Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0052—Gas evolving or heat producing compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0056—Lavatory cleansing blocks
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/12—Carbonates bicarbonates

Definitions

• 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.
• CO 2 carbon dioxide
• 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.
• 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 object of the present invention was therefore to specify a storage-stable mixture of substances which releases CO 2 on contact with liquid water.
• 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.
• 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.
• 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.
• 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).
• sodium disulphite sodium pyrosulphite
• 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 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.
• a perfume oil e.g., 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.
• 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.
• alkyl ester sulfonates alkyl sulfates, carboxylates, phosphates, sulfonates, arylalkyl sulfonates, alkyl ether sulfates and mixtures of the compounds mentioned.
• 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 are linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated by SO 3 .
• 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.
• alkali metal cation eg sodium, potassium, lithium
• 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, tri
• 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
• 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.
• 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.
• 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.
• 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
• 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.
• solubilizers in particular solid solubilisers, which are solid at room temperature, e.g. Fatty alcohol ethoxylates of higher molecular mass.
• solubilizers in particular solid solubilisers, which are solid at room temperature, e.g. Fatty alcohol ethoxylates of higher molecular mass.
• solubilizers in particular solid solubilisers, which are solid at room temperature, e.g. Fatty alcohol ethoxylates of higher molecular mass.
• solubilizers in particular solid solubilisers, which are solid at room temperature, e.g. Fatty
• solubilizers are not used as individual substances but as mixtures of substances with different degrees of ethoxylation and different lengths of alkyl chains.
• 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.
• 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.
• 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.
• 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.
• solid bodies according to the invention can also be coated with a layer of silicone oil which preferably gives gloss.
• 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).
• 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.
• TAED tetraacetylethylenediamine
• 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,
• 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; Buccorightöl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Beaver-absolue; Cedern generallyöl; 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; Fenne
• 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,
• 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.
• a solid according to the invention which has been solidified using polyethylene glycol.
• preference is given to polyethylene glycols whose molar mass is above 1000 g / mol.
• 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.
• toilet bowls attached to baskets are used with perfume oil and other ingredients, or containers that release various kinds of smelling liquids.
• the fragrance is permanently released, it would be desirable to release the fragrance targeted at certain times.
• 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.
• spheres are used in such a process because they can be moved most reliably in the corresponding metering devices.
• 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 .
• the buoyant body consists either of foamed material or - as already indicated above - from a light core and a heavy, CO 2 releasing 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.
• Unattractive color effects in the bodies according to the invention can be colored by dyes, which are of course preferably water-soluble.
• dyes which are of course preferably water-soluble.
• 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.
• a ball with a diameter of 0.5 cm to 0.99 cm is particularly suitable in this context, 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.
• 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.
• 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.
• 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.
• 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 .
• 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.
• 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.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Fats And Perfumes (AREA)
• Detergent Compositions (AREA)

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Cited By (3)

Citations (3)

• 2007
  • 2007-08-31 EP EP07115457A patent/EP2031047A1/fr not_active Withdrawn

Patent Citations (3)

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