GB2365440A

GB2365440A - Method of constituting detergent products

Info

Publication number: GB2365440A
Application number: GB0019019A
Authority: GB
Inventors: Mark Phillip Houghton
Original assignee: Robert McBride Ltd
Current assignee: Robert McBride Ltd
Priority date: 2000-08-04
Filing date: 2000-08-04
Publication date: 2002-02-20
Also published as: GB0019019D0

Abstract

A method of constituting detergent products includes adding a metered amount of a liquid to a pre-formed porous unit-dose detergent mass. The method is most effective when the liquid is sprayed on and is of particular applicability in the perfuming of detergent tablets. Greater perfume intensity than observed from higher apparent surface area powders can be observed by using the method, particularly when tablets of compressed detergent of specified porosity and spray particle size are used.

Description

<Desc/Clms Page number 1> Perfuming of detergents products The present invention concerns a method of individually perfuming unit dose detergents products in the form of a porous mass.

Detergents tablets (i.e. unit dose detergents products in the form of a porous mass) are widely used in the consumer goods market. In such markets the aesthetic characteristics of the product are of equal importance to the consumer as the detergency performance effects of the product. One of these characteristics is smell, typically achieved by the application of a concentrated perfumery oil. Such oils are typically added to a detergent powder composition which is then compressed to form a tablet. This is very widely described in the prior art.

Such an approach offers simplicity and low complexity but suffers from several drawbacks. This is, for example, illustrated by the prior art on the encapsulation of perfumery oils as described in GB 2 335 434 (McBride) and references therein. Such approaches delay perfume release until `activated' by dissolution of the product: However, research has shown that the first impression on encountering a new product (as opposed to when it is actually used) is important for consumers. Hence, `free' perfumery components need to be readily available to the atmosphere. The appropriate perfume oil levels for achieving this (typically 0.5 to 2%) have been refined in the development of concentrated powders as widely described in the art. However, the reduced surface area of tabletted detergents requires increased levels of perfume oils (typically 1 to 3%). Unexpectedly the levels are not proportionate to the change in surface area. Nevertheless, the increased levels are an economic hindrance and the typically hydrophobic perfume oils provide a means of reducing the internal hydrophilicity, hence water uptake and therefore dissolution rate of detergent tablets. The latter issue is one which will be realised as a central theme in much of the prior art on detergents tablets.

In addition it is desirable in consumer products to be able to provide flexibility and variety, functions which are not readily compatible with producing large batches (typically in tonnes) of detergent powders (necessary for achieving steady state conditions) from which to produce individual unit doses (typically in grams), for example as tablets. The ability to modify perfume characteristics per unit dose is desirable.

It is an object of the present invention to obviate or mitigate some or all of these disadvantages with prior art compositions by means of applying the perfumery oils in the form of a metered dose per porous detergent unit. In doing so additional benefits of increased production flexibility, in potentially changing perfumery characteristics per detergent unit, are achievable. The methodology of applying liquids also solves more general problem of tailoring the properties of detergents tablets within a given production run using a common `base' composition.

According to the present invention there is provided a method of adding a metered amount of a liquid to a pre-formed porous unit-dose detergent mass.

We have surprisingly found that using the above mentioned method lower levels of perfumery oils are required to give the same perfumery `impact' than when used with the equivalent amount of higher surface area detergent powder.

Preferably the metered amount of liquid is applied as a spray and the pre-formed porous mass is a detergent tablet.

The liquid is preferably added at between 0.1 and 5% by weight of the detergent mass, more preferably between 0.2 and 1.5% of the mass and most preferably between 0.5 and 1 % of the mass.

The spray is preferably one with an average particle size of between 10 and 500pm, more preferably between 50 and 200pm.

The detergent mass of the invention needs to be capable of adsorbing the liquid added by virtue of its porosity (on whatever scale), however, detergent masses with a void volume of greater than 1 %, more preferably between 2 and 60%, and most preferably between 5 and 20% are required for optimal effect.

The liquid applied is preferably a volatile liquid and the liquid applied should remain substantially as a liquid, unless lost in vapour form, under normal conditions, after being ad- or absorbed into or onto the porous detergent mass.

The porous detergent mass of the invention should be a unitary mass, however, a mass composed of a plurality of interconnected or closely related bodies is within the scope of the invention. The

porous detergent mass may be composed of bodies otherwise separate but effectively associated as one, or bodies participating in a continuity of a liquid application operations (i.e. a continuous spray on passing tablets) are considered within, though imperfectly practising, the invention. Liquid additives The liquid additive is preferably a perfume. A perfume will typically be formulated in a product using the invention. The perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based primarily on aesthetic considerations. Examples of suitable perfume compounds and compositions can be found in US 4,145,184, US 4,209,417, US 4,515,705, US 4,152,272, all of which are patents being incorporated herein by reference. Many suitable perfume ingredients with odour characteristics, and physical and chemical properties, such as molecular weight and boiling point, are given in "Perfume and Flavour Chemicals (Aroma Chemicals)," Steffen Arctander, 1969, publ., Steffen Arctander and is incorporated herein by reference. Examples of the highly volatile, low boiling, perfume ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bornyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate, and vertenex (para-tertiary-butyl cyclohexyl acetate).

Natural or Essential oils are particularly suitable for use in the invention. For example, thymol, eugenol, menthol also tea tree, pineol, eucalyptus, camphor, cedar, oloe vera, citronelol, citrus, lemon, lime, limonene, grapefruit, geranium, mint, peppermint, spearmint, cedarwood, clove, litsea, sassafras, patchouli, coriander oils and the principle sub components thereof.

Also suitable are lavandin, with major components of linalool, linalyl acetate, geraniol and citronellol. Lemon oil and orange terpenes with major components of about 95% d-limonene.

Geraniol, menthol and eucalyptus oils include the moderately volatile perfume ingredients: amyl cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-eugenol, flor acetate, heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta-selinene, trichloromethyl phenyl carbinyl acetate, triethyl citrate, vanillin, and veratraldehyde. Cedarwood terpenes are composed mainly of alpha-cedrene, beta-cedrene, and other alkyl and alkenyl sesquiterpenes. Examples of suitable less volatile, high boiling, perfume ingredients are: benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (1,3,4,6,7,8- hexahydro- 4,6,6,7,8,8- hexamethyl-cyclo-penta-gama-2-benzopyran), hexyl cinnamic aldehyde, lyral (4 - (4 - hydroxy-4-methyl pentyl) - 3 - cyclohexene - 10 - carboxaldehyde), methyl cedrylone, methyl dihydro jasmonate, methyl-beta-naphthyl ketone, musk indanone, musk ketone, musk tibetene, and phenylethyl phenyl acetate. Such components are particularly preferred constituents of any perfume composition used in the invention. Suitable essential oils include patchouli, peppermint, vetiver, geranium, ange, spearmint, thyme, lime, pine, rose and eucalyptol. The above list is illustrative and not limiting.

A method of applying a liquid glue to a detergent unit-dose is out with the scope of the invention unless such glue is applied as a spray. Perfumery solvents Figures given for optimum perfume levels take in to account the incorporation of solvent components which are used to improve handleability and `bulk up' the perfumery essences for commercial application. Such solvents as di propylene glycol, hexanol, diethyl phthalate and ethanol are illustrative examples. It is understood that such materials are normally present at levels in the region of 20 to 70% and the use of perfumes with very high or low levels of such solvents and their recognised equivalents is considered within the scope of the invention, particularly at the preferred levels as expressed as the equivalent normally formulated perfume, i.e. as adjusted to a normalised concentration.

Physical form of the unit dose The unit dose according to the present invention is a porous solid (as described above) in the form of a tablet, bar, briquette, cake, extrudate, `shaped body'. These terms, particularly tablet, briquette, and extrudate are considered synonyms if such are effectively composed of discrete particles and particularly if formed by compression of such particles. A unit dose is a detergent unit suitable for use either singly or in a discrete number of units for a detergency (or similar operation). It is therefore a unit with a surface area of 200 square centimetres external surface per gram, more preferably of less than 50 square centimetres external surface area per gram, most preferably less than 10 square centimetres external surface area per gram. Composition of the detergent The detergent formulation in accordance with the invention will include at least one surface active agent which may, for example, be an anionic, cationic, non-anionic or amphoteric surface active agent. Any of the surface active agents widely used in detergent formulations may be employed in the present invention. Such agents are typically employed in amounts of from 1 to 25% by weight. If an amphoteric surface active agent is used it may be present in the formulation in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5%, even more preferably 1 to 4% on the same basis.

The amphoteric surface active agent may be betaine surface active agent. Preferred betaines may be either of the formula (I) or (II).

In the above formula, R1 and RZ may be the same or different C1.4 alkyl groups whereas R3 is an alkyl group having 8-22 carbon atoms, more preferably 12 to 18 carbon atoms e.g. mixed CIO to C14# The preferred betaine for use is cocoamidopropyl betaine.

An alternative amphoteric surface active agent for use in the formulation of the invention is a glycinate of the formula R'NHCHICO2H where R3 is as defined above. Other suitable materials are as given in chapter 1 of "Amphotenc Surfactants", e.g. Lomax Ed, Marcel Decker, New York 1996.

It is preferred that a cationic surface active agent is employed in conjunction with the amphoteric surface active agent. The cationic surface active agent is preferably used in an amount of up to 6% by weight of the formulation and is conveniently added in conjunction with a clay especially as herein described. Examples of suitable cationic surface active agents include quaternary ammonium salts having three lower (C1.4) alkyl groups (preferably methyl groups) and a long chain (C8-2o) alkyl group, e.g. coco trimethyl ammonium chloride. Further examples include alkyl pyridinium salts and other compounds in which the nitrogen atom of the pyridine assumes a quaternary form, e.g. as in an alkyl pyrridinium bromide. Cationics with C10 to C20, more preferably with, C12 to C18 alkyl chains are preferred.

Further examples of cationic surface active agents which may be used include amine and imidazoline salts.

If an anionic surface active agent is used then it is preferably present in the formulation in an amount of up to 20%, more preferably up to 15 %, even more preferably from 2 to 10% by weight of the formulation. Examples of anionic surface active agents which may be employed include alkylaryl sulphonates, alkyl sulphates, ether sulphates and ether carboxylates a11 as conventionally employed in laundry detergent formulations. Di-anionic surfactants are noted as being particularly useful. Anionics with C10 to C20, more preferably with, C12 to C18 alkyl chains are preferred. If a non-ionic surface active agent is used then it is preferably present in an amount of up to 20% by weight of the formulation, more preferably 2 to 10% on the same basis. Examples of predominantly liqiuid non-ionic surface active agents which may be used include alkoxylates, ethylene oxide/propylene oxide block copolymers, alkanolamides (e.g. monoethanolamides and diethanolamides), esters and amine oxides. Non-ionics with C10 to C20, more preferably with, C12 to C18 alkyl chains are preferred. If a liquid non-ionic surface active agent is to be included then it may for example an alcohol ethoxylate. The alcohol residue (which may be of a primary or secondary alcohol) may for example comprise 8 to 18 carbon atoms and be ethoxylated with an average of 3 to 20 moles of ethylene oxide per mole of alcohol.

Suitable liquid non-ionic surface active agents are available from ICI under the designations Synperonic A3 and Synperonic A7. Mixtures of the A7 and A3 active agents may also be used. Also suitable are Lutensol A03 and Lutensol A07 (ex BASF).

Examples of solid non-ionic surface active agents which may be used in the formulation in accordance with the first aspect of the formulation include alkyl(C8_22)polyglycosides. The preferred glycoside employed in the present invention is a glucoside (i.e. based on glucose), functionalised with a primary alcohol (e.g. C12-C14). More preferably the glucoside is in the form of a polyglucoside, with a preferred degree of polymerisation of between 1-2, most preferably about 1.4. Non-ionic surface active agents may be used in the form of particles or granules containing at least 30% by weight, more preferably at least 40% by weight of solid non-ionic surface active agent.

A suitable polyglycosides are available under the name Glucopan (Henkel). Preferably used as Glucopon G50 granules (50% APG Glucon, 50% sulphate).

The surfactant can be present at up to 25%, more preferably between 1% and 20%. For textile washing compositions the most preferable range is between 10 and 20% and for hard surface cleaning between 1 and 5% and for fabric refresher and air freshener products less than 1%. The preferred surfactant is one carrying an electrical charge, most preferably an amphoteric or anionic surfactant.

Additional detergent components Builder The formulation may include at least one builder salt in a total amount of 0.1 % to 50% by weight of the formulation. Mixtures of builder salts are typically employed. The builder may be for example be an alkali metal phosphate or alkali metal carbonate. The person skilled in the art will select a suitable combination of phosphates from ortho, gyro and triphosphates. In particular alkali metal triphosphates with a Phase 1 content of greater than 40% are preferable for applications requiring rapid dissolution, whereas for applications requiring slow release a Phase 2 content of greater than 40% is desirable. Similarly the degree of hydration of the salts will be chosen, salts with less than 5% water of hydration are preferred. Other suitable builders are zeolites, citric acid, nitrilo tri-acetic acid, Alkali metal carbonates or sodium citrate. Zeolites X, Y and MAP are all considered suitable.

Polymeric components A number of polymeric components will typically be considered for use as part of compositions within the scope of the invention.

A variety of polymers may be added to perform variety of functions. For example as thickeners and anti scaling agents, anti-redeposition agents, colourants, conductive layers, reflective layers, oxygen permeability barriers, moisture permeability barriers, water softeners, heavy metal sequestrants, antioxidants.

Suitable polymers include, Addition polymers - e.g. Poly Vinyl ; ethers, esters, amides,

` carboxylates, maleates, methacrylates, acrylates, alcohols, acetates, sulphonated polymers and amphoteric polymers and copolymers thereof. In particular block copolymers, homo polymer and copolymer prepared using vinyl carboxylates in combination with monomer selected from the group consisting of (meth)acrylonitrile, 2-trimethylsiloxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-trimethyl-siloxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, sorbyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, glycidyl (meth)acrylate, hexyl (meth)acrylate, hexyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylonitrile, lauryl (meth)acrylate, methyl (meth)acrylate, octyl (meth)acrylate, p-tolyl (meth)acrylate, phenyl (meth)acrylate, propyl (meth)acrylate, sorbyl (meth)acrylate, and stearyl (meth)acrylate, may be used. Homo and block polymers of the above monomers are particularly suitable for use in the inks of the invention. Other suitable polymers include condensation polymers - eg Poly ; esters, and urethanes, gelatin, Carrageen, Gum Arabic (eg grade NF FCC ex Sarcom Inc), Agar (eg Agar-Agar NF FCC Gel 10 ex Sarcom Inc), Guar Gum (eg Powder HV-101 NF FCC ex Sarcom Inc), Locust Bean Gum (eg SG-14 FCC ex Sarcom Inc), Ghatti Gum (eg #1 FCC ex Sarcom Inc), Karaya Gum (eg #1 FCC ex Sarcom Inc), Karaya Gum (eg #1 FCC ex Sarcom Inc), Xanthan Gums (eg XAN-90 NF FCC ex Sarcom Inc.) and alginates.

Particularly preferred polymers are the Chitins, Chitosan and derivatives for their synergistic potentiation of antibacterial efficacy in combination with the selected organic bactericides of table 1.

Preferred molecular weights are from 5,000 to 100,000. More preferably from 10,000 to 30,000. Suitable polymeric materials known in the art are Hydrogenated caster oils (eg Croduret 50 ex Croda), acrylic acid polymers (eg ex National Starch) Acrylate maleate polymers (eg Sokolan CP-5 and CP-10 ex BASF) and poly ethylene glycols (eg ex Hoechst), poly vinyl pyrrolidone (eg K50 ex ISP), Carbopol (ex 3V). Suitable levels of polymer inclusion are between 0.1 to 10%0 more preferably between 0.2 and 2% most preferably between 0.3 and 1.2%.

A variety of substantially water insoluble polymers may be added to perform a variety of functions for example soil release agents and tablet excipients. Eg polyoxyethylene terephthalate, polyethylene terephthalate and cellulose and its hydroxy alkyl and carboxy alkyl derivatives.

Such materials when incorporated in liquid compositions within the scope of the invention are preferably used with a particle size of from 0.1 to 50um, more preferably from 1 to 1 Opm. When used in solid detergents compositions they are preferably used with a size from 200 to 3000pm. More preferably from 500 to 2000gm, most preferably from 800 to 1200p,m.

Bleaches A bleaching composition may also be included. The preferred bleaching system for use in the invention comprises a hydrogen peroxide precursor compound and the bleach activator as known in the art which is capable of reacting with the hydrogen peroxide to generate a peracid.

The hydrogen peroxide precursor compound may, for example, be an inorganic persalt e.g. a perborate (in the monohydrate and/or tetra hydrate form), a percarbonate or a persulphate. The alkali metal salts of these compounds are preferred, particularly sodium and potassium salts. Alternatively in the case where the detergent formulation is in solid form, the bleaching agent may be a urea-hydrogen peroxide complex. In the case of a liquid formulation the hydrogen peroxide precursor compound may be hydrogen peroxide per se. Pre-formed per acids known in the art are also considered suitable.

Specific examples of pre-formed per acids bleaches which may be used in the detergent formulations of the invention include phthalimido peroxihexanoic acid eg Eureco (TM) ex Ausimont) and diphthaloyl peroxide.

Specific examples of bleach activators which may be used in the detergent formulations of the invention include tetra alkyl alkylene diamines, particularly tetra acetyl ethylene diamine, glycerol tri alkylates, particularly glycerol triacetate, hexa acetyl sorbitol, hexa acetyl mannitol, penta acetyl glucose and octa acetyl sucrose. Particularly preferred are hexa acetyl sorbitol and hexa acetyl mannitol which may be used in admixture, e.g. as disclosed in EP-A-0 525 239. Further examples are compounds having nitrogen atoms in the basic carbohydrate skeleton, e.g. the peracetylated forms of N-methyl gluxconamide, N-methyl glucamine and glucopyronosyl amine.

It is considered particularly preferable to combine such bleach activators and such pre-formed

per acids with one another to promote antibacterial nd bleachable stain and soils cleaning. Particularly preferred combinations are of per acetic acid precursors with precursors of higher alkyl peracids such as fall in the range propyl to behenate. Particularly preferred are the branched alkyl analogues of such materials.

Such activators may be preferentially provided as a separate encapsulated component, by for example coating with a film forming polymer. Suitable film forming polymers include acrylates, methacrylates, celluloses, starches and their derivatives. Alternatively in solid products separate granules may be provided so as to enhance physical seperation of the bleach source from the undissolved activator during storage.

Chlorine bleaches may also be employed either as a hypochlorite, for example, an alkali metal hypochlorite or as a precursor compound such as Trichloro iso cyanuric acid, sodium dichloro isocyanurate and its di hydrate (eg Oxidan (TM) DCN/WSG ex Sigma). Such systems may be used in conjunction with a suitable catalyst for example as described in EP 937 772 (Procter). Effervescent systems An effervescent system may be employed. Suitable agents include a mixture of an acid and an alkali metal carbonate or bicarbonate, for example citric acid and sodium carbonate. Sodium percarbonate peroxohydrate (eg ex Eka chemicals) is also considered.

Clays A clay may be used in the composition. The clay which is used in the formulation of the invention may be any one of the fabric softening clays having fabric softening properties used in laundry detergent formulations. Such clays are generally of the "lamellar type" and are such that the layers "separate" to become deposited on the garments being washed. The clay may for example be a Smectite such as a Laponite, Bentonite, Montmorrillonite, Hectorite or Saponite. For example, the clay may be a Sodium Montmorrillonite, a Sodium Hectorite, a Sodium Saponite, a Calcium Montmorrillonite or a Lithium Hectorite.

Softener components The term "fabric softening agent" as used herein includes cationic and nonionic fabric softeners used alone and also in combination with each other. A preferred fabric softening agent of the present invention is a mixture of cationic and nonionic fabric softeners. Examples of fabric softening agents that are especially suitable for use in the invention include the compositions described in US 4,103,047, US 4,237,155, US 3,686,025, 3,849,435 and U.S. 4,073,996. Said patents are hereby incorporated herein by reference. Another preferred type of fabric softener is described in detail in U.S. Pat. No. 4,661,269 (Procter), said patent being incorporated herein by reference. Examples of nonionic fabric softeners are the sorbitan esters, C12 - C26 fatty alcohols, and fatty amines described herein. More biodegradable fabric softener compounds can be desirable. Biodegradability can be increased, e.g., by incorporating easily destroyed linkages into hydrophobic groups. Such' linkages include ester linkages, amide linkages, and linkages containing unsaturation and/or hydroxy groups. Examples of such fabric softeners can be found in US patents 3,408,361, 4,709,045, 4,233,451, 4,127,489, 3,689,424, 4,128,485, 4,161,604, 4,189,593, 4,339,391, said patents being incorporated herein by reference.

Enzymes An enzyme may be included in the composition. The enzyme may, for example, be a protease, amylase, lipase, an endo and exo cellulases, cholesterol oxidases (particularly as described in WO 99/45106 (Meiji Seika)) or mixtures thereof such as commonly used in detergent formulations. Examples of suitable enzymes are available under the names Opticlean (TM), Savinase (TM), Esperase (TM); Termamyl (TM), Maxamayl (TM), Lipomax (TM), Lipolase (TM); Celluzyme (TM) and Carezyme (TM). The amount of enzyme incorporated in the formulation will depend on activity but will typically be 0.1 to 3%. This level is particularly suitable for Savinase 6.0T, Termamyl 60T, Celluzyme 0.7T and Lipomax.

It is a preferred that the bactericides listed be combined with one or more enzymatic components. The person skilled in the art will readily identify those materials which do not significantly

inhibit enzymatic activity and thereby identify those were synergistic bactericidal effects are obtained.

It will be appreciated that the formulation may incorporate additional components as conventionally included in a hard surface cleaner, laundry detergent, fabric refresher, fabric conditioner or similar product.

For a laundry detergent formulation it will be appreciated that the formulation may incorporate additional components as conventionally included. One example of such an additional component is a soap or fatty acid which may be used in an amount of up to 5% by weight as an antifoam or processing aid. Particularly preferred are those with C8 to C22 alkyl chains, more preferably C12 to C12 alkyl and with an iodine value less than 5 more preferably less than 1. Mono, di and trifunctional acids are not without the scope of the invention. Particularly suitable are the Prifac (TM) and Pristerine (TM) materials supplied by Uniquema.

Further examples include anti-foam agents, sequestrants (e.g. of the phosphonate type), whiteness maintenance agents (e.g. CMC, polyoxyethylene terephthalate, polyethylene terephthalate), colorants (e.g. dyestuffs), perfume, flow control agents (e.g. a sulphate) flow enhancer (e.g. a zeolite), pH regulators (e.g. a carbonate or bicarbonate), anticorrosion agents, dye transfer inhibitors (e.g. PVP) and optical brighteners (e.g. Tinopal CBS-X and Tinopal DMS-X). These components may, for example, each be present in amounts up to 1 % by weight of the formulation.

Cyclodextrins and cyclodextrinoids, optionally as alcohol, amide, ether, ester, hydrophobised, conjugated, granulated, encapsulated and solubilised, derivitised and embodied as such are all envisaged as being potentially incorporated ways of changing their use provided that they retain some ability to complex smaller molecules. Uncomplexed cyclodextrine are particularly desirable in the fpormulations of detergent tablets for textile washing.

Cyclodextrin incorporation of between 0 and 5%, more preferably between 0.05 and 2%, most preferably between 0.075 and 1.25% is within the scope of the invention.

Bactericide A bactericide may be optionally included in the detergent product or the external carton packaging. Compositions containing bactericide will contain from 5 to 0.0001% bactericide, virucide or anti-microbial agent, preferably from 2 to 0.001 %, more preferably from 1 to 0.005% most preferably from 0.1 to 0.01%. Biocides as listed in annex 1 of the Biocidal Products Directive of the EC. are considered particularly suitable. Such materials may be used in combination, when used in combination such bactericidal, virucidal or anti-microbial agents will each be present at a level of from 5 to 0.00003% bactericide, virucide or anti-microbial agent, preferably from 3 to 0.000l %, more preferably from 1 to 0.0001 % most preferably from 0.1 to 0.001%.

Most preferred are the bactericidal agents in table 1 which are single organic molecules with a molecular weight above 250: Not wishing to be bound by theorey such molecules possess lower potential for human toxicity by virtue of their higher molecular weigh and absence of inorganic materials.

Disintegrants A disintegrant may also be included, for example to aid tablet dispersability. Most preferably any disintegrant is a cellulose based material. Such cellulose based material may for example comprise both crystalline and amorphous cellulose. Examples of suitable materials are disclosed, for example, in WO-A-9855575 (Henkel), WO-A-9840462 (Herzog). The cellulose may be a cross-linked modified cellulose e.g. AC-DI-SOL and/or may comprise micro crystalline cellulose fibres (e.g. HANFLOC). The cellulose based material may be a cellulose derivative which may be cross-linked, e.g. a cross-linked carboxymethyl cellulose.

The disintegrant may be a cellulose derivative, for example a sodium carboxymethyl cellulose. Examples include COURLOSE and NYMCEL. A particularly suitable disintegrant for use in

the invention is available under the trade mark NILYN. (ex FMC), grade LX16 which is an internally cross-linked carboxymethyl cellulose.

Further examples of disintegrants which may be used include various starches such as potato, rice, corn ore maize starch. The disintegrant may be a starch derivative, e.g. carboxymethyl starch such as available under the trade mark PRIMOGEL or a sodium starch glycolate such as available under the trade mark EXPLOTAB.

It is also possible for the disintegrating agent to be a clay. Such clays are generally of the "lamellar type" and may for example be a Smectite such as a Laponite, Bentonite, Montmorrillonite, Hectorite or Saponite. For example, the clay may be a Sodium Montmorrillonite, a Sodium Hectorite, a Sodium Saponite, a Calcium Montmorrillonite or a Lithium Hectorite.

Furthermore, it is possible for the disintegrating agent to be a synthetic polymer, for example a cross-linked polyvinyl pyrrolidone, POLYPLASDONE XL or KOLLIDON XL. Additional optional components The detergent used in the invention may also contain an optical brighteners or fluorescer. For example Tinopal CBS-X (disodium 2,2'-bis-(phenyl-styryl)sisulphonate and Tinopal DMS-X (4,4' bis - (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate) and the various possible alkali metal salts thereof particularly the potassium salts.

EXAMPLES The invention will be further described with reference to the following non-limiting examples.

Encapsulates Perfume Composition 1 Citronellol (racemic mixture) in 50% ethanol. (ex Aldrich chemical co.) 2 Alpha pinene, 98% in 50% ethanol. (ex Aldrich chemical co.) Powder Signature 2 commercial detergent perfume Ex Dragoco fragrances, UK - `Subtle' impact 4 `White Line' commercial detergent perfume ex Pheonix fragrances, Northants UK. - `Brash' impact % Coating by weight 10%, liquid 90%. Composition 1 (Automatic dish washing composition) Component % by weight Sodium Tripolyphosphate To 100% Sodium Disilicate Heavy Granular 25.0 Granular Sodium Carbonate 8.40 Sodium Perborate monohydrate 12.5 Tetra Acetyl Ethylene Diamine 3.00 Dequest 2016D 0.40 Benzotriazole 0.20 Polyethylene Glycol 0.20 Synperonic LF/RA 260 ex ICI I 3.00

The composition was mixed to form a homogeneous powder using a low shear mixing process (Lodige ploughshare horizontal mixer) for 5 minutes. The mixture was then compressed in to tablets of 36mm long by 26mm wide and weighing 20grammes at the pressure indicated.

Tablets of the above composition where prepared. To each tablet (or powder reference with mixing) a measured drop (0.11m1, i.e., 0.5wt% of the tablet/powder weight) was added.

The tablets where then left for 45 minutes to equilibrate.

Another set of tablets where made using the pre-perfumed powder and also left for 15 minutes after tableting. The smell testing on the powder was carried out on the steepest pyramidal pile of unconstrained powder, on a flat surface, that could be formed by normal pouring out the powder from a vessel.

A panel of 20 testers was then asked to smell the tablets/powders and asked to rank the intensity of the smell. The test was split in to 5 sub-tests (i.e. per perfume) at different times to stop the panellists becoming `saturated' with the smelling process and loosing discrimination.

Tablet perfume intensity ranked per perfume variant (i.e. per row).

(1 = strongest perceived smell) Perfume Uncompressed Pressure in kPa to form the Pressure in kPa to form the Powder tablet tablet (comparative) After perfume addition Before perfume addition Density (comparative) 0.96 g/cc 670kPa 6700 kPa 670kPa 6700 kPa None 1 1 1 1 1 (reference) 1 2 3 3 1 1 2 1 2 2 1 1 3 3 5 4 2 1 4 3 4 3 2 1 Repetition of rank score equals equivalence at the 95% confidence interval.

This demonstrates the increased perfume impact achieved by direct application of fragrance to a finished tablet. Surprisingly the tablet formed at the higher pressure gives the better result (greater efficacy). The more efficient utilisation of perfume to obtain the same smell intensity is not proved by these results. The following test was therefore performed.

Pressure in kPa to form the tablet 670kPa 1340 kPa 3350 kPa 5025 kPa 6700 kPa Hardness 12 20 45 60 90 values in Newtons Tablet 0.86 1.04 1.31 1.52 1.57 density in g/cc Calculated 47% 35%0 18% 5% 1.8% void volume* Perfume 3 4 4 3 1 2 ranked intensity (1) Perfume 3 4 4 2 1 3 ranked intensity (2) Perfume 3 3 2 1 1 2 ranked intensity (3) * Based on theoretical non-porous tablet density of 1.6g/cc. Void fraction = actual density/theoretical maximum density of the same mass without porosity. Void volume = Void fraction x 100.

(1) Method as described above for post tableting perfume incorporation. (2) On same samples but one day later.

(3) Perfume applied by a 75pm average droplet size spray.

Repetition of rank score equals equivalence at the 95% confidence interval. These results show that there is an optimum tablet porosity.

It is hypothesised that the less porous tablet fails to incorporate the perfume in to its structure and excessive evaporation results. A comparative of a 5025kPa sample versus a drop of the perfume on a non porous surface ranked the perfume on the tablet strongest after 1 day.

Tablets where prepared as above using perfume 3 and 50251Pa pressure and compared to the untableted powder at various perfume levels. The samples being ranked for intensity.

Perfume added % by weight Powder Tablet made at 5025kPa and post perfumed. 0.6% 5 4 0.8% 4 3 1.0% 3 2 1.25% 1 1 3.0% Saturated smell no differentiation possible. Repetition of rank score equals equivalence at the 95% confidence interval.

These results show the higher perceived weight efficacy in perfuming a pre-formed tablet.

Claims

Claims 1) A method constituting a detergent product by adding a metered amount of a liquid to a preformed porous unit-dose detergent mass.
2) A method of perfuming as described in claim 1 in which the liquid is a perfume.
3) A method as described in claim 2 in which the pre-formed porous mass is a detergent tablet.
4) A method as described in claim 1 in which the metered amount of liquid is applied as a spray.
5) A method as described in claim 1 in which the porous mass has a void volume between 2 and 60%.
6) A method as described in claims 2 and 3 and where liquid is added at between 0.1 and 5% by weight of the detergent mass, which has a void volume of greater than 1%.
7) A method as described in any previous claim in which the detergent mass has a void volume of between 5 and 20% and the liquid is applied as a spray with an average particle size of between 10 and 500pm.
8) A method of constituting a detergent product by adding, using a spray of average particle size between 50 and 200pm a metered amount of a perfumery liquid at between 0.5 and 1 % of final product weight to a pre-formed unit-dose detergent mass of void volume between 5 and 20%.