular weight polyethylene glycols.

i) Composition of Coloured Particles

Procedure: a) Melt the ingredients of Part A. Mix well. (6O ⁰ C - 7O ⁰ C)

b) Add Part B. Mix well.

c) Transfer mixture drop-wise to a cool surface and allow mixture to form into solid particles of various sizes. Alternatively, the hardened

mixture can be crushed in a blender or suitable device to form solid particles,

ii) Soap Formulations

Procedure:

a) Prepare the ingredients of Part A. Mix well.

b) Add the ingredients of Part B. Mix well. c) Add the ingredients of Part C. Mix well and process accordingly in soap plodder at room temperature with no additional heating at extrusion point.

d) Extrude soap billet, cut and stamp soap bars accordingly.

Observations:

a) Formulation 1 produced soaps with a homogenised distribution of the colour dye from the coloured particles. The dye is released almost completely into the soap mass with no major areas of contrasting colours.

b) Formulation 2 produced soaps with areas of varying contrast in colours. There are areas of intense yellow colour from the coloured particles against the blue colour of the soap.

c) Formulation 3 produced soaps with areas of varying contrast in colours. There are areas of intense yellow colour from the coloured particles against the blue colour of the soap.

The melting points of the polyethylene glycols used are given in the following table:

Coloured particles B & C have polyethylene glycols with much higher melting points than Coloured particle A. The varying contrast in colours in the soaps of formulation 2 and 3 indicated a controlled release of the colour dye from the coloured particles.

Examples 4 and 5

This example studies the effect when the extrusion temperature is raised to 45 ⁰ C against the previous example whereby the temperature is set at 3O ⁰ C - 35 ⁰ C.

i) Soap Formulations

Procedure:

a) Prepare the ingredients of Part A. Mix well.

b) Add the ingredients of Part B. Mix well.

c) Add the ingredients of Part C. Mix well and process accordingly in soap plodder at room temperature with additional heating at extrusion point.

d) Extrude soap billet, cut and stamp soap bars accordingly.

Observations:

At the extrusion temperature of 45 ⁰ C ± 2 ⁰ C, Formulation 4 and Formulation 5 produced soaps with a more homogenous release and distribution of the colour dye from the coloured particles. There are slightly more areas of contrasting colours in the soap made according to Formulation 5. The higher melting point of Polyethylene Glycol M. W. 9000 against Polyethylene Glycol M. W. 6000 indicated a slower release of the dye from the coloured particle under similar processing conditions.

Examples 6 and 7 This example studies the behaviour of an oil-soluble colour dye as opposed to the water- soluble dyes used in the previous examples.

i) Composition of Coloured Particles

Procedure:

a) Melt the ingredients of Part A. Mix well. (6O ⁰ C - 7O ⁰ C)

b) Add Part B. Mix well.

c) Transfer mixture drop-wise to a cool surface and allow mixture to form into solid particles of various sizes. Alternatively, the hardened mixture can be crushed in a blender or suitable device to form solid particles.

ii) Soap Formulations

Procedure:

a) Prepare the ingredients of Part A. Mix well.

b) Add the ingredients of Part B. Mix well.

c) Add the ingredients of Part C. Mix well and process accordingly in soap plodder at room temperature with additional heating at extrusion point.

d) Extrude soap billet, cut and stamp soap bars accordingly.

Observations:

Formulations 6 and 7 used an oil-soluble colour dye as opposed to the water-soluble colour dye used in formulations 4 and 5. At the extrusion temperature of 45 ⁰ C ± 2 ⁰ C, the soaps showed varying contrast in colours with areas of intense colour from the coloured particles against surrounding lighter colour tones. The soaps made according to formulation 7 retain much of the whiteness of the base soap indicating a lower degree of release for the colour dye from the coloured particle. This showed that the higher melting point of Polyethylene Glycol M. W. 9000 as against Polyethylene Glycol M. W. 6000 does exert an effect on the rate of release for the colour dye from the coloured particle.

Examples 8 and 9

This example studies the effect of water-soluble and oil-soluble colourants in the coloured particles when used in commercially-available translucent soap.

i) Composition of Coloured Particles

Procedure:

a) Melt the ingredients of Part A. Mix well. (6O ⁰ C - 7O ⁰ C)

b) Add Part B. Mix well.

Transfer mixture drop-wise to a cool surface and allow mixture to form into solid particles of various sizes. Alternatively, the hardened mixture can be crushed in a blender or suitable device to form solid particles.

ii) Soap Formulations

Procedure:

a) Prepare the ingredients of Part A. Mix well.

b) Add the ingredients of Part B. Mix well.

c) Add the ingredients of Part C. Mix well and process accordingly in soap plodder at room temperature with additional heating at extrusion point.

d) Extrude soap billet, cut and stamp soap bars accordingly.

Observations:

In examples 8 and 9, a commercially available translucent soap base is used. At the extrusion temperature of 45 ⁰ C ± 2 ⁰ C, both sets of soaps showed areas of contrasting colours. This showed that the effects of the coloured particles are also evident in translucent soap. In addition, the effects of the coloured particles can be seen within the soaps.

Example 10

Apart from using commercially available translucent soap base, the coloured particles can be used in a translucent soap base converted from an opaque soap base in a streamlined, procedural operation. A common method, well-documented in literature, is to shear the opaque base with a blend of known soap crystal retardants in adequate quantities with sufficient heat till translucency is obtained in the soap mass.

In this example, an opaque soap base (Prisavon 9220 from Uniqema) with a blend of known soap crystal retardants and stearic acid is sheared in a jacketed sigma mixer with constant heat at 6O ⁰ C - 7O ⁰ C till translucency is obtained in the soap mass. The shearing process is preferably conducted in a double-bladed sigma mixer with a counter- directional shearing action. The perfume is added into the blend of soap crystal retardants to take advantage of the mixing and shearing process.

i) Perfumed Blend of Soap Crystal Retardants

Procedure:

1 ) Dissolve BHT in fragrance. (Part A)

2) Prepare Part B. Blend well.

3) Prepare Part C. Mix well to obtain a clear solution.

4) Add Part B to Part C. Mix well to obtain a clear solution.

5) Add Part A to mixture (Part B + Part C). Mix well.

Note: Adjust pH to the range of 6.0 - 6.5 with Citric Acid. ii) Soap conversion formulation

iii) Final soap formulation with coloured particles

Procedure:

1 ) Prepare Part A. Mix well.

2) Add Part B to Part A. Mix well and process accordingly in soap plodder at room temperature with additional heating at extrusion point.

3) Extrude soap billet, cut and stamp soap bars accordingly.

Observations:

The soaps showed areas of contrasting colours and the effects are also perceived within the soap. At the extrusion temperature of 5O ⁰ C ± 2 ⁰ C, the soaps showed a greater degree of colour dye released from the respective coloured pellets than the soaps extruded at a temperature of 45 ⁰ C ± 2 ⁰ C in examples 8 and 9.

Examples 11 and 12

This example studies the effect of different levels of coloured particles and incorporated in the soap mass at a different stage in the manufacturing process.

i) Soap Formulations

In examples 11 and 12, the coloured particles (composition E) are introduced into the soap base at the initial mixing stage and processed under similar conditions. Both sets of soaps showed areas of contrasting intensity of colours. However, example 12 produced soaps whose primary base colour has taken on a slightly stronger bluish tone than soaps produced from example 11. The additional dye released from the coloured particles as a result of an increase in dosage showed that the colour effects in the soaps can also be manipulated by the amount of coloured particles used.

Example 13

This example studies the effect of the coloured particles when incorporated into the soap mass at the end stage prior to extrusion of the manufacturing process.

i) Soap Formulation

In example 13, the same formulation as example 11 is used. However, the coloured particles are introduced into the soap mass at a later stage prior to extrusion. The soaps produced by example 13, showed a whiter primary base colour with a stronger contrast against areas of intense colours in comparison with soaps produced by example 11. This example showed that manipulation in the stages for which the coloured particles are introduced into the soap mass can also influence the development of the coloured effects in the soap.

Figure 1 shows a corresponding soap.

Example 14

The sequence of adding the coloured particles prior to extrusion is repeated in this example with a converted translucent soap base.

The process of converting an opaque soap into a translucent soap is as stated in Example 10.

i) Perfumed Blend of Soap Crystal Retardants

Procedure:

1 ) Dissolve BHT in fragrance. (Part A)

2) Prepare Part B. Blend well.

3) Prepare Part C. Mix well to obtain a clear solution.

4) Add Part B to Part C. Mix well to obtain a clear solution.

5) Add Part A to mixture (Part B + Part C). Mix well.

Note: Adjust pH to the range of 6.0 - 6.5 with Citric Acid. ii) Soap conversion formulation

iii) Final soap formulation with coloured particles

Procedure:

1 ) Prepare Part A. Mix well and process in soap plodder.

2) Add Part B to Part A prior to extrusion. Mix well and process accordingly in soap plodder at room temperature with additional heating at extrusion point.

3) Extrude soap billet, cut and stamp soap bars accordingly.

Ethanol and water can be added to the base to enhance the translucency of the soap.

Observations:

The soap samples showed areas of contrasting intensity of colours. This example showed that manipulation in the stages for which the coloured particles are introduced into the soap mass can also influence the development of the coloured effects in the soap.

Example 15

The sequence of adding the coloured particles prior to extrusion is repeated in this example with a high soap to surfactant ratio combi-bar. Skin-conditioning agents can be added to the soap mass or blended with the perfume prior to addition to the soap mass.

Procedure:

1 ) Prepare Part A. Mix well.

2) Melt the ingredients of Part C. Mix well. (60°C-70°C)

3) Add Part B to Part C. Mix well.

4) Add mixture (Part B + Part C) to Part A. Mix well.

5) Add the ingredients of Part D. Mix well and process accordingly.

6) Add Part E prior to extrusion and process accordingly.

The coloured effects observed are similar to examples conducted on opaque and translucent soap.

Examples 16 & 17 In a comparative example on the choice of solid fatty acids at room temperature, lauric acid and myristic acid were used in place of stearic acid in the composition of Coloured Particle E.

i) Composition of Particles

Procedure:

a) Melt the ingredients of Part A. Mix well. (6O ⁰ C - 7O ⁰ C)

b) Add Part B. Mix well.

c) Transfer mixture drop-wise to a cool surface and allow mixture to form into solid particles of various sizes. Alternatively, the hardened mixture can be crushed in a blender or suitable device to form solid particles.

ϋ) Soap Formulations

In comparison with soaps produced in Example 13, Example 16 & 17 produced soaps with a lesser number of areas with high intense colours. The soaps of Example 16 have a more gradual contrast of colour against the white background of the primary soap base. The soaps of Example 17 have a more homogenous distribution of colour giving the soap a bluish shade against lesser white areas of the primary soap base.

The choice of solid fatty acids in the composition of the coloured particles can exert an influence on the distribution and release of the dye from the particles giving varied coloured effects on the surface of the soap.

Example 18 & 19

In a comparative example, mica is incorporated into the coloured particles for an added effect to the soaps.

i) Composition of coloured particles

ii) Soap Formulations

The coloured effects are evident in both opaque and translucent soap. The example demonstrated that it is possible to include in addition to liquid dyes, coloured minerals such as mica to give an added effect to the soap.

Example 20

The colour effects are replicated in a detergent bar composition produced in a similar manner with the colour particles incorporated prior to the extrusion of the detergent bar. i) Composition of colour particles

Procedure: 1 ) Melt the ingredients of Part A. Mix well. (6O ⁰ C - 7O ⁰ C)

2) Add the ingredients of Part B accordingly. Mix well.

3) Transfer mixture drop-wise onto a cooled surface.

4) Remove hardened droplets of mixture. ii) Detergent bar composition

Procedure:

1 ) Prepare the ingredients of Part A. Mix well in a sigma mixer or kneader.

2) Add Part B to Part A. Mix well for the neutralization process. (10 - 15 minutes)

3) Add the ingredients of Part C according with mixing in the sigma mixer.

4) Transfer the mass to the plodder and process accordingly.

5) Add Part D to the mass prior to extrusion as detergent bars.

The extruded detergent bar, as depicted in figure 2, showed streaks of blue dye across the white primary base with areas of high-intense colours and soft tones. The example demonstrated that the present invention is also applicable to the manufacture of detergent bar.

Example 21 The colour effects in soap are replicated in an example with the fatty acids replaced with glycol stearate (ester of ethylene glycol and stearic acid) in the composition of the coloured particles.

i) Composition of coloured particles.

ii) Soap Formulation

In this example, two different coloured particles at different dosages are incorporated into a soap formulation with resulting perceivable colour effects. This example demonstrated that it is possible to incorporate more than one coloured particle in the soap and the fatty acids in the composition of the coloured particle can be replaced with a glycol stearate as the water-insoluble component.