Patent Description:
A toilet rim block is a block-shaped substance used in flush toilets which slowly dissolves in water. They often come in a small holder that is attached over the rim of a toilet and hangs down into the bowl, so as the toilet gets flushed, the water passes through the holder coming into contact with the block.

Rim blocks work in the same way as an air freshener, emitting constantly the same fragrance. However, the human nose gets used to one scent within like <NUM>, so that the fragrance cannot be valued appropriately anymore. Devices, which change their fragrance impression over the time, are perceived new and fresh. In the toilet, such a scent switch can be triggered by flushing the toilet.

Over the years a lot of effort has been put in devices, which enable a controlled scent release, like for instance in cinematic technique as for example evidenced in <CIT>(WITTEK).

Especially bathrooms are a place, where the scent switch is strongly desired. A rather complicated option is to obtain this scent switch by ventilation of gas from the toilet through a malodor suppressor and then to ventilate the gas back into the room as illustrated by <CIT>(SMITH).

This system has evolved into a much handier version, consisting just of a ventilator, which deodorizes the air passing through <CIT>(HAN).

<CIT> (SCOTT) suggests a scent switch which could be implemented in such a device, by a continuous, automatic exchange of the dispensing device.

Another scent switching device releases its fragrance at the same time, but with different rates is disclosed in <CIT> (WITHERS).

<CIT> (DRÖGE) refers to rim blocks, which are capable of a flush-triggered scent switch, which require sophisticated rim block cages, blocking parts of the formulation from water or air to cease its scent mechanically.

Some tools have been proposed, which even separate two dispensing devices. Therefore, one part delivers constantly its fragrance, while the other only delivers its fragrance, when triggered. Such a triggered scent release is obtained by a solid, water-soluble, fragranced formulation, which is located behind a permeable membrane. When water enters the device, it is released slowly through the membrane, transporting some fragrance as disclosed in <CIT>(BELDER).

Further relevant disclosures are <CIT>, <CIT>, <CIT> and <CIT>.

Therefore, it has been the object of the present preparing a fragranced solid rim block which provides an intensive but only temporary scent change or boost when flushed.

A first object of the present invention refers to a rim block with scent change or boost, comprising or consisting of.

Surprisingly it has been observed that adding perfume oil encapsulated in a maltodextrin matrix to a rim block base already containing another perfume oil, with a scent different from the scent of the encapsulated perfume oil, leads to an intensive, but temporary scent change when flushing the rim block. In case both perfume compounds have the same or a similar flavor, the scent sensation gets boosted.

The rim blocks according to the present invention contain a solid rim block base comprising.

In a preferred embodiment the surfactant (component (a1) of the rim block base is an anionic surfactant (including zwitterionic surfactants), a non-ionic surfactant or a mixture of both.

Alkohol alkoxylates. The added nonionic surfactants are preferably alkoxylated and/or propoxylated, particularly primary alcohols having preferably <NUM> to <NUM> carbon atoms and an average of <NUM> to <NUM> mol ethylene oxide (EO) and/or <NUM> to <NUM> mol propylene oxide (PO) per mol alcohol. C<NUM>-C<NUM>-Alcohol alkoxylates, advantageously ethoxylated and/or propoxylated C<NUM>-C<NUM>-alcohol alkoxylates, particularly C<NUM>-C<NUM> alcohol alkoxylates, with an ethoxylation degree between <NUM> and <NUM>, preferably between <NUM> and <NUM>, and/or a propoxylation degree between <NUM> and <NUM>, preferably between <NUM> and <NUM>, are particularly preferred. The cited degrees of ethoxylation and propoxylation constitute statistical average values that can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates and propoxylates have a narrowed homolog distribution (narrow range ethoxylates/ propoxylates, NRE/NRP). In addition to these nonionic surfactants, fatty alcohols with more than <NUM> EO can also be used. Examples of these are (tallow) fatty alcohols with <NUM> EO, <NUM> EO, <NUM> EO, <NUM> EO, <NUM> EO or <NUM> EO.

Alkylglycosides (APG®). Furthermore, as additional nonionic surfactants, alkyl glycosides that satisfy the general Formula RO(G)x, can be added, e.g., as compounds, particularly with anionic surfactants, in which R means a primary linear or methyl-branched, particularly <NUM>-methyl-branched, aliphatic group containing <NUM> to <NUM>, preferably <NUM> to <NUM> carbon atoms and G stands for a glycose unit containing <NUM> or <NUM> carbon atoms, preferably for glucose. The degree of oligomerization x, which defines the distribution of monoglycosides and oligoglycosides, is any number between <NUM> and <NUM>, preferably between <NUM> and <NUM>.

Fatty acid ester alkoxylates. Another class of preferred nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular, together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters preferably containing <NUM> to <NUM> carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters which are described, for example, in Japanese Patent Application <CIT> or which are preferably produced by the process described in International Patent Application <CIT>. Methyl esters of C<NUM>-C<NUM> fatty acids containing an average of <NUM> to <NUM> EO, particularly containing an average of <NUM> to <NUM> EO, are particularly preferred.

Amine oxides. Nonionic surfactants of the amine oxide type, for example, N-coco alkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The quantity in which these nonionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, particularly no more than half that quantity.

Gemini surfactants. The so-called gemini surfactants can be considered as further surfactants. Generally speaking, such compounds are understood to mean compounds that have two hydrophilic groups and two hydrophobic groups per molecule. As a rule, these groups are separated from one another by a "spacer". The spacer is usually a hydrocarbon chain that is intended to be long enough such that the hydrophilic groups are a sufficient distance apart to be able to act independently of one another. These types of surfactants are generally characterized by an unusually low critical micelle concentration and the ability to strongly reduce the surface tension of water. In exceptional cases, however, not only dimeric but also trimeric surfactants are meant by the term gemini surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German Patent Application <CIT> or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates according to International Patent Application <CIT>. Blocked end group dimeric and trimeric mixed ethers according to German Patent Application <CIT> are especially characterized by their bifunctionality and multifunctionality. Gemini polyhydroxyfatty acid amides or polyhydroxyfatty acid amides, such as those described in International Patent Applications <CIT>, <CIT> and <CIT> can also be used.

Fatty acid amines. Another class of nonionic surfactants encompass condensation products of fatty acids having <NUM> to <NUM> and preferably <NUM> to <NUM> carbon atoms and <NUM> or <NUM>, <NUM> or <NUM> double bonds with amines or alkanolamines, such as methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, methylethylamine, aminoethanol, aminopropanol or their mixtures.

In one embodiment the preferred anionic surfactants are selected from the group consisting of oxo alkyl sulfates (= fatty alcohol sulfates), alkyl ether sulfates (= fatty alcohol ether sulfates), alkyl benzene sulfonates, soaps and mixtures thereof.

In another embodiment the preferred non-ionic surfactants are selected from the group consisting of alkyl polyglycol ethers, alkyl polyglycosides, carboxylic acid amides (=fatty acid amides) and mixtures thereof.

The solid rim block base also contains solvents (component a2) which are selected from the group consisting of water, polyols, mineral oils or mixtures thereof. Preferably the solvent is ethylene glycol, diethylene glycol or glycerol.

The solid rim block base may contain builders including co-builders (component a3).

Fine crystalline, synthetic zeolites containing bound water can be used as builders, for example, preferably zeolite A and/or P. Zeolite MAP. (commercial product of the Crosfield company), is particularly preferred as the zeolite P. However, zeolite X and mixtures of A, X, Y and/or P are also suitable. A co-crystallized sodium/potassium aluminum silicate from Zeolite A and Zeolite X, which is available as Vegobond® RX. (commercial product from Condea Augusta S. ), is also of particular interest. Preferably, the zeolite can be used as a spray-dried powder. For the case where the zeolite is added as a suspension, this can comprise small amounts of nonionic surfactants as stabilizers, for example, <NUM> to <NUM> wt. %, based on the zeolite, of ethoxylated C<NUM>-C<NUM> fatty alcohols with <NUM> to <NUM> ethylene oxide groups, C<NUM>-C<NUM> fatty alcohols with <NUM> to <NUM> ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than <NUM> (test method: volumetric distribution Coulter counter) and preferably comprise <NUM> to <NUM> wt. %, particularly <NUM> to <NUM> wt. % of bound water. Apart from this, phosphates can also be used as builders.

Layered silicates. Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates. These types of crystalline layered silicates are described, for example, in European Patent Application <CIT>. Preferred crystalline layered silicates are those obtained for example, from the process described in International Patent Application <CIT>.

Amorphous silicates. Preferred builders also include amorphous sodium silicates with a modulus (Na<NUM>O:SiO<NUM> ratio) of <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM> and more preferably <NUM>:<NUM> to <NUM>:<NUM>, which dissolve with a delay and exhibit multiple wash cycle properties. The delay in dissolution compared with conventional amorphous sodium silicates can have been obtained in various ways, for example, by surface treatment, compounding, compressing/compacting or by over-drying. In the context of this invention, the term "amorphous" also means "X-ray amorphous". In other words, the silicates do not produce any of the sharp X-ray reflexions typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce indistinct or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted to mean that the products have microcrystalline regions between <NUM> and a few hundred nm in size, values of up to at most <NUM> and especially up to at most <NUM> being preferred. This type of X-ray amorphous silicates, which similarly possess a delayed dissolution in comparison with the customary water glasses, are described, for example, in German Patent Application <CIT>. Compacted/densified amorphous silicates, compounded amorphous silicates and over dried X-ray-amorphous silicates are particularly preferred.

Phosphates. Also the generally known phosphates can also be added as builders, in so far that their use should not be avoided on ecological grounds. The sodium salts of the orthophosphates, the pyrophosphates and especially the tripolyphosphates are particularly suitable. Their content is generally not more than <NUM> wt. %, preferably not more than <NUM> wt. %, each based on the finished composition. In some cases it has been shown that particularly tripolyphosphates, already in low amounts up to maximum <NUM> wt. %, based on the finished composition, in combination with other builders, lead to a synergistic improvement of the secondary washing power. Preferred amounts of phosphates are under <NUM> wt. %, particularly <NUM> wt.

Polycarboxylic acids. Useful organic cobuilders are, for example, the polycarboxylic acids usable in the form of their sodium salts of polycarboxylic acids, wherein polycarboxylic acids are understood to be carboxylic acids that carry more than one acid function. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and its derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

Organic acids. Acids per se can also be used. Besides their building effect, the acids also typically have the property of an acidifying component and, hence also serve to establish a relatively low and mild pH in detergents or cleansing compositions. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are particularly mentioned in this regard. Further suitable acidifiers are the known pH regulators such as sodium hydrogen carbonate and sodium hydrogen sulfate.

Particularly suitable polymeric cobuilders are polyacrylates, which preferably have a molecular weight of <NUM>,<NUM> to <NUM>,<NUM>/mol. By virtue of their superior solubility, preferred representatives of this group are again the short-chain polyacrylates, which have molecular weights of <NUM>,<NUM> to <NUM>,<NUM>/mol and, more particularly, <NUM>,<NUM> to <NUM>,<NUM>/mol. Suitable polymers can also include substances that consist partially or totally of vinyl alcohol units or its derivatives.

Further suitable copolymeric polycarboxylates are particularly those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, which comprise <NUM> to <NUM> wt. % acrylic acid and <NUM> to <NUM> wt. % maleic acid, have proven to be particularly suitable. Their relative molecular weight, based on free acids, generally ranges from <NUM>,<NUM> to <NUM>,<NUM>/mol, preferably <NUM>,<NUM> to <NUM>,<NUM>/mol and especially <NUM>,<NUM> to <NUM>,<NUM>/mol. The (co)polymeric polycarboxylates can be added either as an aqueous solution or preferably as powder. In order to improve the water solubility, the polymers can also comprise allylsulfonic acids as monomers, such as, for example, allyloxybenzene sulfonic acid and methallyl sulfonic acid as in the <CIT>.

Biodegradable polymers comprising more than two different monomer units are particularly preferred, examples being those comprising, as monomers, salts of acrylic acid and of maleic acid, and also vinyl alcohol or vinyl alcohol derivatives, as in <CIT>, or those comprising, as monomers, salts of acrylic acid and of <NUM>-alkylallyl sulfonic acid, and also sugar derivatives. Further preferred copolymers are those that are described in <CIT> and <CIT> and preferably include acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.

Similarly, other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Those polyaspartic acids or their salts and derivatives disclosed in German Patent Application <CIT> as having a bleach-stabilizing action in addition to cobuilder properties are particularly preferred.

Further suitable builders are polyacetals that can be obtained by treating dialdehydes with polyol carboxylic acids that possess <NUM> to <NUM> carbon atoms and at least <NUM> hydroxyl groups, as described in European Patent Application <CIT>. Preferred polyacetals are obtained from dialdehydes like glyoxal, glutaraldehyde, terephthalaldehyde as well as their mixtures and from polycarboxylic acids like gluconic acid and/or glucoheptonic acid.

Carbohydrates. Further suitable organic cobuilders are dextrins, for example, oligomers or polymers of carbohydrates that can be obtained by the partial hydrolysis of starches. The hydrolysis can be carried out using typical processes, for example, acidic or enzymatic catalyzed processes. The hydrolysis products preferably have average molecular weights in the range of <NUM> to <NUM>,<NUM>/mol. A polysaccharide with a dextrose equivalent (DE) of <NUM> to <NUM> and, more particularly, <NUM> to <NUM> is preferred, the DE being an accepted measure of the reducing effect of a polysaccharide in comparison with dextrose, which has a DE of <NUM>. Both maltodextrins with a DE between <NUM> and <NUM> and dry glucose syrups with a DE between <NUM> and <NUM> and also so-called yellow dextrins and white dextrins with relatively high molecular weights of <NUM>,<NUM> to <NUM>,<NUM>/mol may be used. A preferred dextrin is described in <CIT>.

The oxidized derivatives of such dextrins concern their reaction products with oxidizing compositions that are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their manufacture are known for example, from European Patent Applications <CIT>. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate are also further suitable cobuilders. Here, ethylene diamine-N,N'-disuccinate (EDDS), the synthesis of which is described for example, in <CIT>, is preferably used in the form of its sodium or magnesium salts. In this context, glycerine disuccinates and glycerine trisuccinates are also particularly preferred, such as those described in <CIT>. Suitable addition quantities in zeolite-containing and/or silicate-containing formulations range from <NUM> to <NUM>% by weight.

Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids and salts thereof which optionally may also be present in lactone form and which contain at least <NUM> carbon atoms, at least one hydroxyl group and at most two acid groups. Such cobuilders are described, for example, in International Patent Application <CIT>.

The solid rim block base may also contain salts (component a4) which are selected from the group consisting of alkali or alkaline earth sulfates carbonates and chlorides. The preferred salts are sodium sulfate or potassium sulfate.

The solid rim block base may also contain further auxiliary agents (component a5).

Bleaching agents. The rim block base may contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about <NUM>% to about <NUM>%, more typically from about <NUM>% to about <NUM>%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about <NUM>% to about <NUM>%, more typically from about <NUM>% to about <NUM>% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetrahydrate) can be used herein.

Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, <NUM>-nonylamino-<NUM>-oxoperoxybutyric acid and diperoxydodecanedioic acid.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONEO®, manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about <NUM> micrometers to about <NUM>,<NUM> micrometers, not more than about <NUM>% by weight of said particles being smaller than about <NUM> micrometers and not more than about <NUM>% by weight of said particles being larger than about <NUM>,<NUM> micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources. Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used.

Preferred amido-derived bleach activators include (<NUM>-octanamido-caproyl)oxybenzene-sulfonate, (<NUM>-nonanamidocaproyl)oxybenzenesulfonate, (<NUM>-decanamido-caproyl)-oxybenzenesulfonate, and mixtures thereof.

Another class of bleach activators comprises the benzoxazin-type activators disclosed in <CIT>.

Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, <NUM>,<NUM>,<NUM>-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, <NUM>,<NUM>,<NUM>-trimethylhexanoyl valerolactam and mixtures thereof, optionally adsorbed into solid carriers, e. g acyl caprolactams, preferably benzoyl caprolactam, adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. If used, detergent compositions will typically contain from about <NUM>% to about <NUM>%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such manganese-based catalysts are well known in the art and include MnIV<NUM> (u-O)<NUM> (<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM> (PF<NUM>)<NUM>, MnIII<NUM> (u-O)<NUM> (u-OAc)<NUM> (<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM>(ClO<NUM>)<NUM>, MnIV<NUM> (u-O)<NUM> (<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM> (ClO<NUM>)<NUM>, MnIIIMnIV<NUM> (u-O)<NUM> (u-OAc)<NUM> (<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM> (ClO<NUM>);, MnIV (<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)-(OCH<NUM>)<NUM> (PF<NUM>), and mixtures thereof.

As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about <NUM> ppm to about <NUM> ppm, more preferably from about <NUM> ppm to about <NUM> ppm, of the catalyst species in the laundry liquor.

Gelling agents. Any polymeric gelling agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

The polymeric gelling agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least <NUM>, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from <NUM> to <NUM>, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from <NUM> to about <NUM> oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about <NUM>% oxyethylene units and more preferably, especially for such components having about <NUM> to <NUM> oxypropylene units, at least about <NUM>% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C<NUM> oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C<NUM> oxyalkylene terephthalate units is about <NUM>:<NUM> or lower, (ii) C<NUM> - C<NUM> alkylene or oxy C<NUM> - C<NUM> alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least <NUM>, or (iv) C<NUM> - C<NUM> alkyl ether or C<NUM> hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C<NUM> - C<NUM> alkyl ether or C<NUM> hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C<NUM> - C<NUM> alkyl ether and/or C<NUM> hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of from about <NUM>, although higher levels can be used, preferably from <NUM> to about <NUM>, more preferably from <NUM> to about <NUM>. Suitable oxy C<NUM> - C<NUM> alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents.

Polymeric gelling agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL® (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C<NUM> - C<NUM> alkyl and C<NUM> hydroxyalkyl cellulose.

Gelling agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C<NUM> - C<NUM> vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones, see <CIT>, incorporated herein in its entirety. Commercially available soil release agents of this kind include the SOKALAN® type of material, e.g., SOKALAN® HP-<NUM>, available from BASF.

One type of preferred gelling agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent preferably is in the range of from about <NUM>,<NUM> to about <NUM>,<NUM>.

Another preferred polymeric gelling agent is a polyester with repeat units of ethylene terephthalate units contains <NUM>-<NUM>% by weight of ethylene terephthalate units together with <NUM>-<NUM>% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight <NUM>-<NUM>,<NUM>. Examples of this polymer include the commercially available material ZELCON® <NUM> (from DuPont) and MILEASE® T (from ICI).

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in <CIT>. Other suitable polymeric soil release agents include the terephthalate polyesters of <CIT>, the anionic end-capped oligomeric esters of <CIT>, the block polyester oligomeric compounds of <CIT>, and anionic, especially sulfoaroyl, end-capped terephthalate esters of <CIT>.

Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-<NUM>,<NUM>-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, <NUM> terephthaloyl units, oxyethyleneoxy and oxy-<NUM>,<NUM>-propyleneoxy units in a ratio of from about <NUM> to about <NUM>, and two end-cap units of sodium <NUM>-(<NUM>-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from about <NUM>% to about <NUM>%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.

If utilized, gelling agents will generally comprise from about <NUM>% to about <NUM>%, by weight, of the detergent compositions herein, typically from about <NUM>% to about <NUM>%, preferably from about <NUM>% to about <NUM>%.

Polymeric dispersing agents. These additives can advantageously be utilized at levels from about <NUM>% to about <NUM>%, by weight, in the detergent compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about <NUM>% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about <NUM>,<NUM> to <NUM>,<NUM>, more preferably from about <NUM>,<NUM> to <NUM>,<NUM> and most preferably from about <NUM>,<NUM> to <NUM>,<NUM>. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example <CIT>.

Acrylic/maleic-based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about <NUM>,<NUM> to <NUM>,<NUM>, more preferably from about <NUM>,<NUM> to <NUM>,<NUM>, most preferably from about <NUM>,<NUM> to <NUM>,<NUM>. The ratio of acrylate to maleate segments in such copolymers will generally range from about <NUM>:<NUM> to about <NUM>:<NUM>, more preferably from about <NUM>:<NUM> to <NUM>:<NUM>. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in <CIT>, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers, for example, a <NUM>/<NUM>/<NUM> terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about <NUM> to about <NUM>,<NUM>, preferably from about <NUM>,<NUM> to about <NUM>,<NUM>, more preferably from about <NUM>,<NUM> to about <NUM>,<NUM>.

Polyaspartate and polyglutamate dispersing agents can also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg. ) of about <NUM>,<NUM>.

Compounds for reducing or suppressing the formation of suds can be incorporated into the detergent compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.

A wide variety of materials can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example,<NPL>). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of <NUM> to about <NUM> carbon atoms, preferably <NUM> to <NUM> carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Sequestrants and chelating agents. The salts of polyphosphonic acid can be considered as sequestrants or as stabilizers, particularly for peroxy compounds and enzymes, which are sensitive towards heavy metal ions. Here, the sodium salts of, for example, <NUM>-hydroxyethane-<NUM>,<NUM>-diphosphonate, diethylenetriamine pentamethylene phosphonate or ethylenediamine tetramethylene phosphonate are used in amounts of <NUM> to <NUM> wt.

The detergent compositions herein can also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. It is understood that some of the detergent builders described hereinbefore can function as chelating agents and is such detergent builder is present in a sufficient quantity, it can provide both functions.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about <NUM> carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as <NUM>,<NUM>-dihydroxy-<NUM>,<NUM>-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer.

If utilized, these chelating agents will generally comprise from about <NUM>% to about <NUM>% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about <NUM>% to about <NUM>% by weight of such compositions.

Disinfectants. Suitable disinfectants are, in principle, all substances effective against Gram-positive bacteria, such as, for example, <NUM>- hydroxybenzoic acid and its salts and esters, N-(<NUM>-chlorophenyl)-N'-(<NUM>,<NUM>- dichlorophenyl)urea, <NUM>,<NUM>,<NUM>'-trichloro-<NUM>'-hydroxydiphenyl ether (triclosan), <NUM>-chloro-<NUM>,<NUM>-dimethyl-phenol, <NUM>,<NUM>'-methylenebis(<NUM>-bromo-<NUM>-chlorophenol), <NUM>-methyl-<NUM>-(<NUM>-methylethyl)phenol, <NUM>-benzyl-<NUM>-chloro-phenol, <NUM>-(<NUM>-chlorophenoxy)-<NUM>,<NUM>-propanediol, <NUM>-iodo-<NUM>-propynyl butylcarbamate, chlorhexidine, <NUM>,<NUM>,<NUM>'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, oil of cloves, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid N-alkylamides, such as, for example, n-octylsalicylamide or n- decylsalicylamide.

Odour absorbers. Suitable odour absorbers are substances which are able to absorb and largely retain odour-forming compounds. In some cases they may overlap with perfume oils forming group (b) of the rim blocks according to the present invention. They lower the partial pressure of the individual components, thus also reducing their rate of diffusion. It is important that perfumes must remain unimpaired in this process. Odour absorbers are not effective against bacteria. They comprise, for example, as main constituent, a complex zinc salt of ricinoleic acid or specific, largely odour-neutral fragrances which are known to the person skilled in the art as "fixatives", such as, for example, extracts of labdanum or styrax or certain abietic acid derivatives. The odour masking agents are fragrances or perfume oils, which, in addition to their function as odour masking agents, give the deodorants their respective fragrance note. Perfume oils which may be mentioned are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts from flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches, and resins and balsams. Also suitable are animal products, such as, for example, civet and castoreum. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexylpropionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, and the aldehydes include, for example, the linear alkanals having <NUM> to <NUM> carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the ionones and methyl cedryl ketone, the alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linaool, phenylethyl alcohol and terpineol, and the hydrocarbons include mainly the terpenes and balsams. Preference is, however, given to using mixtures of different fragrances which together produce a pleasing fragrance note. Essential oils of relatively low volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamon leaf oil, linden flower oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil and lavandin oil. Preference is given to using bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, _phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, clary sage oil, β- damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur, iso-E-super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat alone or in mixtures.

Colours and pigments. Suitable colours and pigments include cochineal red A (C. <NUM>), patent blue V (C. <NUM>), indigotin (C. <NUM>), chlorophyllin (C. <NUM>), quinoline yellow (C. <NUM>), titanium dioxide (C. <NUM>), indanthrene blue RS (C. <NUM>) and madder lake (C. Luminol may also be present as a luminescent dye. Advantageous coloured pigments are for example titanium dioxide, mica, iron oxides (e.g. Fe<NUM>O<NUM> Fe<NUM>O<NUM>, FeO(OH)) and/or tin oxide. Advantageous dyes are for example carmine, Berlin blue, chromium oxide green, ultramarine blue and/or manganese violet.

In another preferred embodiment the rim block base comprises.

For the sake of good order it should be understood that mixtures as explained above which add up to less or more than <NUM> wt. -% are neither covered by the invention nor by the claims. A skilled person, however, understands how to adjust the components within the suggested ranges to end up with a <NUM> wt. -% composition without any further investigation.

Basically, the choice of specific perfume oil for both component (b) and component (c) is not critical. For scent change it is that the two fragrances show different scents so that an individual is able to recognize a scent shift once the encapsulated fragrance is released after flushing the toilet. For scent boost the two perfume oil should have the same or a similar scent.

The perfume oil from component (b) in the rim block base can be perceived at all times. Its profile has to be pleasant and consist of top, middle and base notes. Preferably, it has a high water-solubility, its intensity ceases when wet. Thereby, the scent switch effect is enhanced at the cost of fragrance intensity after flush.

In component (c), perfume oils, consisting of mainly top notes, exhibit the most intensive effect. Even in low doses, they can be well perceived and their effect wears off after a short time, so that the system can return to its initial state. Perfume oils with low water-solubility are especially preferred, because they are rinsed away with the waste water in smaller extent.

Examples for suitable perfume oils, fragrances or scents - the three terms are used as synonyms - encompass natural and synthetic products. Natural perfumes include the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert. butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing <NUM> to <NUM> carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. Examples of suitable ketones are the ionones, ▪-isomethylionone and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable perfume. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil and lavendin oil. The following are preferably used either individually or in the form of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat.

Particularly, the synthetic fragrances represent aldehydes, ketones, alcohols, ethers, esters, hydrocarbons their mixtures. In the following these types of fragrances are illustrated but not limited by examples:.

Examples for suitable fragrances showing an aldehyde structure encompass melonal, triplal, ligustral, adoxal, anisaldehyde, cymal, ethylvanillin, florhydral, floralozon, helional, heliotropin, hydroxycitronellal, koavon, laurinaldehyde, canthoxal, lyral, lilial, adoxal, anisaldehyde, cumal, methyl-nonyl-acetaldehyde, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, bourgeonal, p-tert. -bucinal, phenylacetaldehyde, undecylenaldehyde, vanillin; <NUM>,<NUM>,<NUM>-trimethyl-<NUM>-undecenal, <NUM>-dodecen-I-al, α-n-Amylzimtaldehyde, <NUM>-methoxy-benz-aldehyde, benzaldehyde, <NUM>-(<NUM>-tert-butylphenyl)-propanal,<NUM>-methyl-<NUM>-(para-methoxy-phe-nylpropanal), <NUM>-methyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>(<NUM>)-cyclohexen-<NUM>-yl)butanal,<NUM>-phenyl-<NUM>-pro-penal, cis-/trans-<NUM>,<NUM>-dimethyl-<NUM>,<NUM>-octadien-I-al, <NUM>,<NUM>-dimethyl-<NUM>-octen-I-al,[(<NUM>,<NUM>-dimethyl-<NUM>-octenyl)-xy]-cetaldehyde, <NUM>-isopropylbenzyaldehyde, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-octahydro-<NUM>,<NUM>-dimethyl-<NUM>-naphthaldehyde, <NUM>,<NUM>-dimethyl-<NUM>-cyclohexen-<NUM>-carboxyaldehyde, <NUM>-methyl-<NUM>-(isopropyl-phenyl)propanal, decyl aldehyde, <NUM>,<NUM>-dimethyl-<NUM>-heptenal; <NUM>-(tricyclo[<NUM>. <NUM> (<NUM>,<NUM>)]-decylidene-<NUM>)-butanal; octahydro-<NUM>,<NUM>-methano-IH-indenecarboxaldehyde; <NUM>-ethoxy-<NUM>-hydroxybenzaldehyde, para-ethyl-alpha,alpha-dimethylhydrozimtaldehyde, α-methyl-<NUM>,<NUM>-(methylenedioxy)-hydrocinnamaldehyde, <NUM>,<NUM>-methylenedioxybenzaldehyde, α-n-hexyl-cinnamaldehyde, m-cymene-<NUM>-carboxaldehyde, α-methylphenylacetaldehyde, <NUM>-hydroxy-<NUM>,<NUM>-dimethyl octanal, undecenal, <NUM>,<NUM>,<NUM>-trimethyl-<NUM>-cyclohexene-l-carboxalde-hyde,<NUM>-(<NUM>)(<NUM>-methyl-<NUM>-pentenyl)-<NUM>-cyclohexen-carboxaldehyde, <NUM>-dodecanal, <NUM>,<NUM>-dimethyl-cyclohexene-<NUM>-carboxaldehyde,<NUM>-(<NUM>-hydroxy-<NUM>-methylpentyl)-<NUM>-cylohexene-I-carboxal-dehyde, <NUM>-methoxy-<NUM>,<NUM>-dimethyloctan-<NUM>-al, <NUM>-methyl undecanal, <NUM>-methyl decanal, <NUM>-nonanal, <NUM>-octanal, <NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>-undecadienal, <NUM>-methyl-<NUM>-(<NUM>-tertbutyl)propanal, <NUM>-(<NUM>-ethylphenyl)-<NUM>,<NUM>-dimethylpropanal, <NUM>-(<NUM>-methoxyphenyl)-<NUM>-methylpropanal, methylno-nylacetaldehyde, <NUM>-phenylpropan-<NUM>-al, <NUM>-phenylprop-<NUM>-en-<NUM>-al, <NUM>-phenyl-<NUM>-pentylprop-<NUM>-en-<NUM>-al, <NUM>-phenyl-<NUM>-hexylprop-<NUM>-enal, <NUM>-(<NUM>-isopropylphenyl)-<NUM>-methylpropan-<NUM>-al, <NUM>-(<NUM>-ethylphenyl)-<NUM>,<NUM>-dimethylpropan-<NUM>-al, <NUM>-(<NUM>-tert-butylphenyl)-<NUM>-methyl-propanal, <NUM>-(<NUM>,<NUM>-Methylendioxy-phenyl)-<NUM>-methylpropan-<NUM>-al,<NUM>-(<NUM>-Ethylphenyl)-<NUM>,<NUM>-dimethylpropanal, <NUM>-(<NUM>-Isopropylphenyl)-butan-<NUM>-al, <NUM>,<NUM>-Dimethylhept-<NUM>-en-<NUM>-al,Dihydrozimtaldehyde, <NUM>-methyl-<NUM>-(<NUM>-methyl-<NUM>-pentenyl)-<NUM>-cyclohexene-<NUM>-carboxaldehyde, <NUM>- or <NUM>-Methoxyhexahydro-<NUM>,<NUM>-methanoindan-<NUM> or <NUM>-carboxyaldehyde, <NUM>,<NUM>-dimethyloctan-<NUM>-al, <NUM>-undecanal, <NUM>-undecen-<NUM>-al, <NUM>-hydroxy-<NUM>-methoxybenzaldehyde, <NUM>-methyl-<NUM>-(<NUM>-methylpentyl)-<NUM>-cyclohexene-carboxyaldehyde, <NUM>-hydroxy-<NUM>,<NUM>-dimethyloctanal; trans-<NUM>-decenal, <NUM>,<NUM>-nonadienal, p-tolylacetaldehyde; <NUM>-methylphenylacetaldehyde, <NUM>-methyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>-cyclohexen-<NUM>-yl)-<NUM>-butenal, o-methoxyzimtaldehyde, <NUM>,<NUM>,<NUM>-trimethyl-<NUM>-cyclohexenecarboxaldehyde, <NUM>,<NUM>-dimethyl-<NUM>-methylene-<NUM>-octenal, phenoxyacetaldehyde; <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-decadienal, peony aldehyde (<NUM>,<NUM>-dimethyl-<NUM>-oxa-<NUM>,<NUM>-undecadien-<NUM>-al), hexahydro-<NUM>,<NUM>-methanoindan-<NUM>-carboxaldehyde, octanal, <NUM>-methyl octanal, alpha-methyl-<NUM>-(I-methylethyl)benzeneacetaldehyde, <NUM>,<NUM>-dimethyl-<NUM>-norpinene-<NUM>-propionaldehyde, p-methyl phenoxy acetaldehyde, <NUM>-methyl-<NUM>-phenyl-<NUM>-propen-<NUM>-al, <NUM>,<NUM>,<NUM>-trimethylhexanal, hexahydro-<NUM>,<NUM>-dimethyl-<NUM>-naphthaldehyde, <NUM>-propyl-bicyclo[<NUM>. <NUM>]-hept-<NUM>-ene-<NUM>-carbaldehyde, <NUM>-decenal, <NUM>-methyl-<NUM>-phenyl-<NUM>-pentanal, methylnonyl acetaldehyde, <NUM>-p-menthene-q-carboxaldehyde, citral or its mixtures, lilial citral, <NUM>-decanal, n-undecanal, n-dodecanal, hlorhydral, <NUM>,<NUM>-dimethyl-<NUM>-cyclohexen-<NUM>-carboxaldehyde <NUM>-methoxybenzaldehyde, <NUM>-methoxy-<NUM>-hydroxy-benzaldehyde, <NUM>-ethoxy-<NUM>-hydroxybenzaldehyde, <NUM>,<NUM>-methylendioxybenzaldehyde, <NUM>,<NUM>-dimethoxybenzaldehyde and their mixtures.

As explained above, said ketones or said aldehydes may show an aliphatic, cycloaliphatic, aromatic, ethylenically unsaturated structure or a mixture of these elements. The components may also include heteroatoms or show a polycyclic structure. Suitable substituents for all these structures are hydroxyl and/or amino groups. Further fragrances are compiled in the following document: <NPL>and<NPL>,<NPL>".

Examples for suitable fragrances showing a ketone structure encompass buccoxime, iso jasmone, methyl beta naphthyl ketone, moschus indanone, tonalid/moschus plus, α-damascone, β-damascon, δ-damascone, Iso-damascone, damascenone, damarose, methyl-dihydrojasmonate, menthone, carvone, campher, fenchone, alphalonen, β-iononw, dihydro-β-Ionone, γ-methylionone, fleuramone, dihydrojasmone, cis-Jasmon, iso-E-Super, methyl cedrenylk etone, or methyl cedrylon, acetophenone, methyl aceto phenone, p-methoxyacetophenone, methyl-β-naphtyl ketone, benzylacetone, benzophenone, p-hydroxy phenylbutanone, celery Ketone or livescon, <NUM>-osopropyl-deca-hydro-<NUM>-naphtone, dimethyloctenone, freskomenth, <NUM>-(I-ethoxyvinyl)-<NUM>,<NUM>,<NUM>,<NUM>,-tetramethylv cyclohexanone, methylheptenone, <NUM>-(<NUM>-(<NUM>-Methyl-<NUM>-cyclohexen-<NUM>-yl)propyl)-cyclopentanone, <NUM>-(p-menthene-<NUM>(<NUM>)-yl)-<NUM>-propanone,<NUM>-(<NUM>-Hydroxy-<NUM>-methoxyphenyl)-<NUM>-butanone, <NUM>-Acetyl-<NUM>,<NUM>-dimethyl-norbornan, <NUM>,<NUM>-dihydro-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>(<NUM>)-indanone, <NUM>-damascol, dulcinyl or cassione, gelsone, hexalone, isocyclemone E, Methylcyclocitrone, methyl lavender ketone, orivone, p-tert-butyl cyclohexanone, verdone, delphone, muscone, neobutenone, plicatone, veloutone, <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-oct-<NUM>-en-<NUM>-one, tetrameran, hedion and their mixtures. The preferred ketones are selected from the group comprising α-damascone, δ-damascone, iso-damascone, carvone, γ-methyl ionone, Iso-E-Super, <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-oct-<NUM>-en-<NUM>-one, benzylacetone, β-damascone, damascenone, methyl dihydrojasmonate, methyl.

Suitable fragrance alcohols encompass for example <NUM>-undecen-<NUM>-ol, <NUM>,<NUM>-dimethylheptan-<NUM>-ol, <NUM>-methylbutanol, <NUM>-methylpentanol,<NUM>-phenoxyethanol, <NUM>-phenylpropanol, <NUM>-tert-Butycyclohexanol, <NUM>,<NUM>,<NUM>-trimethylcyclohexanol, <NUM>-hexanol, <NUM>-methyl-<NUM>-phenylpentanol, <NUM>-octanol, <NUM>-octen-<NUM>-ol, <NUM>-phenylpropanol,<NUM>-heptenol, <NUM>-isopropylcyclohexanol, <NUM>-tert-butycyclohexanol, <NUM>,<NUM>-dimethyl-<NUM>-nonanol,<NUM>-nonen-<NUM>-ol, <NUM>-decen-<NUM>-ol, α-methyl benzylalcohol, α-terpineol, amylsalicylat, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethyl benzylcarbinol, dimethyl heptanol, dimethyl octanol, ethyl salicylate, ethyl vanilin, anethol, eugenol, geraniol, heptanol, hexyl salicylat, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, para-menthan-<NUM>-ol, phenylethylalkohol, phenol, phenyl salicylat, tetrahydro geraniol, tetrahydro linalool, thymol, trans-<NUM>-cis-<NUM>-nonadienol, trans-<NUM>-nonen-<NUM>-ol, trans-<NUM>-octenol, undecanol, vanillin, cinnamalcohol and their mixtures.

Examples for suitable fragrances showing a ketone structure encompass benzyl acetate, phenoxyisobutyrate, p-tert. -butylcyclohexylacetate, linalylacetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramat, melusat, jasmacyclatat and their mixtures.

Examples for suitable fragrances showing a ketone structure encompass benzylethyl ether or ambroxan.

Hydrocarbons. Examples for suitable fragrances representing hydrocarbons encompass terpenes, e.g. limonen and pinen.

A critical feature for the present invention is using as component (c) perfume oils which are encapsulated in a maltodextrin matrix, more particularly obtained from a melt of maltodextrin, polysaccharides (such as for example Gum Arabic) and fragrances by fluidized-bed agglomeration. This type of capsules (also called "pearls") is disclosed in <CIT> (SYMRISE) which as far as the manufacture of the capsules is concerned is hereby incorporated by reference.

More particularly the process for obtaining said capsules or pearls encompasses the following steps: fluidized-bed spray agglomeration, in which a flavoring preparation and/or perfume preparation is sprayed into a fluidized bed, wherein the mean residence time after the flavoring preparation and/or perfumed preparation is sprayed in is less than <NUM> minutes in the fluidized bed; the flavorings and perfumes are selected from the group consisting of berries, citrus, pome fruit, cheese, meat, fish, seafood, spices, herbs, vegetables, coffee, chocolate, mint, tobacco, wood and flowers; the flavoring loadings are in the range from <NUM> to <NUM>% by weight, and the retentions of the flavorings during the agglomeration process are in the range of the <NUM> to <NUM>% by weight; and forming internal granulation nuclei in the fluidized bed during said fluidized-bed spray agglomeration step, wherein resulting encapsulated flavoring and/or perfume preparation granules comprise coated internal granulation nuclei, wherein said encapsulated flavoring and/or perfume preparation granules exiting said fluidized bed are dust-fee, wherein said fluidized-bed spray agglomeration is carried out continuously.

In terms of scent intensity and long-lasting impression it has been found advantageous using capsules showing.

In another preferred embodiment the rim blocks comprise:.

on condition that all amounts add to <NUM> wt.

Preferably component (c) is dosed at <NUM>-<NUM> wt. The pearls are typically loaded with <NUM> wt. -% of perfume oil corresponding to <NUM> to 6wt. -% of the encapsulated perfume oil. The overall preferred dosage is <NUM> to <NUM> wt. - % encapsulated perfume oil and therefore <NUM> to <NUM>% perfume oil in the capsule. However, economic dosages, as demanded by costumer are typically <NUM> to <NUM> wt. -% of the capsules, equivalent to <NUM> to <NUM> wt. -% perfume oil in the capsules.

Again, it should be understood that mixtures as explained above which add up to less or more than <NUM> wt. -% are neither covered by the invention nor by the claims. A skilled person, however, understands how to adjust the components within the suggested ranges to end up with a <NUM> wt. -% composition without any further investigation.

Another object of the present invention refers to a method for preparing a rim block with improved scent performance, particularly either scent change or scent boost, consisting or encompassing the following steps:.

Finally, the present disclosure also encompasses the use of perfume oils in a maltodextrin matrix for making solid rim blocks and/or solid soaps.

For the sake of good order it is stated that all preferred embodiments, combinations and ranges associated with the rim blocks or parts thereof as cited above also apply for the method as claimed. Therefore no repetition is necessary.

In a first attempt, several different fragranced maltodextrin pearls with the same fragrance were mixed into a rim block formulation showing the following composition:.

The rim blocks were prepared with a tablet press. The compositions were evaluated in the wet and dry state in order to decide, which pearls perform best. For this purpose the rim blocks were put in separate plastic cans and the intensity of their fragrance was evaluated by nine panelists in dry and wet state on a scale of <NUM> (low) to <NUM> (high). The results are shown in Table <NUM>:.

The pearls according to Examples <NUM> and <NUM> have a very low loading and therefore perform worse compared to the high loaded pearls according to Examples <NUM>-<NUM>. Too small particles seem to release portions of their perfume oil in the dry state, because of their very big surface. Bigger pearls performed much better.

In the following, rim blocks were prepared, containing different perfume oils and fragrances maltodextrin pearls with a diameter of <NUM> and loaded with <NUM> wt. -% lime flavor. The compositions are provided in Table <NUM>:.

In a triangle test, <NUM> panelists tried to distinguish between wet and dry samples in a jar of brown glass. In each experiment, only one fragrance was used, namely:.

<NUM>% of the panelists could smell a difference, which proves a highly significant difference between the fragrances of the rim blocks. When both samples had dried, several hours later, they were submitted once more to a triangle test. Now, only <NUM>% of the panelists found out the dissimilar sample, which is the statistic share, suggesting no difference between the fragrances emitted by the samples. After one of the rim blocks was made moisty for a second time, <NUM>% of the panelists could recognize it. This shows again a highly significant fragrance difference.

were placed in closed cabins, invisible to a panel of <NUM> untrained people, who were asked to describe the fragrance. Their descriptions were rated according to their accuracy from <NUM> (inaccurate description of the scent switch effect) to <NUM> (description perfectly matches both perfume oil => accurate description of the scent switch effect). In this test, the scent switch effect attained an average value of <NUM>. The results are shown in Table <NUM>.

Claim 1:
A rim block with improved scent performance, comprising or consisting of
(a) a solid rim block base,
(b) at least one non-encapsulated perfume oil, and
(c) at least one perfume oil same or different from component (b) encapsulated in a matrix, wherein said encapsulated fragrances show a fragrance loading of about <NUM> to about <NUM> wt.-%
and characterized in that said matrix is a maltodextrin matrix and further characterized in that said encapsulated fragrances show an average particle size of about <NUM> to about <NUM>.