EP2981601B1 - Flüssigreinigungszusammensetzung - Google Patents

Flüssigreinigungszusammensetzung Download PDF

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Publication number
EP2981601B1
EP2981601B1 EP14710300.6A EP14710300A EP2981601B1 EP 2981601 B1 EP2981601 B1 EP 2981601B1 EP 14710300 A EP14710300 A EP 14710300A EP 2981601 B1 EP2981601 B1 EP 2981601B1
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Prior art keywords
copolymer
weight
composition according
liquid cleaner
cleaner composition
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French (fr)
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EP2981601A1 (de
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Adam Peter Jarvis
James Merrington
Stephen John Singleton
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • This invention relates to a liquid cleaner composition. It particularly relates to a liquid cleaner composition comprising a copolymer which is effective as suspending active. The invention also relates to a method for preparing the liquid cleaner composition and use of the liquid cleaner composition.
  • a particular challenge is provided when it is desired to incorporate particles or gases in a formulation. For many applications these should be suspended in the formulation without separating by precipitation, creaming or phase separation. Particles of very small dimensions may be kept in a dispersed state by means of colloidal stabilisation. Such stabilisation is much harder for larger particles or encapsulates or for instance air bubbles.
  • it is often desirable to incorporate and stabilise particles of visible dimensions in a formulation for instance to provide a visual cue to the consumer, or to enable abrasive cleaning. In these cases it would be impractical or very unattractive if such particles needed to be re-suspended, for instance by shaking, every time a consumer wants to use the composition. It is therefore an object of the present invention to provide cleaning compositions with rheological characteristics enabling suspension of particles or air bubbles.
  • Hydrodynamic thickeners work by utilizing acid groups in their structure that form anionic charges when the pH is high enough (e.g. at neutral pH). These charges repel each other causing the polymer chains to expand and entangle. Thickening and suspending effects of the neutralized polymers are due to increased physical packing of the molecules. These materials are also known as "space filling” or "volume exclusion”. Both viscosity and yield point increase with concentration. The alkali swellable emulsions (ASE) and carbomers fall within this category.
  • WO 2010/026097 A1 describes rheology modifiers for use in home and personal care compositions. These modifiers are formed from four monomers. They include an amino-substituted vinyl monomer, a hydrophobic nonionic vinyl monomer (such as a C1-C30 alkyl ester of acrylic or methacrylic acid), an associative-like monomer (with a polyoxyalkylene unit end-capped with a hydrophobic group), and a further associative-like vinyl monomer.
  • a hydrophobic nonionic vinyl monomer such as a C1-C30 alkyl ester of acrylic or methacrylic acid
  • an associative-like monomer with a polyoxyalkylene unit end-capped with a hydrophobic group
  • a further associative-like vinyl monomer such associative-like vinyl monomer.
  • (meth)acrylic acid refers to "methacrylic acid and/or acrylic acid”. The same applies mutatis mutandis to "(meth)acrylate” and its derivatives.
  • the composition is sprayable, and even more preferred that the composition is sprayable from a trigger spray bottle.
  • sprayable it is meant that the composition is suitable to be dispensed in the form of a spray or a mist of fine droplets, for instance by expelling the composition through a suitable nozzle.
  • the composition is suitable to be dispensed in the form of a foam.
  • the C 1 -C 10 alkyl(meth)acrylates forming the above chain are preferably selected from one or more of methyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl-hexyl (meth)acrylate. Furthermore, it is preferred that the C 1 -C 10 alkyl(meth)acrylates are C 1 -C 10 alkylmethacrylates, because these alkylmethacrylates are more favourably prepared by catalytic chain transfer polymerisation. It is even more preferred that the C 1 -C 10 alkylmethacrylates are selected from one or more of methylmethacrylate, butyl methacrylate, and 2-ethyl-hexyl methacrylate. Homo- or copolymers of these monomers have shown to be particularly efficacious.
  • A preferably comprises from 70 to 100 %, more preferably from 80 to 100% and even more preferably from 90 to 100% of C 1 -C 10 alkyl(meth)acrylates by weight with respect to the weight of A.
  • A comprises from 0 to 30 %, more preferably from 0 to 20 % and even more preferably from 0 to 10 % of (meth)acrylic acid by weight with respect to the weight of A.
  • the macromonomer has a number average molecular weight ranging from 500 to 10,000.
  • the number average molecular weight of A is between 500 and 2000, and more preferably between 700 and 1500.
  • Table 1 shows the structures of three preferred macromonomers.
  • Table 1 Macromonomer Structure PMMA (1) PBMA (2) PEHMA (3) (1) polymethylmethacrylate macromonomer (2) poly-n-butylmethacrylate macromonomer (3) poly-(2-ethyl-hexyl)methacrylate macromonomer
  • the value of a (indicating the amount of A in the copolymer) ranges from 0.5 to 25% by weight of the copolymer. Preferably, a ranges from 5 to 18 % by weight, more preferably from 8 to 17 % by weight of the copolymer.
  • cross-linking monomers will be polyunsaturated.
  • Illustrative, non-limiting examples are divinyl benzene, divinyl naphthalene, trivinyl benzene, triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylol propane diallyl ether, 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, trimethylol propane tri(meth)acrylate, polyethoxylated glycol di(meth)acrylate, alkylene bisacrylamides, bisphenol A, polyethyoxylated dimethacrylate, trimethylol propane polyethoxylated trimethacrylate and similar materials.
  • Preferred for the present invention are bisphenol A polyethoxylated glycol diacrylate, trimethylol propane triacrylate and pentaerythritol allyl ether. It is more preferred that wherein D is pentaerithrytol allyl ether.
  • d ranges from 0 to 5% by weight of the copolymer.
  • d ranges from 0 to 2 % by weight, more preferably from 0.5 to 1.5 % by weight, and even more preferably form 0.7 to 1.0 % by weight of the copolymer.
  • the number average molecular weight of the one or more rheology modifier copolymers according to the present invention is preferably 50 000 or more.
  • the number average molecular weight typically is in the range of from 5 ⁇ 10 4 to 5 ⁇ 10 5 g ⁇ mol -1 .
  • the number average molecular weight typically is in the rage of from 5-10 5 to 5 ⁇ 10 6 g ⁇ mol -1 .
  • surfactant i.e. anionic, cationic, nonionic, zwitterionic or amphoteric
  • the one or more surfactants are generally chosen from anionic and non-ionic detergent actives.
  • the cleaning composition may further comprise cationic, and zwitterionic or amphoteric surfactants.
  • Suitable synthetic (non-soap) anionic surfactants are water-soluble salts of organic sulphuric acid mono-esters and sulphonic acids which have in the molecular structure a branched or straight chain alkyl group containing from 6 to 22 carbon atoms in the alkyl part.
  • anionic surfactants water soluble salts of:
  • the preferred water-soluble synthetic anionic surfactants are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkyl-benzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl-naphthalene-sulphonate.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene
  • the amount present in the cleaning compositions of the invention will generally be from 0.1 to 10 %-wt, preferably from 1 to 9, more preferably from 2 to 7 %-wt, and even more preferably from 4 to 6 %-wt.
  • a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom.
  • the length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group can be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants with the right HLB.
  • Particular examples include:
  • nonionic surfactants are:
  • the liquid cleaner composition according to the present invention comprises non-ionic surfactants. It is even more preferred that at least 50 %, still more preferably at least 75 %-wt and still more preferably at least 90% by weight of the surfactants are non-ionic surfactants. Even more preferably, the one or more surfactants are non-ionic surfactants. Thus, it is preferred that the liquid cleaner composition comprises from 0.1 to 10 %-wt, preferably from 1 to 9, more preferably from 2 to 7 %-wt, and even more preferably from 4 to 6 %-wt of one or more non-ionic surfactants.
  • the non-ionic surfactants are selected from ethoxylated alkyl alcohols and alkyl polyglucosides. More preferably the surfactants are ethoxylated alkyl alcohols and even more preferably ethoxylated C 8 -C 12 alkyl alcohols, whereby yet more preferably the average degree of ethoxylation is between 5 and 8.
  • Particular effective (and therefore preferred) surfactants are ethoxylated C 9 -C 11 alkyl alcohols with an average degree of ethoxylation of 8, including for instance the commercially surfactant Neodol 91-8.
  • amphoteric, cationic or zwitterionic surfactants in said compositions.
  • Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane-sulphonate and sodium N -2-hydroxy-dodecyl- N- methyltaurate.
  • a specific group of surfactants are the tertiary amines obtained by condensation of ethylene and/or propylene oxide with long chain aliphatic amines.
  • the compounds behave like nonionic surfactants in alkaline medium and like cationic surfactants in acid medium.
  • Suitable zwitterionic surfactants can be found among derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance betaine and betaine derivatives such as alkyl betaine, in particular C 12 -C 16 alkyl betaine, 3-( N , N -dimethyl- N- hexadecyl-ammonium)-propane-1-sulphonate betaine, 3-(dodecylmethyl-sulphonium)-propane-1-sulphonate betaine, 3-(cetylmethyl-phosphonium)-propane-1-sulphonate betaine and N , N -dimethyl- N -dodecyl-glycine.
  • betaines are the alkylamidopropyl betaines e.g. those wherein the alkyl
  • surfactants may be chosen from the surfactants described in well-known textbooks like " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , and/or the current edition of " McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 ; " Handbook of Industrial Surfactants” (4th Edn.) by Michael Ash and Irene Ash; Synapse Information Resources, 2008 .
  • the liquid cleaner composition of the present invention comprises water.
  • the composition comprises at least 70 %-wt, more preferably between 76 and 98 wt-%, even more preferably between 84 and 93 %-wt of water.
  • the composition has a pH of between 8 and 13, more preferably between 10 and 12 and even more preferably between 10 and 11.
  • the pH of the composition can suitably be adapted to fall within the required or preferred range by means of a pH modifier.
  • pH modifiers are well-known in the art.
  • the composition preferably comprises a pH modifier selected from ethanolamine, potassium hydroxide, sodium hydroxide and mixtures thereof.
  • the liquid cleaner composition of the present invention is particularly efficacious at providing suspension to materials dispersed in the liquid. Therefore, in the context of this invention, a suspendable is an entity that is capable of being suspended by the liquid cleaner composition. Typically, a suspendable would cream or sediment in a Newtonian liquid of equivalent density, since a Newtonian liquid is incapable of suspension. Typically, a suspendable is in a different phase than the liquid, so it may be gaseous or solid. A suspendable typically is immiscible and/or insoluble in the liquid cleaner composition (at least at a timescale corresponding to the shelf life of the composition). The following are non-limiting examples of suspendables.
  • the suspendables may for instance act as visual cues, providing a sense of cleaning activity to the user of the cleaner liquid.
  • visual cues suitable to be suspended include mica platelets, mica/silica particles ( e.g . Timeron MP1001 ex Merck), or wax beads.
  • abrasives may be used as suspendables, including for example calcite (e.g . OmyaCarb 30AV, ex Omya), or silica particles or olive stone fragments.
  • calcite e.g . OmyaCarb 30AV, ex Omya
  • silica particles or olive stone fragments e.g., silica particles or olive stone fragments.
  • the suspendables may be encapsulates, containing encapsulated substances, including for example fragrance, insecticide, antibacterial agents or enzymes.
  • the suspendables need not be solid. Thus, gas bubbles, including e.g . air, or nitrogen can also be efficiently suspended.
  • the size of the suspendables preferably is in the size range of 1 ⁇ m to 2 mm, more preferably of 10 ⁇ m to 1 mm, and even more preferably of 100 to 500 ⁇ m. Nevertheless, it is noted that when the suspendable consists of air bubbles, the size may be larger than 2 mm. In case the liquid cleaner composition is intended to be suitable for spraying, suitable suspendables are preferably smaller than 500 ⁇ m.
  • Suspendable abrasive particles preferably have a volume average median diameter d(0.5) of 100 ⁇ m or below, more preferably of between 20 and 70 ⁇ m.
  • the liquid cleaner composition according to the present invention preferably comprises a polymeric amine ingredient, wherein the polymeric amine ingredient includes a (co-)polymer selected from the group consisting of poly(ethylene imine)s, alkoxylated poly(ethylene imine)s, alkylated poly(ethylene imine)s, poly(vinyl amine)s, alkoxylated poly(vinyl amine)s, alkylated poly(vinyl amine)s.
  • a polymeric amine ingredient includes a (co-)polymer selected from the group consisting of poly(ethylene imine)s, alkoxylated poly(ethylene imine)s, alkylated poly(ethylene imine)s, poly(vinyl amine)s, alkoxylated poly(vinyl amine)s, alkylated poly(vinyl amine)s.
  • the polymeric amine is selected from the group consisting of poly(ethylene imine)s, alkoxylated poly(ethylene imine)s, alkylated poly(ethylene imines) and mixtures thereof. Even more preferably, the polymeric amine is selected from poly(ethylene imine)s, alkoxylated poly(ethylene imine)s and mixtures thereof.
  • the concentration of the polymeric amine in the cleaning composition of the invention is preferably in the range of from 0.01 to 5.0% by weight, more preferably 0.01 to 2.0% by weight, most preferably 0.05 to 1.0% by weight.
  • the polymeric amine preferably has a number average molecular weight of from 500 to 1 ⁇ 10 7 , more preferably from 500 to 2 ⁇ 10 6 , still more preferably from 1000 to 2 ⁇ 10 6 .
  • the liquid cleaner composition according to the invention comprises between 0.01 and 1 %-wt, more preferably between 0.05 and 0.5 %-wt, even more preferably between 0.1 and 0.4 %-wt and still more preferably between 0.2 and 0.3 %-wt of one or more polymeric amines selected from the group consisting of polyethylenimines and hydroxyethylated polyethylenimines.
  • polyethylenimines and hydroxyethylated polyethylenimines include branched polyethylene imines (e.g. Lupasol® PS) and ethoxylated branched polyethylene imine (e.g. Lupasol® SC 61 B).
  • the cleaning composition of the present invention may include abrasives.
  • the composition of the present invention does not contain an abrasive.
  • the composition may contain other ingredients which aid in its cleaning performance.
  • the composition may contain detergent builders and mixtures of builders in an amount of up to 25%; in particular when the composition contains one or more anionic surfactants. If present, the builder preferably will form at least 0.1 % of the cleaning composition. Suitable inorganic and organic builders are well known to those skilled in the art.
  • a further optional ingredient of the composition of the invention is a suds regulating material, which can be employed in compositions which have a tendency to produce excessive suds in use.
  • a suds regulating material which can be employed in compositions which have a tendency to produce excessive suds in use.
  • Soaps are salts of fatty acids and include alkali metal soaps such as the sodium, potassium and ammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Particularly useful are the sodium and potassium and mono-, di- and triethanolamine salts of the mixtures of fatty acids derived from palm oil, coconut oil and ground nut oil. When employed, the amount of fatty acid or soap can form at least 0.005%, preferably 0.1 % to 2% by weight of the composition.
  • the composition comprises one or more additional organic solvents. It is preferred that the organic solvent is water-immiscible. It is more preferred that the organic solvent is suitable to serve as a co-surfactant. It is even more preferred that the liquid cleaner composition of the invention comprises from 0.01 to 0.5 %-wt of a water-immiscible organic solvent, preferably dipropylene glycol monobutyl ether.
  • Compositions may also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colorants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1,2-benzisothiazolin-3-one), hydrotropes and perfumes.
  • various other optional ingredients such as colorants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1,2-benzisothiazolin-3-one), hydrotropes and perfumes.
  • the liquid cleaner composition favourably includes one or more next-time cleaning benefit agents.
  • a "next time cleaning benefit” refers to an improved ease of removal of soil after re-soiling of a hard surface cleaned using a composition comprising a next-time cleaning benefit agent. This improved ease may for example be indicated by an increased amount of soil being removed from a metal surface using a certain fixed cleaning effort (e.g. the same no. of wiping actions using the same force per wiping action).
  • Suitable next-time cleaning benefit agents include for example the polymeric amines as specified above, tannic acid (or related compounds such as gallic acid and/or propyl gallate) or malonic acid.
  • the liquid cleaning composition of the invention may be stored in and dispensed by any suitable means, but spray applicators are particularly preferred. Pump dispensers (whether spray or non-spray pumps) and pouring applicators (bottles etc) are also possible.
  • the invention also provides the use of a liquid cleaning composition according to the invention for cleaning a surface, wherein the composition is comprised in a container, and wherein the container further comprises a spray dispenser for dispensing the composition in the form of a spray.
  • the spray dispenser is preferably a trigger spray dispenser but may be any mechanical means for ejecting the liquid in spray or aerosol form.
  • the surface preferably is a hard surface, more preferably a vertical hard surface. This use of the composition of the invention optimally exploits the advantageous suspension, sprayability and cling properties of the composition.
  • liquid cleaner composition of the invention can advantageously be prepared by a method, comprising the steps of
  • the optional alkali serves to provide suitable alkaline conditions, if these are not already inherently provided by the copolymer.
  • the aqueous solution in which the copolymer is dissolved preferably has a pH of above 8, more preferably above 10 and even more preferably above 12.
  • Suitable alkali materials are the pH modifiers as specified above.
  • the copolymer need not be dissolved in all the water that is comprised in the final composition. It is particularly advantageous to first prepare a relatively concentrated solution of the copolymer.
  • a concentrated solution preferably is in the form of a gel and preferably comprises 1 to 20 %-wt, more preferably 5 to 15 %-wt and even more preferably 8 to 12 %-wt of the copolymer. Subsequently, this concentrated solution may conveniently be combined with an aqueous solution comprising the surfactant under step c.
  • Additional ingredients of the composition are preferably added after step b, more preferably during or after step c.
  • Macromonomers were synthesised by a catalytic chain transfer polymerisation reaction.
  • Azo- iso butyronitrile (0.70g) (AIBN) was dissolved in 2-ethylhexyl methacrylate (150mL) and butanone (150mL) in a 2-arm round bottomed flask fitted with a condenser.
  • the solution was purged with nitrogen for 45 minutes before addition of Cobaloxime Boron Fluoride (COBF) (10.3mg).
  • COBF Cobaloxime Boron Fluoride
  • Samples were taken periodically for conversion and molecular weight analysis using 1 H NMR analysis.
  • the resulting macromonomers were purified by removal of solvent and excess monomer in vacuo.
  • Butanone (150mL) was added to the viscous oil and removed again in vacuo. This cycle was repeated three times to reduce residual monomer content.
  • Macromomonomers of methylmethacrylate and n -butylmethacrylate were prepared in a similar fashion.
  • the copolymers according to the present invention were prepared by precipitation polymerisation.
  • Stock solutions of acrylic acid (250mL, 50 w.%), maleic anhydride (250mL, 15 wt.%), macromonomer (250mL, 5 wt%), pentaerythritol allyl ether (250mL, 1wt%), AIBN (250mL, 0.25wt%), and potassium carbonate were made up with ethyl acetate/cyclohexane (54/46v/v%) in Schott Duran 200mL flasks. Each flask was purged with nitrogen for 30 minutes before being added to a Chemspeed Swing Platform.
  • PMMA 1400 polymethylmethacrylate macromonomer (Mn is about 1400 Da) Table 3 - Macromers Example A B C D PBMA 950 macromer PMMA 1500 macromer Acrylic Acid Maleic Anhydride Pentaerythritol allyl ether wt-% wt-% wt-% wt-% wt-% CP1 10.3 - 86.2 2.6 0.9 CP2 15.2 - 81.4 2.5 0.9 CP3 - 10.3 88.8 0 0.9
  • Liquid cleaner compositions were formulated as specified in Table 4.
  • the process involved initial swelling of the copolymer in alkali solution before addition of remaining materials in any order.
  • the swelling of the copolymer involved firstly mixing with water on a 1:9 weight ratio to form a rough gel, followed by addition of the copolymer gel to a mixture of NaOH and water with stirring.
  • the yield stress of the cleaning liquids was determined and used as a measure of the suspending capability of the liquids.
  • the maximum value of G' the elastic or storage modulus, was measured by oscillatory rheological measurement using an Anton Paar ASC rheometer, fitted with a smooth 'cup and bob' geometry (CC27), run in oscillation mode at 25°C. The bob was oscillated at 1 Hz with increasing strain (rotational amplitude) from 0.01 to 100% of full rotation.
  • the cleaning liquids were sprayed using a Cif trigger spray device. If the liquids were sprayable, the volume average mean diameter D[4,3] of the droplets of the spray was determined using a Spraytec spray particle analyser (ex Malvern).
  • a cleaning liquid clings to a typical household surface after spraying was determined. For every measurement, a glass tiles of 150 ⁇ 150 mm was cleaned using calcite and rinsed with demineralised water and dried (with absorbent tissue). After weighing the tile, between 2 and 3 grams of the cleaner composition was sprayed onto the horizontal tile from a conventional Cif spraying device at a distance of 30 cm. Subsequently, the tile was weighed again to obtain the initial product weight. The tile was then held vertically for 10 seconds, was returned to a horizontal orientation and reweighed to obtain the weight of the composition remaining on the tile. The cling value is reported as the average percentage by weight of the sprayed composition that remained on the tile in three repeated tests.
  • compositions according to the invention there was no difference in visual appearance of the material after applying the material to a horizontal surface and rotating it to vertical compared to applying the material to a vertical surface. This indicates that good cling occurs very rapidly after application.
  • Table 5 Interpretation of test results Good Acceptable Unacceptable Suspension Test No sedimentation of bentonite particles observed. Bentonite particles separated into lower 99 to 90% of test liquid. Bentonite particles separated into less than 90% of test liquid. Yield Stress Yield Stress >1.0 Pa Yield Stress >0.6 Pa Yield Stress ⁇ 0.6 Pa Spray Test Droplet size D[4,3] between 190 and 240 ⁇ m; no observation of non-nebulised liquid in spray-cone.
  • liquid cleaner compositions according to the invention all provided good general cleaning efficacy.
  • results of table 6 show that liquid cleaning compositions according to the invention also provide the desired characteristics of good suspension, sprayability and cling.
  • Ex. (2:1), (2:2) and (2:3) shows the efficacy of three different copolymers according to the invention.
  • a comparison of Ex. (2:1), (2:4), and (2:5) shows the efficacy in the presence of different surfactants.
  • Ex. (2:6), (2:7) and (2:8) are comparative examples showing that suspension and cling of a composition are not acceptable when the pH is outside the specified range (2:6), when a commercial rheology modifier is used (2:7), or when the surfactant is present at a level outside the specified range (2:8).

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Claims (15)

  1. Flüssige Reinigungszusammensetzung, umfassend
    0,1 bis 10 Gew.-% eines oder mehrerer Tenside,
    0,4 bis 1 Gew.-% eines oder mehrerer Rheologie-modifizierender Copolymere und Wasser,
    wobei die Zusammensetzung einen pH zwischen 8 und 13 aufweist und
    wobei das eine oder die mehreren Rheologie-modifizierenden Copolymeren aus der Gruppe von Copolymeren der Formel
    Figure imgb0007
     ausgewählt sind,
    worin a, b, c und d Gewichtsprozent darstellen, mit dem jede(s) Wiederholungseinheit oder abgeleitete Monomer innerhalb des Copolymers enthalten ist,
    wobei
    a zwischen 0,5 und 25 Gewichts-% des Copolymers liegt,
    b zwischen 70 und 98 Gewichts-% des Copolymers liegt,
    c zwischen 0 und 15 Gewichts-% des Copolymers liegt und
    d zwischen 0 und 5 Gewichts-% des Copolymers liegt,
    und wobei
    A ein Makromonomer darstellt, das an mindestens einem Ende eine polymerisierbare Gruppe enthält, die während der Polymerisation mit mindestens einem der B-, C- und D-Monomeren reaktiv ist, wobei die polymerisierbare Gruppe an dem mindestens einen Ende des Makromonomers mit einer Kette verknüpft ist, die von einem Homo- oder Co-Polymer von C1-C10-Alkylacrylaten, C1-C10-Alkylmethacrylaten, Methacrylsäure, Acrylsäure oder Kombinationen davon gebildet ist, wobei das Makromonomer ein zahlenmittleres Molekulargewicht von 500 bis 10.000 aufweist, und
    B eine Acryl- oder Methacrylsäure oder ein Salz davon ist,
    C, wenn es vorliegt, ein mehrbasiges Vinylmonomer ist, das aus der aus Maleinsäure, Fumarsäure, Itaconsäure, Citraconsäure, Mesaconsäure, Kombinationen davon und Anhydriden und Salzen davon bestehenden Gruppe ausgewählt ist, und
    D, wenn es vorliegt, ein vernetzendes Monomer zum Einführen von Verzweigung und zum Steuern des Molekulargewichts darstellt, wobei das vernetzende Monomer polyfunktionelle Einheiten umfasst, die mehrfach reaktive Funktionalisierungsgruppen tragen, die aus der aus Vinylverbindungen, allylischen Verbindungen und funktionellen Mischungen davon bestehenden Gruppe ausgewählt sind,
    wobei die Gruppen A, B, C und D in einem statistischen, Block- oder vernetzten Copolymer-Format eine mit der anderen kovalent gebunden sind.
  2. Flüssige Reinigungszusammensetzung nach Anspruch 1, wobei das zahlengemittelte Molekulargewicht A zwischen 500 und 2000 liegt.
  3. Flüssige Reinigungszusammensetzung nach Anspruch 1 oder 2, wobei c zwischen 2 und 4 Gewichts-% liegt.
  4. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 3, wobei d zwischen 0,5 und 1,5 Gewichts-% liegt.
  5. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 4, wobei A 70 bis 100% C1-C10-Alkyl(meth)acrylate, in Gewicht, im Hinblick auf das Gewicht von A, umfasst.
  6. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 5, wobei die C1-C10-Alkyl(meth)acrylate unter einem oder mehreren von Methyl(meth)acrylat, Butyl(meth)acrylat und 2-Ethyl-hexyl(meth)acrylat ausgewählt sind.
  7. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 6, wobei B Acrylsäure oder ein Salz davon ist.
  8. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 7, wobei C unter Maleinsäure, Maleinsäureanhydrid und Mischungen davon ausgewählt ist.
  9. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 8, wobei D Pentaerithrytallylether ist.
  10. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 9, wobei das Rheologie-modifizierende Copolymer unter der Gruppe von Copolymeren ausgewählt ist, worin
    • A ein Poly-n-butylmethacrylat-Makromonomer mit einem zahlengemittelten Molekulargewicht zwischen 500 und 2000 ist und a zwischen 5 Gew.-% und 20 Gew.-% liegt,
    • B Acrylsäure ist,
    • C Maleinsäureanhydrid ist und c in dem Bereich zwischen 2 und 4 Gew.-% liegt und
    • D Pentaerythritallylether ist und d in dem Bereich zwischen 0,75 und 1 Gew.-% liegt;
    oder der Gruppe von Copolymeren, worin
    • A ein Poly-methylmethacrylat-Makromonomer mit einem zahlengemittelten Molekulargewicht zwischen 500 und 2000 ist und a in dem Bereich zwischen 5 Gew.-% und 20 Gew.-% liegt,
    • B Acrylsäure ist,
    • C Maleinsäureanhydrid ist und c in dem Bereich zwischen 0 und 4 Gew.-% liegt,
    • D Pentaerythritallylether ist und d in dem Bereich zwischen 0,75 und 1 Gew.-% liegt,
    und worin sich die angegebenen Prozente auf das Gewicht des Copolymers beziehen.
  11. Flüssige Reinigungszusammensetzung nach Anspruch 10, wobei das Rheologie-modifizierende Copolymer unter einem oder mehreren Copolymeren ausgewählt ist, worin
    • A ein Poly-n-butylmethacrylat-Makromonomer mit einem zahlengemittelten Molekulargewicht zwischen 500 und 2000 ist und a in dem Bereich zwischen 8 Gew.-% und 12 Gew.-% liegt,
    • B Acrylsäure ist,
    • C Maleinsäureanhydrid ist und c in dem Bereich zwischen 2 und 3 Gew.-% liegt,
    • D Pentaerythritallylether ist und d in dem Bereich zwischen 0,75 und 1 Gew.-% liegt.
  12. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 11, worin das eine oder die mehreren Tenside nicht-ionische Tenside sind, bevorzugter ethoxylierte C8-C12-Alkohole, wobei sogar bevorzugter der Durchschnittsgrad der Ethoxylierung zwischen 5 und 8 liegt.
  13. Flüssige Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 12, wobei die Zusammensetzung 0,01 bis 1 Gew.-% eines oder mehrerer polymerer Amine umfasst, die aus der aus Polyethyleniminen und hydroxyethylierten Polyethyleniminen bestehenden Gruppe ausgewählt sind.
  14. Verfahren zur Herstellung einer flüssigen Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 13, umfassend die Schritte
    a. Bereitstellen von Wasser, der ein oder mehreren Rheologie-modifizierenden Copolymeren und gegebenenfalls Alkali,
    b. Auflösen des Copolymers in Wasser unter alkalischen Bedingungen und
    c. Zugabe des Tensids zu der Zusammensetzung, die das dispergierte Copolymer enthält.
  15. Verwendung einer flüssigen Reinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 13 zur Reinigung einer Oberfläche, wobei die Zusammensetzung von einem Behälter umfasst ist und worin der Behälter des Weiteren einen Sprühverteiler zur Abgabe der Zusammensetzung in Form eines Sprays umfasst.
EP14710300.6A 2013-04-03 2014-03-17 Flüssigreinigungszusammensetzung Active EP2981601B1 (de)

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EP13162083 2013-04-03
PCT/EP2014/055238 WO2014161714A1 (en) 2013-04-03 2014-03-17 Liquid cleaning composition
EP14710300.6A EP2981601B1 (de) 2013-04-03 2014-03-17 Flüssigreinigungszusammensetzung

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US11097031B2 (en) 2016-08-01 2021-08-24 The Procter & Gamble Company Phase-stable, sprayable freshening compositions comprising suspended particles
JP6977022B2 (ja) 2016-08-01 2021-12-08 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company 懸濁した粒子を含む相安定で噴霧可能なフレッシュニング組成物及びこれらを用いて空気又は表面を清浄にする方法
WO2018026625A1 (en) 2016-08-01 2018-02-08 The Procter & Gamble Company Sprayable freshening product comprising suspended particles and methods of freshening the air or a surface with the same
WO2018026627A1 (en) 2016-08-01 2018-02-08 The Procter & Gamble Company Phase-stable, sprayable freshening compositions comprising suspended particles
BR112019022895B1 (pt) * 2017-05-29 2023-10-31 Dow Global Technologies Llc Composição de limpeza de superfície dura, e, método para limpar uma superfície dura
WO2021122692A1 (en) * 2019-12-18 2021-06-24 Basf Se Textile coated with malodor reducing polymers

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ZA201507331B (en) 2017-11-29
EA028607B1 (ru) 2017-12-29
PL2981601T3 (pl) 2017-02-28
WO2014161714A1 (en) 2014-10-09
EA201591909A1 (ru) 2016-02-29

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