EP2031047A1 - Body and powder mixture for releasing CO2 - Google Patents

Abstract

Solid body or powder mixture for the release of carbon dioxide in contact with liquid water, comprises 10-45 wt.% of carbonate- and disulfite-salts. An independent claim is included for fragrancing, cleaning and disinfecting toilet and/or reducing, covering and/or preventing bad smells of toilet, comprising providing the solid body or powder mixture, filling a dosing device with the solid body or powder, and bringing the dosing device into the toilet, so that the solid body or powder is dosed into the toilet to a predetermined time and the solid body or powder is contacted with water.

Description

The invention relates to a solid or powder mixture for releasing CO ₂ on contact with liquid water, comprising in each case 10 to 45% by weight of a carbonate salt and a disulfite salt. It also relates to the use of a disulfite salt to improve the storage stability of a solid carbonate or powder mixture comprising a carbonate salt. In particular, it also relates to a method for scenting, cleaning, disinfecting a toilet and / or for bonding, covering and / or preventing bad odors of a toilet and a storage stable, in contact with water bubbling float for performing this method.

For many applications it is desirable for powder or solid to release carbon dioxide (CO ₂ ) on contact with water. This helps to increase the dissolution rate and makes the dissolution process or effect visually perceptible. Such applications include, for example, effervescent tablets for medicinal agents, vitamins and / or minerals, toilet cleansing tablets, denture cleansing tablets, cleansing tablets for swimming pools, Colorant tablets, disinfectant tablets, bath salts and much more. The rapid release of CO ₂ from a solid / powder can be effectively achieved by combining a carbonate salt with an acid: this combination, once in contact with water, causes rapid evolution of carbon dioxide. In contrast, the acid and the carbonate salt in the solid state can usually be in contact with each other without a corresponding reaction occurs with elimination of CO ₂ .

The storage of the described combination of carbonate salt and an acid is problematic, however, since atmospheric moisture can unintentionally trigger the CO ₂ release reaction. In particular, therefore, a longer storage in places with high humidity such as kitchens or bathrooms or in the open only limited or not possible. For this reason, the above-mentioned products such as effervescent tablets or bath salt balls are either stored sealed with desiccant or waterproof welded. This is not possible for certain applications such as in a toilet dispenser, since the dosage should be done automatically, eg with the movement of the toilet lid, so that a tearing or screwing a package is out of the question. The construction of a toilet dispenser, which sufficiently protects the combination of carbonate salt and acid from atmospheric moisture, is conceivable, but so expensive that market compatibility would not exist.

The object of the present invention was therefore to specify a storage-stable mixture of substances which releases CO ₂ on contact with liquid water.

This object is achieved according to the invention by a solid or a powder mixture for releasing CO ₂ on contact with liquid water, comprising in each case from 10 to 45% by weight, preferably from 15 to 42.5% by weight, more preferably from 20 to 40% by weight. % of a carbonate salt and a disulfite salt, wherein the particular preferred amount of fraction can apply regardless of the other component for only one of the two types of salts.

When sodium is used as the counterion and bicarbonate as the anion of the carboxylic salt, stoichiometrically, one mol of sodium disulfite MW = 190.1 and two moles of sodium hydrogencarbonate MG = 84.0 should form two moles of carbon dioxide, one mole of water and two moles of sodium sulfate. This results in a weight ratio of sodium bisulfite to sodium bicarbonate of 190.1 to 168.0.

In practice, in the case of the inventively preferred increase of sodium disulfite to 1.5 times, more preferably twice the amount (by weight) of the sodium bicarbonate, better carbon dioxide yields are obtained. When other cations than Na ^{+ are used} as counterions, slightly different preferred mass ratios of disulfite to bicarbonate salt result according to the molecular masses of the corresponding counterions.

In other words, it is preferred for the solid / powder mixture according to the invention if the stoichiometric ratio of disulfite to bicarbonate anions is 1.5: 2, more preferably 1: 1, or the ratio disulfide to carbonate anions 1.5: 1, more preferred 2: 1.

The solid according to the invention or the powder mixture according to the invention are storage-stable, i. they can be stored at room temperature at a humidity of 100% for more than 20 days, without any substantial deformation of the solids due to the reaction of the disulfite (after hydrolysis) with the carbonate salt. For comparison with succinic anhydride, the solid breaks down after 6 days, with citric acid after 3 days, with phthalic anhydride after 2 days and with tartaric acid after less than one day.

Surprisingly, the effect of the improved storage stability is not based solely on the fact that a disulfite salt is the salt of an acid anhydride and the respective acid anions are released only by reaction with water. An improvement in the storage stability by the use of other acid anhydrides is significantly lower than that with disulfite stays completely (see above).

By using sodium disulphite (sodium pyrosulphite), it is possible to store solids or powder mixtures for the release of CO ₂ on contact with liquid water in the long term and without special protective measures such as, for example, a sheath of water-impermeable material or a watertight vessel. For example, it is only possible to use it in a toilet dispenser.

• Es bindet bei einer Hydrolyse Wasser, so dass bei wenig zur Verfügung stehendem Wasser (hohe Luftfeuchtigkeit) unerwünschtes Wasser gebunden wird.
• Die Hydrolyse erfolgt schnell, so dass unerwünschte Feuchtigkeit (Luftfeuchtigkeit) schnell im erfindungsgemäßen Festkörper oder Pulvergemisch gebunden wird, so dass selbst wenn bereits hydrolysiertes Natriumdisulfit - also Natriumhydrogensulfit vorliegt, es zu keiner Anfeuchtung des erfindungsgemäßen Festkörpers oder Pulvergemisch es kommt, die eine Säurebasereaktion und damit die Freisetzung von CO₂ ermöglichen würde. Die schnelle Hydrolyse führt dagegen bei einem Überschuss von Wasser dazu, dass schnell ausreichend Sulfitanionen bzw. Hydrogensulfitanionen gebildet werden können, um verhältnismäßig große Mengen CO₂ freizusetzen.
• Salze von Disulfiten liegen nicht als Säure vor, stellen aber unter Hydrolysebedingungen schnell die für die Reaktion mit Carbonatsalzen nötigen Verbindungen bzw. lonen zur Verfügung.

Sodium disulfite has a number of advantages for use in a solid or powder mixture for the release of CO ₂ :

• It binds with a hydrolysis water, so that with little available water (high air humidity) unwanted water is bound.
• The hydrolysis takes place rapidly, so that unwanted moisture (humidity) is rapidly bound in the solid or powder mixture according to the invention, so that even if already hydrolyzed sodium disulfite - ie sodium bisulfite is present, there is no moistening of the solid or powder mixture according to the invention, which is an acid base reaction and thus would allow the release of CO ₂ . On the other hand, the rapid hydrolysis, with an excess of water, leads to the rapid formation of sufficient sulfite ions or hydrogen sulphite anions to release relatively large quantities of CO ₂ .
• Salts of disulfites are not present as acid, but readily provide the compounds or ions necessary for reaction with carbonate salts under hydrolysis conditions.

Preference is given to a powder mixture according to the invention, wherein the carbonate salt is selected from the group consisting of K ₂ CO ₃ , KHCO ₃ , Na ₂ CO ₃ and NaHCO ₃ and / or the disulfite salt is selected from the group consisting of Na ₂ S ₂ O ₅ and K ₂ S ₂ O ₅ .

Preference is given to a solid or a powder mixture according to the invention comprising a perfume oil, a surfactant, a binder, a water-soluble dye, a disinfectant, a bleaching agent and / or a substance for binding, covering, neutralizing and / or preventing bad odors. Depending on the intended application, in each case one or more representatives of the named substance groups as well as one, several or all substance groups can be contained in the solid body or powder mixture according to the invention.

The amount of perfume oil present in the solid or powder mixture according to the invention is selected by the person skilled in the art, depending on the desired intensity of the scent. Their proportion is 0 or 0.00001 to 10 wt .-%, preferably 0.5 to 9 wt .-%, more preferably 1 to 8 wt .-%. Particularly suitable is an amount of 3 to 7 wt .-%. All statements in wt .-% made in this text refer in each case to the total mass of the solid according to the invention or of the powder mixture according to the invention.

Preferred surfactants are sec. Alkanesulfonates, but also alkyl ester sulfonates, alkyl sulfates, carboxylates, phosphates, sulfonates, arylalkyl sulfonates, alkyl ether sulfates and mixtures of the compounds mentioned. In the following, some of the candidate types of anionic surfactants will be described in more detail:

Secondary alkanesulfonates: secondary alkanesulfonates are surfactants of the formula R-SO ₃ M whose alkyl group R is saturated or unsaturated, linear or branched and which can also carry hydroxyl groups, the terminal carbon atoms of the alkyl chain having no sulfonate group. Counterion M may be sodium, potassium, ammonium, mono-, di- or tri-alkanol ammonium, calcium, magnesium ion or mixtures thereof. Preference is given to sodium salts of the secondary alkanesulfonates.

Alkyl Ester Sulfonates: Alkyl ester sulfonates are linear esters of C ₈ -C ₂₀ carboxylic acids (ie fatty acids) which are sulfonated by SO ₃ .

Alkyl sulfates: Alkyl sulfates are water-soluble salts or acids of the formula ROSO ₃ M, wherein R preferably has a C ₁₀ -C ₂₄ -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C ₁₂ -C ₁₈ -alkyl represents - or hydroxyalkyl. M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation, such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.

Alkyl ether sulfates: Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ -alkyl or hydroxyalkyl radical having 10 to 24 C atoms, preferably a C ₁₂ -C ₂₀ -alkyl - or hydroxyalkyl radical, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy moiety, m is a number greater than 0, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is a hydrogen atom or a cation such as a metal cation (eg, sodium, potassium , Lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Examples which may be mentioned are C ₁₂ -C ₁₈ -alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ -alkyl polyethoxylate (2,25) sulfate, C ₁₂ -C ₁₈ -alkyl polyethoxylate (3.0 ) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate, wherein the cation is sodium or potassium.

Other anionic surfactants suitable for use are C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolysis products of alkaline earth metal citrates, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, alkyl phenol ether sulfates, primary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N Acyltaurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates and diesters of sulfosuccinates, acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl glycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COOM where R is C ₈ -C ₂₂ alkyl, k is 0 to 10 and M is a soluble salt-forming cation.

Particularly preferred are surfactants having a high HLB value (the HLB value describes the ratio between hydrophilic and lipophilic portions of the surfactant molecule), ie a high proportion of hydrophilic groups, called solubilizers, in particular solid solubilisers, which are solid at room temperature, e.g. Fatty alcohol ethoxylates of higher molecular mass. Examples of these are polyethylene glycol-25-palmitin / stearic acid mixtures (HLB = 41), polyethylene glycol-50-palmitin / stearic acid mixtures (HLB = 43), polyethylene glycol-80-palmitin / stearic acid mixtures (HLB = 55). Polyethylene glycol (25) stearyl ether is preferred in this context

As a rule, the solubilizers are not used as individual substances but as mixtures of substances with different degrees of ethoxylation and different lengths of alkyl chains.

The amount of solubilizers used depends on the proportion of apolar components in a solid or powder mixture according to the invention. Regularly apolar is perfume oil if available. According to the invention, the proportion of solid solubilizer is from 1 to 60% by weight, preferably from 5 to 45% by weight, particularly preferably from 10 to 30% by weight.

If additional properties such as foam or increased cleaning performance when using the solid or the powder mixture according to the invention are desired, especially surfactants with the corresponding properties can also be added.

If, in particular, several solid bodies according to the invention are stored together, it is advantageous if a binder is added to the solid body is to prevent sticking together of the solid according to the invention.

Preferred binders are starch, gum arabic, talc, gelatin, polyvinylpyrrolidone and substituted celluloses particularly preferred are hydroxyethyl cellulose.

The proportion of binder in the solid or powder mixture according to the invention is preferably from 0.0001 to 5% by weight, preferably from 0.1 to 1% by weight.

Preferably, a solid according to the invention or a powder mixture according to the invention also contains water-soluble dyes which, depending on the application, can provide an appealing appearance of the solid / powder mixture. In addition, water-containing liquids can be changed in their color by the dissolution of the solid according to the invention or the powder according to the invention with appropriate dyes. For solid reasons, solid bodies according to the invention can also be coated with a layer of silicone oil which preferably gives gloss.

In the mass of a solid according to the invention or of a powder mixture according to the invention, it is possible to incorporate various additives for additional effects which are advantageous in a toilet. This can e.g. Disinfectants, bleaches or substances that prevent the perception of bad odors.

Preferred disinfectants are surface active compounds having antimicrobial activity, e.g. Benzalkonium chloride, various phenol derivatives, and bleaching agents, which also act as a disinfectant (see next paragraph).

From 0 to 20% by weight of oxygen-based bleaching agents may be used, such as e.g. B. salts of perborates, percarbonates, persulfates, hydrogen peroxide, Sodium hypochlorite, chloroisocyanurates, and mixtures thereof. As an activator for these oxygen suppliers can z. As tetraacetylethylenediamine (TAED) can be used

Fragrances that can mask and / or neutralize unpleasant odors are preferably selected from the group consisting of (some industry-standard product names and brand names are given): 1-phenyl-2-methyl-2-propyl acetate, 2-methylbutyl butyrate, Aldron ( 4 - [(3,3-dimethylbicyclo [2.2.1] hept-2-yl) methyl] -2-methylcyclohexanone), allyl 2-cyclohexyloxyglycolate, allyl 2-pentyloxyglycolate, allyl 3-cyclohexylpropionate, allylcapronate, amarocite ( 1,1-dimethoxy-2,2,5-trimethyl-4-hexene), ambral (dodecahydro-3,8,8,11a-tetramethyl-5H-3.5a-epoxynaphth [2.1-c] oxepine), Hexadecene-16-olide), ambrinol S (1,2,3,4,4a, 5,6,7-octahydro-2,6,6-trimethyl-2-napthalenol), ambrinolepoxide, ambrocenide (4aR, 5R, 7aS, 9R) octahydro-2,2,5,8,8,9a-hexamethyl-4H-4a, 9-methanoazuleno (5,6-d) -1,3-dioxole), ambroxide (3a, 6,6 , 9a-tetramethyldodecahydronaphtho [2,1-b] furan), amyl formate, Aurelione (7-cyclohexadecen-1-one and 8-cyclohexadecen-1-one), boronal [2-methyl-4- (2,6,6 trimethyl-1-cyclo witch n-1-yl) butenal], brahmanol [2-methyl-4- (2,2,3-trimethyl-3-cyclopentenyl) -butanol], buccoxime (1,5-dimethylbicyclo [3.2.1] octane-8 -onoxime), butyl acetate, cantryl (2,2,3-trimethyl-3-cyclopentenyl-1-acetonitrile), Cassix 150 (4-methoxy-2-methyl-2-butanethiol), chrysanthemum [1- (2,4- Dimethyl-3-cyclohexen-1-yl) -2,2-dimethyl-1-propanone], cis-3-hexenyl acetate, citronellyl butyrate, citronellyltiglinate (3,7-dimethyl-6-octenyl-2-methylcrotonate), citronitrile (3 Methyl-5-phenyl-2-pentenenitrile), citrowanil B (alpha-ethenyl-alpha-methylbenzene-propenitrile), claritone (2,4,7-tetramethyl-6-octen-3-one), Corps Racine VS [2- (2- 3-phenylpropyl) pyridine], coumarone (1- (2-benzofuranyl) -ethanone), cyclogalbanate (allylcyclohexyloxyacetate), cyclohexylmagnol (alpha-methylcyclohexanepropanol), datilate (1-cyclohexylethylcrotonate), ethyl 2-methylbutyrate, ethylisobutyrate, ethylisovalerate, ethyltricyclo [5.2.1.0 ^2,6 ] decan-2-yl carboxylate, farenal (2,6,10-trimethyl-9-undecenal), filbertone (5-methyl-2-hepten-4-one), fleursandol (4- (3a, 4,5,6,7,7a-hexahydro-4,7-methano-1H-inden-6-yl) -3-methyl-3-buten-2-ol), florazone (4-ethyl) alpha, alpha-dimethyl benzenepropanal), Floropal (2,4,6-trimethyl-4-phenyl-1,3-dioxane), Fragolane [(2,4-dimethyl- [1,3] dioxolan-2-yl) acetic acid ethyl ester )], Frutinate (But-2-enoic acid-1,3-dimethylbutyl ester), gamma-decalactone, geranyl acetate, geranyl butyrate, geranyltiglinate (trans-3,7-dimethyl-2,6-octadienyl-2-methyl crotonate), Globalide [(11/12 Pentadecene-15-olide], globanone (8-cyclohexadecen-1-one), hexyl butyrate, hydrocitronitrile (beta-methyl-benzene pentanenitrile), Indianol (4- [3a, 4,5,6,7,7a-hexahydroxy) 4,7-methano-1H-indene-5 (6) -yl] -3-methyl-3-buten-2-ol), indofloro (4,4a, 5,9b-tetrahydoindeno [1,2-d] - m -dioxin), irisonitrile (2-nonenylnitrile), isoamyl acetate, isoamylisovalerate, isodamascon [1- (2,4,4-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one], isomuscon ( Cyclohexadecanone), Jacinthaflor (2-methyl-4-phenyl-1,3-dioxolane), ketamber (dodecahydro-3,8,8,11a-tetramethyl-5H-3,5a-epoxynaphth [2.1-c] oxepine), lactojasmon (4-hexyl-4-methyl-butyrolactone), leguminal (propanal-methyl-cis-3-hexenyl-acetal), macrolides (oxacyclohexadecan-2-one), madranol (mixture of different hexahydro methylionones), magnolane (2,4-hexanyl-acetal) Dimethyl 5,6-indeno-1,3-dioxane), Majantol [2,2-dim ethyl 3- (3-methylphenyl) -propanol], mandaril (3,12-tridecadienitrile), menthyl acetate, methyl butyrate, methyl dihydrojasmonate, methyl isobutyrate, mintonate (3,3,5-trimethylcyclohexyl acetate), mugetanol [1- (4-isopropylcyclohexyl) ethanol], nerolione [1- (3-methyl-2-benzofuranyl) -ethanone], octyl acetate, ozonil (2-tridecenenitrile), palisandane (1,1-dimethoxycyclododecane), palisandin (cyclododecylmethyl ether), parmanyl [3- (cis 3-hexenyloxy) -propanenitrile], passiflorane (3-acetylthiohexylacetate), peacholide (cis- and trans-3-methyl-gamma-decalactone), prenylsalicylate, profarnesal (2,6,10-trimethyl-5,9-undecadienal) , Projasmon P (2-heptylcyclopentanone), pyroprunate (But-2-enoic acid bicyclopenten-2-yl ester), Rholiate (carbonic acid ethyl-2,3,6-trimethylcyclohexyl ester), rosaphene (2-methyl-5-phenylpentane-1 -ol), rose oxide, Sandel 80 (trans-3-isocamphylcyclohexanol), sandranol (2-ethyl-4- (2,2,3-trimethyl-3-cyclpentene-1-yl) -2-buten-1-ol) , Symrose (4-isoamylcyclohexanol), Symroxane (4- (3-methylbutyl) -cyclohexanol (Z)), tabanone [4- (2-butenylidene) -3,4,5-trimethyl-2-cyclohexen-1-one], terpineol-4, timberol (2,2,6-trimethyl-alpha-propyl) cyclohexanepropanol), tolylacetate dia. D para (4-methyl-benzeneacetaldehyde), tricyclodecenyl-propionate, tropicol (2-mercapto-2-methylpentan-1-ol), vertosine [2- (2,4- (or 3,5) -dimethyl Methyl-3-cyclohexen-1-yl) -methyleneaminobenzoate], formula (octahydro-4,7-methano-1H-indenecarbaldehyde), vetectol acetate (1,3-dimethyl-3-phenylbutylacetate), vetival (4-cyclohexyl-4-) methylpentan-2-one), Ysamber K (spiro hexahydro-1 ', 1', 5 ', 5'-tetramethyl- [1,3-dioxolane-2,8' - (5'H) - [2H-2,4a] -methanonaphthalene].

Fragrances which are advantageously suitable can be found e.g. in S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, NJ 1969, Eigenverlag, or K. Bauer et al., Common Fragrance and Flavor Materials, 5th Edition, Wiley-VCH, Weinheim 2006. In detail called:

Extracts from natural raw materials such as essential oils, concretes, absolues, resines, resinoids, balsams, tinctures such as e.g.

ambergris tincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Beifussöl; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar; Bitter almond oil; Savory oil; Buccoblätteröl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Beaver-absolue; Cedernblätteröl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de Brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam; gurjun balsam oil; Helichrysum absolute; Helichrysumöl; Ginger oil; lriswurzel absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Camomile oil Roman; Carrot seed oil; Kaskarillaöl; Pine needle oil; spearmint; Seed oil; labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Lime oil pressed; linaloe; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute; Musk seed oil; musk tincture; Clary sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; myrtle; Clove leaf oil; Clove flower oil; neroli; Olibanum absolute; olibanum; Opopanaxöl; Orange blossom absolute; Orange oil; oregano; Palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; chilli; pine oil; Poleyöl; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Sage oil Dalmatian; Sage oil spanish; sandalwood; Celery seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Pine needle oil; Tea tree oil; turpentine; Thyme oil; Tolu; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; verbena; vetiver; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; ylang oil; hyssop oil; Civet absolute; cinnamon leaf; Cinnamon bark oil and fractions thereof, or ingredients isolated therefrom.

Individual fragrances from the group of hydrocarbons, such as 3-carene; alpha-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1,3,5-undecatriene; styrene; diphenylmethane; the aliphatic alcohols such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octene-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3,7-dimethyl-7-methoxyoctane-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; the aliphatic aldehydes and their acetals such as hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methyl nonanal; (E) -2-hexenal; (Z) -4-heptenal; 2; 6-dimethyl-5-heptenal; 10-undecenal; (E) -4-decenal; 2-Dodecena1; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; Heptanaldiethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; (1-methoxy-propoxy) 1- - 3-ene (E / Z); the aliphatic ketones and their oximes such as 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; the aliphatic sulfur-containing compounds such as 3-methylthio-hexanol; 3-Methylthiohexylacetat; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol; the aliphatic nitriles such as 2-nonenitrile; 2-Undecensäurenitril; 2-Tridecensäurenitril; 3,12-Tridecadiensäurenitril; 3,7-dimethyl-2,6-octadiensäurenitril; 3,7-dimethyl-6-octensäurenitril; the ester of aliphatic carboxylic acids such as (E) - and (Z) -3-hexenylformate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate; (E) - and (Z) -3-hexenylacetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl; hexyl butyrate; (E) - and (Z) -3-hexenyl isobutyrate; hexyl crotonate; Ethylisovalerianat; Ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; Ethyl (E, Z) -2,4-decadienoate; Methyl-2-octinat; Methyl-2-noninat; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl-crotonate; the acyclic terpene alcohols such as citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3,7-dimethyl-4,6-octadiene-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; the acyclic terpene aldehydes and ketones such as geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; the cyclic terpene alcohols such as menthol; isopulegol; alpha-terpineol; Terpinenol-4; Menthane-8-ol; Menthane-1-ol; Menthane-7-ol; borneol; soborneol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; the cyclic terpene aldehydes and ketones such as menthone; menthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-lron; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1- (2,4,4-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8 (5H) -one; 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-butenal; nootkatone; Dihydronootkaton; 4,6,8-Mega stigma triene-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone); the cyclic alcohols such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-lsocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyl tetrahydro-2H-pyran-4-ol; the cycloaliphatic alcohols such as alpha, 3,3-trimethylcyclohexylmethanol; 1- (4-isopropylcyclohexyl) ethanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) butanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) pentan-2-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 3,3-Dimethyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 1- (2,2,6-trimethylcyclohexyl) pentan-3-ol; 1- (2,2,6-trimethylcyclohexyl) hexan-3-ol; the cyclic and cycloaliphatic ethers such as cineole; cedryl methyl ether; cyclododecyl; 1,1-Dimethoxycyclododecan; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; 3a, 6,6,9a-tetramethyldodecahydronaphtho [2,1-b] furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho [2,1-b] furan; 1,5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; rose oxide; 2- (2,4-dimethyl-3-cyclohexen-1-yl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane; the cyclic and macrocyclic ketones such as 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-Dihydro-1,1,2,3,3-pentamethyl-4 (5H) -indanon; 8-cyclohexadecen-1-one; 9-cycloheptadecen -1-one; cyclopentadecanone; cyclohexadecanone; the cycloaliphatic aldehydes such as 2,4-dimethyl-3-cyclohexene carbaldehyde; 2-methyl-4- (2,2,6-trimethyl-cyclohexen-1-yl) -2-butenal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene carbaldehyde; 4- (4-methyl-3-penten-1-yl) -3-cyclohexene carbaldehyde; the cycloaliphatic ketones such as 1- (3,3-dimethylcyclohexyl) -4-penten-1-one; 2,2-dimethyl-1- (2,4-dimethyl-3-cyclohexen-1-yl) -1-propanone; 1- (5,5-dimethyl-1-cyclohexen-1-yl) -4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphtalenylmethylketon; Methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienylketon; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone; the ester of cyclic alcohols such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-Trimethylcyclohexylacetat; Decahydro-2-naphthyl acetate; 2-Cyclopentylcyclopentylcrotonat; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenyl acetate, respectively; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenylpropionate, respectively; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenyl isobutyrate, respectively; 4,7-Methanooctahydro-5, or 6-indenyl acetate; the ester of cycloaliphatic alcohols such as 1-cyclohexylethyl crotonate; the esters of cycloaliphatic carboxylic acids such as allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; cis- and trans-methyldihydrojasmonate; cis- and trans-methyl jasmonate; Methyl-2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl-2-methyl-1,3-dioxolan-2-acetate; the araliphatic alcohols such as benzyl alcohol; 1-phenylethyl; 2-phenylethyl; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1,1-dimethyl-2-phenylethyl; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl; 1- (4-isopropylphenyl) ethanol; the ester of araliphatic alcohols and aliphatic carboxylic acids such as benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-Phenylethylisovalerianat; 1-phenylethyl acetate; alpha-Trichlormethylbenzylacetat; alpha, alpha-Dimethylphenylethylacetat; alpha, alpha-Dimethylphenylethylbutyrat; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the araliphatic ethers such as 2-phenylethyl methyl ether; 2-Phenylethylisoamylether; 2-phenylethyl-1-ethoxyethyl ether; phenylacetaldehyde; phenylacetaldehyde; Hydratropaaldehyddimethylacetal; Phenylacetaldehydglycerinacetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a, 5,9b-tetrahydroindeno [1,2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethylindeno [1,2-d] -m-dioxin; the aromatic and araliphatic aldehydes such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; propanal, 2-methyl-3- (4-tert-butylphenyl); 2-methyl-3- (4-isobutylphenyl) propanal; 3- (4-tert-butylphenyl) propanal; cinnamic aldehyde; alpha-Butylzimtaldehyd; alpha-amyl cinnamic aldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3- (4-methoxyphenyl) propanal; 2-methyl-3- (4-methylenedioxyphenyl) propanal; the aromatic and araliphatic ketones such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; 2-Benzofuranylethanon; (3-methyl-2-benzofuranyl) ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1- [2,3-dihydro-1,1,2,6-tetramethyl-3- (1-methylethyl) -1H-5-indenyl] ethanone; 8'-hexamethyl-2-acetonaphthone, 5 ', 6', 7 ', 8'-tetrahydro-3', 5 ', 5', 6 ', 8'; the aromatic and araliphatic carboxylic acids and their esters such as benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; Benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; cyclohexyl; Cis-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenylglycidate; Ethyl-3-methyl-3-phenylglycidate; the nitrogen-containing aromatic compounds such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; cinnamic acid; 3-methyl-5-phenyl-2-pentensäurenitril; 3-methyl-5-phenylpentansäurenitril; methyl anthranilate; Methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde; 6-lsopropylchinolin; 6-lsobutylchinolin; 6-sec.-butylquinoline; 2- (3-phenylpropyl) pyridine; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; the phenols, phenyl ethers and phenyl esters such as estragole; anethole; eugenol; Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-Naphthylethylether; beta-Naphthylisobutylether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2-ethoxy-5- (1-propenyl) phenol; p-Kresylphenylacetat; heterocyclic compounds such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; the lactones such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1.15 pentadecanolide; cis- and trans-11-pentadecene-1,15-olide; cis and trans-12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecene-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; Ethylene-1,12-dodecanedioate; Ethylene-1,13-tridecandioat; coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin.

Particularly preferred fragrances are isobornyl acetate, limonene, Ylanat® (Oryclone®, 4-tert-butylcyclohexyl acetate), eucalyptol, dihydromyrcenol, amyl salicylate, benzyl acetate, geranyl nitrile, nerol, geraniol, 2-methyl undecanal and phenylethyl alcohol.

For many applications, such as Packing for use for toilet scenting or for use in tablet form, it is useful to use a solid according to the invention, which has been solidified using polyethylene glycol. In this context, preference is given to polyethylene glycols whose molar mass is above 1000 g / mol. In order to adjust the solubility for certain uses, mixtures of different polyethylene glycols may also be used. The proportion of the polyethylene glycol used in the total mass of the solid according to the invention can be between 1 and 70% by weight, preferably 2 to 50% by weight, more preferably 3.5 to 25% by weight and particularly preferably 5 to 50% by weight. be. The polyethylene glycols used should have a molar mass between 1000 and 10000 g / mol, preferably the mass is between 5000 and 7000 g / mol.

A preferred solid according to the invention is floatable, ie it has a density which is lower than that of water (1 g / cm ³ ). Such a buoyant solid is particularly suitable for use in scenting, cleaning, Disinfecting a toilet and / or tying, covering and / or preventing bad odors of a toilet.

There are various ways to clean toilets, while simultaneously cleaning, disinfecting and / or binding, covering and / or preventing bad odors is possible. For example, toilet bowls attached to baskets are used with perfume oil and other ingredients, or containers that release various kinds of smelling liquids. As a rule, the fragrance is permanently released, it would be desirable to release the fragrance targeted at certain times.

One way to achieve this is to dose body according to the invention, for example via a lid dispenser when opening or closing the toilet lid in the toilet bowl. An appropriate dispenser for toilets is in the WO 2006/040293 A2 described. Preferably, spheres are used in such a process because they can be moved most reliably in the corresponding metering devices.

For the application area "toilet" body of the invention must meet certain conditions: they must dissolve quickly and on the water surface. Dissolve too slowly, the desired fragrance is released too late and the balls do not float, then sink into the back of the toilet siphon, where the fragrance delivery is ineffective because they are too deep in the water or on the wrong Side of the siphon. This problem is also in the published patent application DE 32 09 333 A1 (Method for producing a buoyant acid tablet for toilet cleaning). The buoyancy of the acid tablet described there is based on the fact that necessary for the boost carbon dioxide is produced extremely fast and so the body with high. Part of the buoyancy is also due to the fact that the carbon dioxide temporarily remains in contact with the body via a foam.

The low density of the preferred body according to the invention and thus the buoyancy can be achieved by including a water-soluble floating body, such as a sugar foam, can be achieved by air bubbles in the body or by a hollow body. The density of the body according to the invention is preferably well below the density of the water, ie <0.9 g / cm ^3, more preferably <0.8 g / cm ³ . However, it may be advantageous if a sufficiently high density is present, so that the body dives to a large extent in the water, so as to produce the strongest possible bubbling effect.

Preferably, the buoyant body consists either of foamed material or - as already indicated above - from a light core and a heavy, CO ₂ releasing shell. In the variant "light core and heavy shell", the core consists of material of significantly lower density than water, for example, from a gas-foamable water-soluble mass. The water solubility of the mass is preferred for many applications, but especially in the field "WC", otherwise the water-insoluble parts would remain in the toilet bowl and float and would be difficult or impossible to wash away due to their low density.

A mass for such a light core can be e.g. from heat-melted sugar by adding sodium bicarbonate. The foam can be pressed in molds into the desired shape.

An alternative possibility is the stirring of air in soap (cf. WO 99/66022 , Process for the preparation of liquid soap and mixing system) or Syndetmasse.

Unattractive color effects in the bodies according to the invention can be colored by dyes, which are of course preferably water-soluble. Thus, for example, in the case of the different density of core and sheath, the two of the body according to the invention can be adapted to one another or else deliberate color shades / color contrasts can be set.

Preferred solids of the invention have a volume of 0.5 cm ³ to 34 cm ³ , which is approximately a diameter for a spherical solid of 0.5 cm to 2 cm corresponds. Solid bodies of this size can be used particularly well in a dosing dispenser. In principle, they can take any desired form such as cube shape, conical shape, cylindrical shape, tablet shape, pyramid shape, cuboid shape or spherical shape, where, as already indicated above, the spherical shape is preferred for use in connection with dispensers, since it has the best mechanical properties. Particularly suitable in this context is a ball with a diameter of 0.5 cm to 0.99 cm, as in this sufficient perfume oil (or other agents) for the desired application (especially in the application for scenting toilets) can be introduced , At the same time, the balls are small enough to accommodate a larger number in a dosing dispenser.

For use in the toilet area, a preferred dissolution rate for balls is 5 to 10 minutes (depending on the water temperature) and the proportion of salt for carbonate release.

Also part of the invention is the use of a disulfite salt to improve the storage stability of a solid comprising a carbonate salt or a powder mixture comprising a carbonate salt which is suitable for releasing CO ₂ upon contact with liquid water.

As already described above, the finding that the disulfite salt significantly increases the storage stability of a solid or powder mixture according to the invention in comparison with other acid anhydrides is an essential core of the invention. Finally, the use according to the invention makes it possible to substantially expand the range of use of solids or powder mixtures which release CO ₂ on contact with liquid water.

For the use according to the invention it is preferred that the carbonate salt is selected from the group consisting of K ₂ CO ₃ , KHC0 ₃ , Na ₂ CO ₃ and NAHCO ₃ and / or the disulfite salt is selected from the group consisting of Na ₂ S ₂ O ₅ and K ₂ S ₂ O ₅ .

1. a) Bereitstellen eines erfindungsgemäßen Festkörpers oder eines Pulvergemisches,
2. b) Bereitstellen einer geeigneten Dosiervorrichtung für den Festkörper oder das Pulver,
3. c) Befüllen der Dosiervorrichtung mit dem Festkörper oder dem Pulver und
4. d) Anbringen der Dosiervorrichtung in der Toilette, so dass der Festkörper oder das Pulver zu einem vorbestimmten Zeitpunkt so in die Toilette dosiert wird, so dass der Festkörper oder das Pulver mit Wasser in Berührung kommt.

A component of the invention is also a method for scenting, cleaning, disinfecting a toilet and / or for binding, covering and / or preventing bad odors of a toilet, comprising the steps:

1. a) providing a solid or a powder mixture according to the invention,
2. b) providing a suitable metering device for the solid or the powder,
3. c) filling the metering device with the solid or the powder and
4. d) attaching the dosing device in the toilet, so that the solid or the powder is dosed at a predetermined time in the toilet, so that the solid or the powder comes into contact with water.

Predetermined times may in this context e.g. the time of movement of the toilet lid, the operation of flushing, entering or leaving the toilet room by a person or regularly spaced time points (e.g., electronically controlled). The process according to the invention can be carried out particularly advantageously on account of the improved storage stability of the solids or of the powder.

example

In the following example formulations all data are - unless otherwise stated - wt .-%.

In each case the following perfume oil with rose smell was used: parts by weight Acetophenone, 10% in DPG 10 n-undecanal 5 Aldehyde C14 so-called (peach aldehyde) 15 Allylamyl glycolate 10% in DPG 20 amylsalicylate 25 benzyl 60 Citronellol 80 d-Limonene 50 Decenol trans-9 15 dihydromyrcenol 50 dimethyl benzyl 30 diphenyl 5 eucalyptol 10 geraniol 40 nerol 20 geranium 15 Hexenol cis-3, 10% in DPG 5 Hexenyl salicylate cis-3 20 Indole, 10% in DPG 10 Ionone alpha 15 Ionone beta 5 lilial 60 linalool 40 methyl phenylacetate 10 phenylethyl 275 Styrolylacetat 20 terpineol 30 tetrahydrolinalool 50 cinnamic alcohol 10 Total: 1000

Example formulation 1:

22.00% Polyethylene glycol (29) Cetyl / stearyl ether (solubilizer, e.g., Emuldac AS-25, INCI: Ceteareth-29) 6.78% Polyethylene glycol (150) (solvent, e.g., Lipoxol 6000, INCI: PEG-150) 31.00% Carbonate salt (e.g., sodium bicarbonate) 35.00% sodium metabisulfite 0.20% Hydroxyethylcellulose (binder, for example: Natrosol 250 HHR, INCI: hydroxyethylcellulose) 0.02% Dye (e.g., Dragocolor Brilliant Blue, INCI: Blue 1 C.I. 42090) 5.00% Perfume oil (INCI: Perfume)

Example formulation 2:

30.00% Polyethylene glycol (29) Cetyl / stearyl ether (solubilizer, e.g., Emuldac AS-25, INCI: Ceteareth-29) 2.50% N- (2-hydroxyethyl) coconut fatty acid amide (foam enhancer, e.g., Comperlan 100 7.00% Polyethylene glycol (150) (solvent, e.g., Lipoxol 6000, INCI: PEG-150) 38.97% Carbonate salt (e.g., sodium bicarbonate) 18.00% sodium metabisulfite 0.20% Hydroxyethylcellulose (binder, for example: Natrosol 250 HHR, INCI: hydroxyethylcellulose) 0.01% Dye (e.g., Dragocolor Brilliant Blue, INCI: Blue 1 C.I. 42090) 3.50% Perfume oil (INCI: Perfume)

Solubilizer and solvent are melted together and the remaining components stirred at just 50 ° C. The resulting waxy mass is applied to the cores e.g. applied in the heat with sodium bicarbonate foamed sugar cores and rolled round, shaped as a hollow ball (possibly as two halves and then put together) or foamed.

All of the bodies made in the three ways described had a spherical shape and a diameter of a little less than 1 cm. The bodies completely dissolved upon contact with water at room temperature with bubbling and release of a well perceived fragrance within 5 to 10 minutes.

Claims (14)

A solid or powder mixture for releasing CO ₂ when in contact with liquid water, comprising in each case 10-45% by weight of a carbonate salt and a disulfite salt. A solid or powder mixture according to claim 1, wherein
the carbonate salt is selected from the group consisting of K ₂ CO ₃ , KHCO ₃ , Na ₂ CO ₃ and NAHCO ₃ and / or
the disulfite salt is selected from the group consisting of Na ₂ S ₂ O ₅ and K ₂ S ₂ O ₅ . A solid or powder mixture according to claim 1 or 2, comprising a perfume oil, a surfactant, a binder, a water-soluble dye, a disinfectant, bleaching agents and / or substances for binding, neutralizing, covering and / or preventing bad odors. Solid according to one of the preceding claims comprising polyethylene glycol of a molar mass of 1000 to 10,000 g / mol. A solid according to any one of the preceding claims, wherein the solid has a density of less than 1 g / cm ³ . A solid according to any one of the preceding claims, wherein the body has a volume of 0.5 cm ³ -34 cm ³ . Solid according to one of the preceding claims, wherein the solid has cube shape, conical shape, cylindrical shape, tablet shape, pyramid shape, cuboid shape or spherical shape. Solid according to one of the preceding claims, wherein the solid has the shape of a sphere with a diameter of 0.5 cm to 0.99 cm. Solid according to one of the preceding claims, wherein the solid has been coated on at least parts of its surface with a silicone oil. Solid according to one of the preceding claims or powder mixture according to one of claims 1 to 3, comprising 0.00001 to 10% by weight of perfume oil. A solid according to any one of the preceding claims or a powder mixture according to any one of claims 1 to 3 or 10, wherein the solid or powder mixture comprises one or more fragrances selected from the group consisting of isobornyl acetate, limonene, ylanate, eucalyptol, dihydromyrcenol, amyl salicylate, benzyl acetate, Geranyl nitrile, nerol, geraniol, 2-methyl undecanal and phenylethyl alcohol. Use of a disulfite salt for improving the storage stability of a carbonate salt-comprising solid or powder mixture which is suitable for releasing CO ₂ upon contact with liquid water. Use according to claim 12, wherein
the carbonate salt is selected from the group consisting of K ₂ CO ₃ , KHCO ₃ , Na ₂ CO ₃ and NAHCO ₃ and / or
the disulfite salt is selected from the group consisting of Na ₂ S ₂ O ₅ and K ₂ S ₂ O ₅ . A method for scenting, cleaning, disinfecting a toilet and / or for binding, covering and / or preventing bad odors of a toilet, comprising the steps of: a) providing a solid according to any one of claims 1 to 11 or a powder mixture according to any one of claims 1 to 3 or 10 to 11, b) providing a suitable metering device for the solid or the powder, c) filling the metering device with the solid or the powder and d) attaching the dosing device in the toilet, so that the solid or the powder is dosed at a predetermined time in the toilet, so that the solid or the powder comes into contact with water.