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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/046—Insoluble free body dispenser
• • 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
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap 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
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

• the present invention relates to tablets or unit doses comprising an effervescent system suitable for preparing liquid detergent or cleaning compositions, liquid compositions prepared by dissolving said tablet or unit dose in water and to the use of such tablets or unit doses for preparing said liquid compositions.
• Detergent compositions in the form of tablets or solid unit doses offer advantages in storage, transport and packaging.
• one major disadvantage is that tablets and other unit portions are usually compressed or compacted and therefore do not always disintegrate, dispense or dissolve satisfactorily in water. This might result in an inefficient delivery of the active agents or to any remainder of the tablet in the water.
• One solution for this problem presented in the prior art is the incorporation of effervescent systems into a tablet, which form gas upon contact with water and thereby contribute to improved disintegration, dissolution and dispersion of the tableted or portioned composition.
• effervescent systems advantageously allows the very rapid disintegration, dispensing and dissolution of the solid dosage forms, such as tablets and other unit portions.
• minimal to none manipulation is needed in order to ensure appropriate mixing of the constituents including the active agents of the solid dosage compositions, in particular tablets, such that uniform applications can be assured with the reconstituted aqueous solutions, including water softening, cleaning and detergent solutions.
• tablets/unit portions of detergent compositions comprising effervescent systems based on an acid-base system are sometimes difficult to store, especially in a humid or moist environment as too high air humidity can already start the effervescent reaction which results in physical instability of the tablet or unit portion.
• compositions comprising effervescent systems which are intended to be offered as tablets/unit portions have to be carefully balanced in view of storage stability, dissolution properties and performance aspects.
• WO-A-98/24873 describes tablets containing an effervescent and disintegrant system in the core and are coated with a coating to increase the stability thereof.
• the additional step of incorporating a coating causes the manufacturing method to be more complex than desired.
• WO-A-93/08255 describes effervescent tablets comprising perfume and sorbitol as a vehicle.
• EP-A-1134281 describes detergent tablets comprising a non-compressed phase, in which components which are sensitive to compression are found, and a compressed phase, such that the washing process can be better controlled. Nevertheless, the method for manufacturing same is complex.
• WO-A-00/04117 and WO-A-00/04124 describe multi-phase detergent tablets, in which an effervescent system acting as a disrupting agent for the tablet is found in one of the phases.
• the preferred embodiments thereof also describe that the different phases are compressed at different pressures, thereby complicating the manufacturing method.
• WO-A-02/086048 describes an effervescent tablet comprising a compound with germicidal properties and an effervescent system formed by an acid component and a basic component. Nevertheless, they must be stored at a temperature lower than room temperature and a humidity of less than 20 percent.
• WO-A-02/99026 describes a method for enhancing the dissolution of a solid material in a liquid involving the use of an effervescent system including an enzyme and a substrate for the enzyme to generate gas therefrom.
• WO-A-03/062360 describes a detergent tablet including an effervescent system, polyethylene glycol and an organic compound with two polar groups, such as 1,6-hexanediol for improving the dissolution of the components of the formulation, for example.
• WO-A-2012/045907 describes compositions comprising between 20 percent and 30 percent by weight of sodium lauryl sulfate and an effervescent disintegrant adjuvant formed by citric acid and sodium carbonate or sodium bicarbonate.
• WO-A-2016/087639 describes effervescent detergent compositions comprising pectin as storage and disintegration supporting material.
• US-A-20180105766 describes detergent tablets including an effervescent system based on an organic acid and an alkaline carbonate or bicarbonate, an alkylsulfate-type anionic surfactant and a disintegrating agent.
• the object of the present invention is to provide a detergent composition in dry, pre-portioned, compact, weight and space saving form allowing to prepare a liquid detergent / cleaning composition by the consumers themselves in an easy and plastic waste avoiding manner.
• the liquid detergent / cleaning composition should be preparable fast, non-elaborately and without any solid, greasy or unattractive remainders in the liquid composition.
• the detergent or cleaning compositions in form of a tablet or unit dose for preparing a liquid composition according to the invention.
• the tablet or unit dose for preparing the cleaning or detergent compositions according to the present invention comprise an effervescent system, a nonionic surfactant and a further chelating agent, which is different from citric acid /citrate, preferably an amino acid-based chelating agent.
• a cleaning or detergent composition in form of a tablet or a unit dose comprising an effervescent system can be suitably stored and readily dissolved in water resulting in a ready-to-use liquid cleaning composition, e.g. for cleaning hard surfaces, if said tablet / unit dose comprises besides said effervescent system at least a nonionic surfactant and a chelating agent.
• effervescent system relates to a combination of compounds or mixture of compounds which result in the generation and release of a gas when administered to a liquid or when in contact with a liquid.
• Any effervescent system known in the art may be used according to the invention.
• the effervescent system is preferably present in an amount ranging from 25 to 95 wt.-%, dependent from the type of liquid composition to be prepared, e.g. a bath, kitchen, floor cleaning, dish washing or a further detergent composition.
• Such a tablet or unit dose cleaning or detergent composition may comprise the effervescent system in an amount of 30 to 90 wt.-%, preferably 35 to 87,5 wt.-%, more preferred 40 to 85 wt.-%, even more preferred 45 to 82,5 wt.-% or 50 to 80 wt.-% of the solid cleaning or detergent composition
• Each individual ingredient of the effervescent system according to the invention is soluble in water of 20°C up to at least 5 gram per 100 ml.
• the acidic component is preferably selected from tricarboxylic acids, dicarboxylic acids, including unsaturated dicarboxylic acids, inorganic acids, and salts thereof or derivatives thereof, e.g. naturally occurring unsaturated variants of the acids cited below (like e.g. aconitic acid, an unsaturated variant of citric acid).
• suitable acidic components of the present invention include citric acid, isocitric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, malic acid, adipic acid, amidosulfonic acid, maleic acid, glutaconic acid, acrylic acid, methacrylic acid, mono sodium citrate, di sodium citrate; one particularly preferred acidic component is citric acid or salts thereof, even more preferred is anhydrous citric acid or a salt thereof, in particular sodium citrate, or a combination of citric acid and a citrate. It is preferred to add citrate, in particular sodium citrate to the composition to reduce foaming of the liquid during dissolution of the tablet / unit dose.
• the acidic compound in this invention is most preferably anhydrous. Further the acidic compound is preferably free of Ca and Mg ions (this means no components are included comprising Ca or Mg as counter-ions).
• the acidic component(s) of the effervescent system is/are preferably present in a total amount ranging from 10 wt.-% to 90 wt.-%, preferably in a total amount ranging from 25 wt.-% to 85 wt.-%, more preferably in a total amount ranging from 30 wt.-% to 80 wt.-%, even more preferred 40 to 70 wt.-% based on the total weight of the effervescent system.
• the basic / alkaline component is preferably selected from carbonates, bicarbonates, percarbonates, sesquicarbonates, and derivatives thereof including for example sodium and potassium forms, and derivatives thereof.
• Preferred basic components are carbonates and/or bicarbonates, particularly preferred are sodium or potassium carbonate / bicarbonate, even more preferred are anhydrous sodium or potassium bicarbonate. These compounds can be included either separately, or in combination. According to the invention it might be preferred that the effervescent system includes at least one carbonate and at least one bicarbonate.
• the basic component(s) is/are essentially free of calcium of magnesium salts or ions, wherein "essentially free” means that the basic component comprises less than 1% of such ions, preferably less than 0.5%, more preferred less than 0.2%, less than 0.1% or less than 0.05%. Most preferred the basic component is free of such ions.
• the basic component in this invention is most preferably anhydrous.
• the effervescent system according to the invention comprises at least citric acid and sodium bicarbonate; or at least citric acid, sodium citrate and sodium bicarbonate; or at least citric acid, sodium citrate, sodium and/or potassium carbonate and sodium bicarbonate; or consists of said components.
• the basic component of the effervescent system is preferably present in a total amount ranging 10 wt.-% to 90 wt.-%, preferably in a total amount ranging from 25 wt.-% to 85 wt.-%, more preferably in a total amount ranging from 30 wt.-% to 80 wt.-%, even more preferred 40 to 70 wt.-% based on the total weight of the effervescent system.
• the effervescent system consists of the acidic and the basic components.
• the ratio of the acidic to the basic component in the effervescent system preferably ranges from 1:6 to 10:1, more preferably from 1:6 to 6:1, even more preferably from 1:2 to 6:1, most preferably from 1:1 to 4:1 (wt/wt).
• the molar ratio of acid groups to carbonate-groups (CO 3 2- ) or bicarbonate-groups (HCO 3 - ) in the effervescent system ranges from 8:1 to 1:1, more preferably from 7:1 to 1.25:1, more preferably from 6:1 to 1.5:1, most preferably from 5:1 to 2:1.
• the acid groups are carboxylic acid groups.
• the molar ratio of tricarboxylic acid to carbonate-groups (CO 3 2- ) or bicarbonate-groups (HCO 3 - ) in the effervescent system ranges from 2.7:1 to 0.3:1, more preferably from 2.3:1 to 0.4:1, more preferably from 2:1 to 0.5:1, most preferably from 1.7:1 to 0.7:1.
• the effervescent system according to the invention comprises a water content ranging from 0 to 5, preferably from 0 to 4, more preferably from 0 to 3, even more preferably from 0 to 2, still even more preferably from 0 to 1, still even more preferably from 0 to 0.5, and most preferably from 0 to 0.25 wt.-% of the total composition.
• the water content is defined by the amount of water which evaporates when the composition or components are heated to 105 °C.
• the detergent or cleaner composition comprises at least one nonionic surfactant. It has been found that the presence of a nonionic surfactant, particularly at least one of the surfactants described herein just below, results in a fast and effective water absorption of the tablet / unit dose and furthermore limits the foam development, thus preventing that the liquid solution during preparation foams over the container. Therefore, it can be avoided that the user has to come in contact with the solution or has to clean the container outer surface.
• Preferred nonionic surfactants are alkoxylated fatty alcohols, alkoxylated fatty acids or combinations thereof.
• the relative hydrophilic alkoxy-chain comprises or essentially consists of ethylene oxide, propylene oxide or butylene oxide or combinations thereof.
• Preferably said alkoxy-chain comprises or essentially consists of ethylene oxide or propylene oxide units, in particular ethylene oxide units.
• the length of the alkoxy chain can vary between averagely 15 and averagely 200 ethylene oxide-, propylene oxide- or butylene oxide-groups or combinations thereof, including 15, 16, 18, 20, 25, 30, 40, 50, 80, 100 and the ranges between the particularly mentioned. It is preferred that the chain comprises mainly or consists of ethylene oxide. Ethoxylated fatty alcohols are particularly preferred.
• the relative hydrophobic hydrocarbon-chain of the fatty alcohol or fatty acid can be saturated, mono-unsaturated or poly-unsaturated and linear or branched.
• the length of this hydrocarbon-chain varies between 4 and 30 carbon molecules, including 6, 8, 10, 11, 12, 14, 16, 18, 20, 22, 24, 26 or 28.
• Preferred surfactants of this type may be represented by the formula R 1 O-(CH 2 CH 2 O) x -(CH(CH 3 )CH 2 O) y -H, wherein R 1 is a linear or branched, saturated or unsaturated hydrocarbon residue having 4 to 30 C atoms, preferably 6 to 26, even more preferred 10 to 24 C atoms, x preferably is an integer of from 15 to 200 (including 16, 18, 20, 25, 30, 40, 50, 80, 100), preferably from 20 or from 25 to 100, y preferably is an integer of from 0 to at most 100 and x+y is below 200. In a preferred embodiment in at least one of the nonionic surfactants x is at least 26, preferably at least 30, and even more preferred at least or more than 40, however, below 200. R 1 preferably is a linear, saturated hydrocarbon residue.
• alcohol ethoxylates that can be prepared by ethoxylation of a fatty chain alcohol.
• the preferred alcohol ethoxylates have a hydrocarbon-chain that ranges from 4 up to 26 carbon molecules, including 4, 6, 8, 10, 12, 14, 16, 18, 20, 22 and between averagely 15 and averagely 200 ethylene oxide-groups, including averagely 16, 18, 20, 25, 30, 40, 50, 80, 100 ethylene oxide-groups.
• Ethoxylated fatty alcohols having at least 20 EO units are preferred, such having at least 25 EO units are particularly preferred.
• One example of such a preferred surfactant is C16-18 fatty alcohol 25 EO, commercially available as Lutensol AT25 from BASF.
• fatty acid ethoxylates that can be prepared by a reaction of fatty acid with ethylene oxide or a polyglycol with the general formula RCOO - (CH 2 CH 2 O) n H.
• a polyglycol When a polyglycol is used a mixture of mono- and di-esters (RCOO - (CH 2 CH 2 O) n -OCOR) is produced.
• the preferred fatty acid has a hydrocarbon-chain R that varies from 4 up to 26 carbon molecules, including 4, 6, 8, 10, 12, 14, 16, 18, 20, 22.
• the number of ethylene oxide-groups in the fatty acid ethoxylate is between averagely 15 and averagely 200 ethylene oxide-groups, including averagely 16, 18, 20, 25, 30, 40, 50, 80, 100 ethylene oxide-groups.
• the nonionic surfactant(s) described above is/are present in a total amount of 1 to 20 wt.%, preferably in an amount of 2 to 18 wt.%, more preferred in an amount of 3 to 15 wt.%, even more preferred in an amount of 4 to 12 wt.%, based on the total weight amount of the tablet or unit dose composition.
• nonionic surfactant(s) Besides the here mentioned nonionic surfactant(s) further surfactants can be present, as discussed below.
• the composition of the present invention contains a chelating agent.
• the chelating agent(s) have the double-function of chelating ions in the solution to prevent any precipitation in the liquid composition, and further to support the cleaning result of the composition in particular in removing calc staining, even by use of alkaline liquid compositions.
• Chelating agents can include any of those known in the art, however, according to the invention are different from citric acid or citrate. This means that besides the citric acid or citrate of the effervescent system a further chelating agent is present in the composition.
• Preferred chelating agents are biodegradable chelating agents like amino acid-based chelating agents, in particular methyl glycine di-acetic acid (MGDA) and di-carboxymethyl glutamic acid (GLDA), preferably as alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof, in particular as sodium salts.
• Another preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
• Further carboxylate chelating agents include oxalic acid, salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, lactic acid or mixtures thereof.
• Ethylenediamine N,N'- disuccinic acids especially the (S,S) isomer have been extensively described in US patent 4, 704, 233 .
• Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
• Further amino carboxylates that may be used herein include ethylene diamine terra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
• DTPA diethylene triamine pentaacetate
• DTPA diethylene triamine pentaacetate
• DTPA diethylene triamine pentaacetate
• DTPA diethylene triamine pentaacetate
• DTPA diethylene triamine pentaacetate
• DTPA diethylene triamine pentaacetate
• PDTA propylene diamine tetracetic
• Suitable phosphonate chelating agents are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
• EDTA ethylenediamine-N,N'-tetraacetic acid
• EDDS ethylenediamine-N,N'-disuccinic acid
• Preferred EDTA or EDDS compounds are the free acid form and the sodium salt or complex thereof.
• Still other chelating agents are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP 0317542 A2 and EP 0399133 A1 .
• the tablet or unit dose compositions according to the present invention comprise a total amount of from 0,1 up to about 15 wt.%, preferably from 0,3 to 10 wt.%, more preferably from 0,5 to 8 wt.%, even more preferred from 0,8 to 5 wt.% or 1 to 3 wt.% of a chelating agent, or a mixture of chelating agents (different from citric acid or citrate) based on the total weight amount of the tablet or unit dose composition
• the compositions comprise only biodegradable chelating agents, most preferred selected from MGDA and GLDA, or a combination of those.
• the tablet or unit dose composition of the present invention is intended to provide a ready-to-use liquid detergent or cleaning composition, in particular a detergent or cleaning composition for hard surfaces, by just adding one tablet or unit dose to a predetermined amount of water.
• the tablet or unit dose is therefore provided in a defined weight amount, calculated to be dissolved in a defined volume of water.
• the weight amount of the tablet preferably is calculated for a water volume in the range of 300 ml to 1 I, e.g. 300 ml, 400 ml, 500 ml, 600 ml, 700 ml, 750 ml, 800 ml or 1 I.
• the tablet or unit dose for providing the liquid composition in this volume preferably is provided in a weight amount of from 3 to 20 g, calculated such that preferably an amount of 4 to 10 g, more preferred 5 to 8 g is added to 500 ml of water.
• the amounts mentioned herein should be considered as preferred examples, not as limiting the invention to said specific amounts.
• the liquid detergent or cleaning composition obtained by adding one of the tablet / unit dose to water should not comprise any solid remainder(s), preferably no greasy/oily film on the surface and should be pleasantly to prepare and to use. Therefore, it is particularly preferred that the composition comprises only ingredients fully dissolvable in water in the amounts as calculated for the tablet / unit dose ingredients in the water volume as specified. Dissolution of the tablet and remaining all the ingredients of the composition dissolved during storage is noticeably increased by the use of a combination of the above-mentioned nonionic surfactants and a chelating agent.
• the tablet of unit dose composition is essentially free of Ca and Mg ions, thus, doesn't comprise any component including Ca or Mg, wherein "essentially free” means that the composition comprises less than 1% of such ions, preferably less than 0.5%, more preferred less than 0.2%, less than 0.1% or less than 0.05%. Most preferred the water softener composition is free of such ions.
• the tablet or unit dose composition of the present invention when solved in water either provides an acidic pH or an alkalic pH due to the components of the composition.
• the pH of the obtained liquid composition is acidic.
• the pH obtainable by adding the composition into water is in the range of pH 1 to 6, preferably 2 to 5,8 and most preferred 3 to 5,5.
• This pH is obtained by applying a unit amount of a 12-14 g tablet into 1 I of water (20°C) after full disintegration.
• a composition resulting in a solution providing said pH ranges is herein named "acidic" composition.
• compositions can be suitably used as "bath cleaners", for cleaning all surfaces being often in contact with water, but also if desired as kitchen or floor cleaners.
• pH of the liquid composition is neutral to slightly alkaline, thus, in range of pH 7 to 11, preferably from pH 7 to 10.
• the tablet or unit dose composition according to the invention comprises a water content ranging from 0 to 5, preferably from 0 to 4, more preferably from 0 to 3, even more preferably from 0 to 2, still even more preferably from 0 to 1, still even more preferably from 0 to 0.5, and most preferably from 0 to 0.25 wt.-% of the total composition.
• the water content is defined by the amount of water which evaporates when the composition or components are heated to 105 °C.
• the detergent or cleaning composition according to the invention comprises besides the effervescent system, the nonionic surfactant(s9 and the chelating agent(s) as cited above at least one or more further component(s) selected from: further surfactants, pH adjusting ingredients, colorants, dyes, preservatives, perfumes, and optionally builders, bleaching agents or bleaching compositions, water soluble fillers, enzymes, water soluble tablet binders and disintegrants. More preferably the composition comprises at least one component selected from: further surfactants, pH adjusting agents and preservatives; most preferably the composition comprises at least at least one further surfactant.
• Said one or more additional component(s) amount(s) to a total amount of 2 to 50 wt.-% based on the total weight of the tablet or unit dose composition, preferably 5 to 45 wt.-%, more preferred 7 to 40 wt.-%, even more preferred 8 to 35 wt.-% of the total weight of the composition.
• the cleaning or detergent composition may comprise additionally a total amount of 0.5 to 50 wt.-%, preferably 1 to 40 wt.-%, 2 to 30 wt.-%, 2.5 to 20 wt.-% or 3 to 15 wt.-% of any further surfactant(s).
• the mentioned ranges refer to the total amount of the added additional surfactants, thus, if a mixture of surfactants is comprised in the composition the sum of the added amounts shall be inside the mentioned ranges and refers to the total amount of the tablet or unit dose composition.
• Suitable surfactants for additional use in the composition herein may be further nonionic surfactants (differing from them cited above), gemini surfactants, amphoteric surfactants, anionic surfactants, zwitterionic surfactants, cationic surfactants or a combination thereof, wherein anionic and non-ionic surfactants are particularly preferred.
• Suitable further nonionic surfactants are e.g. alkyl amine oxides, in particular amine oxides having one alkylene chain with C 6-25 , including 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 carbon atoms, and two short alkyl chains including 1, 2 or 3 carbon atoms.
• a particularly preferred amine oxide is N-dodecyl-N,N-dimethyl amine oxide.
• nonionic surfactants are alkoxylated fatty alcohols or alkoxylated fatty acids, wherein the alkoxy-chain comprises or essentially consists of less than 15 ethylene oxide, propylene oxide or butylene oxide units or combinations thereof.
• said alkoxy-chain comprises or essentially consists of ethylene oxide or propylene oxide units, in particular ethylene oxide units.
• the length of the alkoxy chain of the additional surfactants is below 15 and preferably ranges from 2 to 14, more preferred from 3 to 10, even more preferred from 3 to 8, including 4, 5, 6, and 7. It is preferred that the chain comprises mainly or consists of ethylene oxide. Ethoxylated fatty alcohols are particularly preferred.
• the hydrocarbon-chain of the fatty alcohol or fatty acid can be saturated, mono-unsaturated or poly-unsaturated and linear or branched.
• the length of this hydrocarbon-chain varies between 4 and 30 carbon molecules, including 6, 8, 10, 11, 12, 14, 16, 18, 20, 22, 24, 26 or 28.
• Nonionic surfactants can be "end-capped” by a methyl or an ethyl group at the end of the alkoxy-chain. This effects the properties of the surfactant, e.g. it decreases the foaming behaviour. It is also known that nonionic surfactants can be "end-capped” with a fatty alcohol or a fatty acid where the hydrocarbon-chain varies from 4 up to 26 carbon molecules, including 4, 6, 8, 10, 11, 12, 14, 16, 18, 20, 22. The structure of the surfactants than is "hydrocarbon chain - alkoxy chain - hydrocarbon chain".
• additional nonionic surfactants are amine ethoxylates that can be prepared by addition of ethylene oxide to primary or secondary fatty amines. With primary amines both hydrogen atoms on the amine group react with ethylene oxide. These surfactants have a cationic character when there are a few ethylene oxide units and the pH is low. Under alkaline conditions the surfactant is water soluble when the alkyl chain is not long.
• ethylene oxide-propylene oxide co-polymers which may be prepared with a starting material that reacts with ethylene oxide (EO) or propylene oxide (PO) or a mixture of EO and PO (resulting in block copolymers).
• the starting materials that can be used are (difunctional) poly(oxypropylene glycol) or (difunctional) poly(oxyethylene glycol) or glycerol (for trifunctional products) or ethylene diamine (for tetrafunctional products).
• sucrose esters that may be produced by esterification of sucrose with fatty acids or fatty glycerides.
• Alkyl polyglucosides may be produced by a reaction of a fatty alcohol with a glucose.
• Preferred APGs can have averagely one to averagely four glucose units and has a hydrocarbon-chain that varies from 4 up to 26 carbon molecules, including 4, 6, 8, 10, 12, 14, 16, 18, 20, 22.
• composition may comprise anionic surfactants.
• anionic surfactants comprise or consist of a hydrophobic chain and an anionic hydrophilic group.
• the hydrophilic group can be a carboxylate, C n H 2n+1 COO - X, a sulphate, C n H 2n+1 OSO 3- X, a sulphonate, C n H 2n+1 SO 3- X, phosphate, C n H 2n+1 OPO(OH)O - X, a sulphosuccinate, a isethionate, a taurate or an other anionic hydrophilic group.
• Particularly preferred anionic surfactants are sulphates and sulphonates.
• Sulphate surfactants can be produced by a reaction of an alcohol with sulphuric acid, chlorosulphonic or sulphur dioxide and are esters of sulphuric acid.
• the surfactant properties can optionally be modified by for example introducing ethylene oxide units in the chain so it becomes an alcohol ether sulphate.
• Suitable examples of preferred anionic surfactants are alkyl benzene sulfonates, alkanesulfonates, fatty alcohol sulfates or similar suitable anionic surfactants.
• Common types of sulphonate surfactants are alkyl aryl sulphonate (e.g. sodium alkyl benzene sulphonate, naphthalene sulphonate, alkyl naphthalene sulphonate), paraffin sulphonates, linear alkyl benzene sulphonate (LABS), alpha-olefin sulphonates, sulphosuccinates (as mono- or di-esters or a mixture thereof).
• alkyl aryl sulphonate e.g. sodium alkyl benzene sulphonate, naphthalene sulphonate, alkyl naphthalene sulphonate
• paraffin sulphonates e.
• Alpha-olefin sulphonates can be prepared by reacting linear alpha-olefin with sulphur trioxide, yielding in a mixture of alkene sulphonates, 3- and 4-hydroxyalkane sulphonates, di-sulphonates and other species.
• the properties of sulphonate surfactants can optionally be modified by introducing ethylene oxide units in the chain.
• Preferred alkyl phosphates and alkyl ether phosphates can be made by treating fatty alcohols or alcohol ethoxylates with a phosphorylating agent which yields in a mixture of mono- and di-esters of phosphoric acid.
• Such surfactants have typically a quartery nitrogen and usually four alkyl chains independently with C 1 to C 20 .
• alkyl chains are independently methyl-, ethyl-, propyl-, butyl- as typical short chains and lauryl-, myristyl-, palmityl- or stearyl-chains as typical long chains.
• a typical cationic surfactant has at least one short chain, often two short chains e.g. methyl, and at least two longer chains, independently selected from lauryl-, myristyl-, palmityl- or stearyl-chains.
• amphoteric (zwitterionic) surfactants can be additionally added.
• the most representative amphoteric surfactants are betains or sulphobetains.
• the tail can for example consists of glucoside, poly-glucoside or a hydrocarbon chain.
• the hydrocarbon chain can be saturated or unsaturated, branched or linear.
• the ion-group can be cationic (e.g. ammonium), anionic (e.g. phosphate, sulphate, carboxylate) or nonionic.
• the spacer can be short or long methylene groups, rigid (stilbene), polar (polyether, polyethyleenoxide), and nonpolar (aliphatic, aromatic).
• the pH of the liquid detergent or cleaning composition may directly result from the ratio of the acidic and basic components of the effervescent system. Nonetheless, it might be further suitable to adapt the pH of the solution by adding further pH adjusting agents to the tablet or unit dose composition.
• acidifier/acidification agents any component which when released, acts such as to reduce the pH of the wash solution containing the dissolved/dispersed composition.
• Suitable acidification agents for use in the composition of the present invention include inorganic and organic acids including, for example, carboxylate acids except citric acid or citrate, like e.g. succinic acids, oxalic acid, or polycarboxylate acids, such as polyacrylic acid, and also acetic acid, boric acid, malonic acid, adipic acid, fumaric acid, lactic acid, glycolic acid, tartronic acid, maleic acid, their derivatives and any mixtures of the foregoing.
• Alkaline agents for raising the pH above 7 - besides the alkaline / basic components of the effervescent system - might be selected from soap, NaOH and KOH.
• Suitable perfumes include blooming perfumes, perfume oils, and perfume raw materials comprising alcohols, ketones, aldehydes, esters, ethers, nitriles alkenes, and mixtures thereof.
• ester type perfumes include benzylacetate, phenoxyethylisobutyrat, p-tert.-butylcyclohexylacetat, linalylacetat, dimethylbenzyl-carbinylacetate, phenylethyl acetate, linalyl benzoate, benzylformiate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionats and benzylsalicylate.
• ether type perfumes are benzylethylether, and for example linear C 8 -18 alkanals, citral, citronellal, citronellyl oxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
• ketones are ionones, alpha -isomethylionone and methyl-cedrylketone
• examples for alcohols are anethol, citronellol, eugenol, geraniol, linalool, phenylethylalkohol and terpineol
• examples for carbohydrates are terpene including limonen and pinen.
• fragrances may be preferred. These may include naturally occurring oils such as for example from pine, citrus, jasmine, patchouli, rose, ylang ylang, sage, camomille, cloves, balm, mint, orange flower, orange peel, sandel wood, neroliol, cinnamon, lime-tree blossom, juniper berry, vetiver, olibanum, galbanum and labdanum.
• naturally occurring oils such as for example from pine, citrus, jasmine, patchouli, rose, ylang ylang, sage, camomille, cloves, balm, mint, orange flower, orange peel, sandel wood, neroliol, cinnamon, lime-tree blossom, juniper berry, vetiver, olibanum, galbanum and labdanum.
• the amount of perfumes may preferably be present in an amount of up to 3 wt.-%, more preferably in an amount of from 0,1 to 2,5 wt.-%, based on the total weight of the composition.
• Suitable colorants and dyes include all kinds of colorants and dyes Particularly suitable are colorants which are water soluble or soluble in at ambient temperature liquid organic solvents.
• a preferred type of colorants are polymeric colorants, sold by Milliken under the name “liquitint®” in several colours.
• colorants include anionic dyes like for example anionic nitroso dyes.
• One possible suitable dye is naphthol green (Colour Index (CI) part 1: Acid Green 1; Part 2: 10020), which is commercially available as Basacid TM Green 970 from BASF, (Ludwigshafen, Germany) and mixtures thereof with suitable blue dyes.
• Pigmosol TM Blue 6900 (CI 74160), Pigmosol TM Green 8730 (CI 74260), Basonyl TM Red 545 FL (CI 45170), Sandolan TM Rhodamin EB400 (CI 45100), Basacid TM Yellow 094 (CI 47005), Sicovit TM Patentblue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol TM Blue GLW (CAS 12219-32- 8, CI Acidblue 221), Nylosan TM Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) und/oder Sandolan TM Blue (CI Acid Blue 182, CAS 12219-26-0).
• the amount of colorants is preferably from 0,01 to below 1 wt.%, preferably below 0.5 wt.-%, more preferably below 0.1 wt.-%.
• Suitable preservatives for use herein include compounds with antimicrobial effect.
• suitable preservatives according to the present invention may be selected from the group including alcohols, aldehydes, antimicrobial acids, carbonic acid esters, acid amides, phenols, phenol derivatives, sorbates like sodium or potassium sorbate, diphenyls, diphenyl alkans, urea derivatives, oxygen-nitrogen-acetales, formates, benzamidines, substituted isothiazoles, and hydrated isothiazol derivatives, such as for example isothiazolinen and isothiazolidinen, phthalimid derivatives, pyridine derivatives, antimicrobial surfactants, such as for example antimicrobial quarternary surfactants, guanidines, antimicrobial amphoteric compounds, chinoline, 1,2-dibrom-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, io
• Materials which can be binders and/or disintegrants according to the present invention include organic materials such as starches, for example, corn, maize, rice and potato starches and starch derivatives, such as carboxymethyl starch, modified or pregelatinized starch and sodium starch glycolate; celluloses and cellulose derivatives, for example, carboxymethyl cellulose, cross-linked modified cellulose, and microcrystalline cellulose; pectin, sugars (for example, glucose, sucrose, lactose, mannitol, sorbitol, dextran, maltodextrin, mannitol,); carrageenan, alginate; shellac; xanthan gum; naturally derived waxes like bees wax and hydrogenated jojoba wax, carnauba and rice bran wax and synthetic waxes, paraffin, talcum, gelatine, lanolin, and various synthetic organic polymers, notably polyethylene glycol and derivatives, polyvinylalcohol, polyvinylacetate, polyvinyl
• the binder/disintegrant - if present - is preferably used in a combined amount within the range of from 0.01 to 10 wt.-%, more preferably from 0,1 to 8 wt.-%, most preferably from 0,5 to 5 wt.-% based on the total weight of the tablet or unit dose composition.
• Enzymes may be present as components of the compositions, dependent from their desired use. E.g. in dishwashing compositions suitable enzyme are preferably included. Where present, said enzymes are selected from proteases, cellulases, hemicellulases, gluco-amylases, amylases, mannanases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, glucanases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, arabinosidases,, hyaluronidase, chondroitinase, laccase, or mixtures thereof, without being limited to the mentioned.
• particularly preferred enzymes include protease, amylase, lipase, cellulases, mannanase or mixtures thereof, optionally in conjunction with one or more plant cell wall degrading enzymes.
• Said enzymes are normally incorporated in the compositions herein at levels from 0.0001 % to 2% of active enzyme by weight of the compositions/tablets.
• the enzymes can be added as separate single ingredients (pills, granulates, stabilized liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (e. g. co-granulates).
• Kit of use tablet / unit dose and container for the liquid composition
• the present invention further refers to a kit comprising at least one container for preparing the liquid detergent or cleaning composition therein by adding a tablet or unit dose of the composition to a specified volume of water.
• Said kit comprises at least one tablet or unit dose of the composition of the present invention and a container.
• the kit preferably comprises at least 2, more preferred at least 3, at least 5, at least 8 or at least 10 tablets or unit doses of the composition of the present invention and a container.
• Said container preferably is adapted to the intended use, e.g. can be provided with a pull-to open cap, a push-to-open cap, a turn-to-open cap, a spray head, a dosing system etc. Further, the container provides an opening designed concerning size and shape so that the tablet or unit dose can be fed through and/or included into the container without any difficulties. Preferably the container comprises the opening at the top, which after addition of the tablet or unit dose is closed with the cap or head suitable for use.
• the tablet or unit dose may be provided in any suitable package.
• Tablets for cleaning compositions have been prepared having the compositions as shown in table 1. Each of the tablets had a weight of 6 g and they have been used to prepare cleaning compositions by adding any of the tablets into 500 ml of water. Properties of the liquid cleaning compositions are determined. Compositions A to D are according to the invention, R 1 and R 2 are references. Table 1.
• Formulations of tablets amounts in wt.% Formulation A B C D E R2 R3 Citric acid 20 35 20 20 45 30 30 Sodium citrate 10 5 2 5 1 Sodium carbonate 25 25 20 25 20 8 8 Sodium bicarbonate 5 2 10 5 5 20 20 Pottash 10 12 C16-18 fatty alcohol 25EO Lutensol AT25 8,5 8,5 7 9 5 8 C10/C13 aminoxide 3 4 3 5 2 Na laurylsulfate 2 2 1 4 4 soap 2 Alpha olefin sulfate Hostapur OSB (Clariant) 5 MGDA 2 5 2 1,5 5 3 Acidifier, preservatives, perfumes, colorants, binders etc.

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• 2019
  • 2019-11-21 EP EP19210596.3A patent/EP3825392A1/de active Pending

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