CA2157570A1 - A floor cleaning composition - Google Patents
A floor cleaning compositionInfo
- Publication number
- CA2157570A1 CA2157570A1 CA002157570A CA2157570A CA2157570A1 CA 2157570 A1 CA2157570 A1 CA 2157570A1 CA 002157570 A CA002157570 A CA 002157570A CA 2157570 A CA2157570 A CA 2157570A CA 2157570 A1 CA2157570 A1 CA 2157570A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composition
- floor cleaning
- cleaning composition
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- C11D3/16—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
-
- 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
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/662—Carbohydrates or derivatives
-
- 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
Abstract
An aqueous floor cleaning composition containing nonionic surfactant, anionic surfactant and at least 1% by weight of alkali-soluble polymeric polycarboxylate wherein at least 25% by weight of the nonionic surfactant component consists of alkyl polyglycosides.
Description
Translation -WO 94/20595 2157~70 PCT/EP94/00530 A floor cleaning compositio~
This invention relates to an aqueous composition which may be used in diluted form for the cleaning and care of hard surfaces, more particularly floors.
Many new processes and compositions for the cleaning and care of floors have been developed over recent years and decades, not least because of the development of new materials for floor coverings. In practice, the choice of the composition is largely determined by whether cleaning or preservation of the surface is the priority.
Thus, compositions which produce more or less hard and resistant films are mainly used for the care and preser-vation of surfaces. To this end, the compositions contain - generally in emulsified form - waxes or film-forming polymers and crosslinking agents, generally heavy metal salts, which together form self-shine or polishable films on the treated surfaces after drying. Long-lasting protection of the surfaces can be obtained in this way, severe mechanical stressing also being effectively toler-ated depending on the quality of the film. However, the removal of such films, as necessitated for example by soiling or damage, is only possible under extreme condi-tions. By contrast, compositions which are mainly in-tended for cleaning have high contents of surfactants, often together with alkaline substances, organic solvents or abrasives. In many cases, soil and old films can be thoroughly removed with such compositions although the surfaces thus cleaned are generally then exposed to resoiling without protection unless they are subsequently subjected to a preserving treatment.
Since, in many cases, cleaning and care of the floor surface are desirable in equal measure, compositions with which cleaning and preservation are possible in a single 2157~ 70 operation have also been developed in addition to the compositions mentioned above. Examples of such composi-tions can be found, for example, in GB-PS 1,528,592 and in German patent application 35 33 531. These composi-tions, which are also known as floor wiping compositions,contain sufficient quantities of surfactants, more particularly nonionic and anionic surfactants, in addi-tion to film-forming polymers so that the compositions may be used equally for care and cleaning. Certain difficulties arise with the compositions in question where emphasis is placed on particularly low foaming in application and, for this reason, relatively large quantities of low foaming nonionic surfactants are used in the compositions. The correspondingly formulated compositions are often not stable to separation at low temperatures and show poor residue behavior when used on to smooth floors, fairly significant resoiling of the films occasionally being observed as well. Providing an improvement in this regard without affecting the other favorable properties of known compositions was one of the problems addressed by the present invention.
The present invention relates to an aqueous floor-cleaning composition containing nonionic surfactant, anionic surfactant and alkali-soluble polymeric polycar-boxylate, at least 25% by weight of the nonionic surfac-tants present in this composition consisting of alkyl polyglycosides.
The new composition has excellent cleaning power and, after drying on the floor surface, forms very uniform films which show extremely high transparency and only a very slight tendency towards resoiling. A feature particularly worth noting is the high stability of the composition to separation during storage at low tempera-tures, even when very low-foaming nonionic surfactants with relatively poor solubility in water are used in the interests of particularly low foaming and/or the composi-tion has very high surfactant concentrations.
The surfactants present in the composition are based on a mixture of nonionic and anionic surfactants. The nonionic surfactants make up at least 50% by weight of the total surfactant content of the composition according to the invention. Their percentage content is preferably between 65 and 95% by weight.
In principle, suitable nonionic surfactants for the compositions according to the invention are any types of nonionic surfactants providing they meet the low foaming requirement. Corresponding nonionic surfactants are, above all, the adducts of 3 to 20 moles of ethylene oxide (EO) with primary C820 alcohols, for example with coco-fatty alcohol or tallow fatty alcohol, oleyl alcohol, oxoalcohols or secondary alcohols with the same chain length. Other suitable nonionic surfactants are the corresponding ethoxylation products of other long-chain compounds, for example fatty acids and fatty acid amides containing 12 to 18 carbon atoms and alkylphenols con-taining 8 to 16 carbon atoms in the alkyl moiety. In all these products, the ethylene oxide may be partly replaced by propylene oxide (Po). Other suitable nonionic surfac-tants are mono- and diethanolamides of fatty acids and long-chain amine oxides or sulfoxides, for example the compound N-cocoalkyl-N,N-dimethylamine oxide. Other nonionic surfactants which may be used in accordance with the invention are the water-soluble adducts - containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups - of ethylene oxide with polypropylene glycol, alkylenediamine polypropylene glycol and with alkyl polypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain performs a hydrophobic func-tion. Of the nonionic surfactants mentioned above, the adducts of 3 to 10 moles of ethylene oxide with long-chain primary alcohols containing 10 to 16 carbon atoms from the group of oxoalcohols and natural fatty alcohols are preferably present in the compositions according to the invention, the fatty alcohol ethoxylates being most particularly preferred.
In addition to the nonionic surfactants mentioned above, the compositions according to the invention also always contain alkyl polyglycosides as nonionic surfac-tants. Alkyl polyglycosides are surfactants correspond-ing to general formula I:
R~O(~G)n in which R is a long-chain alkyl radical containing 8 to 22 carbon atoms, G is a monosaccharide residue attached by a glycoside bond and n has a value of 1 to 10.
Alkyl polyglycosides have been known as surface-active substances for more than 50 years and can be produced by various methods, cf. European patent applica-tion 362 671 where literature on earlier processes is also cited.
A synthesis of industrial relevance essentially comprises the acid-catalyzed condensation of monosac-2S charides of the aldose (HO-G) type with long-chain alcohols (R-OH) containing 8 to 22 and preferably 8 to 18 carbon atoms. Alkyl glycosides corresponding to formula I:
R~O(~G)n in which the value of n can be varied within wide limits through the choice of the reaction conditions, are formed with elimination of water. Alkyl glycosides of formula I where n = 1 to 10 may be used in accordance with the invention. Compounds with values for n of 1 to 6 and, more particularly, 1 to 2 are preferred. In products where n is greater than 1, n is of course a statistical mean value.
Alkyl glycosides can also be produced from oligosac-charides or polysaccharides which, in the course of theacid-catalyzed reaction, are first depolymerized to lower fragments by hydrolysis and/or alcoholysis before the alkyl glycosides of formula I are formed. Mixtures of various reducing monosaccharides or polysaccharides containing various monosaccharide units may also be used as starting materials, in which case alkyl glycoside molecules of correspondingly mixed composition can be formed where n is greater than 1.
The following monosaccharides are preferred starting materials: glucose, mannose, galactose, arabinose, apiose, lyxose, gallose, altrose, idose, ribose, xylose and talose and the oligo- and polysaccharides composed of these monosaccharides, for example maltose, lactose, maltotriose, hemicellulose, starch, partial hydrolyzates of starch and sugar sirup. However, alkyl glycosides synthesized from the same monosaccharide units are pre-ferred for the purposes of the invention. Alkyl glyco-sides in which the residue (-G) is derived from glucose are particularly preferred. For these compounds which are also known as alkyl glucosides, glucose, maltose, starch and other oligomers of glucose are correspondingly used as starting materials.
In the above-described production process, the alkyl moiety R is derived from long-chain, optionally unsatura-ted, preferably primary alcohols which may be branched,but are preferably not branched. Examples are the synthetic oxoalcohols containing 9 to lS carbon atoms and the fatty alcohols containing 8 to 22 carbon atoms obtained from natural fatty acids. Fatty alcohols containing 8 to 18 carbon atoms and oxoalcohols contain-` 2157S70 ing 11 to 15 carbon atoms are preferred, fatty alcoholscontaining 8 to 10 carbon atoms or 12 to 14 carbon atoms being particularly preferred.
In addition to the actual alkyl glycosides corre-sponding to formula I, industrially produced productsgenerally also contain certain amounts of free alcohol R-OH and non-acetalized saccharides, optionally in oligo-merized form. In most cases, these technical impurities do not interfere with the intended application. If the alkyl glycosides are produced from alcohol mixtures, for example from alcohols based on natural fats, the alkyl glycosides are of course also mixtures with a correspond-ingly broad meaning of R in formula I.
Alkyl polyglycosides of which the glycoside com-ponent consists of l to 2 glucose units and of which thealkyl component is derived from fatty alcohols containing 8 to 10 carbon atoms are preferably used in accordance with the present invention. The alkyl polyglycosides make up at least 25% by weight of the total nonionic surfactant content of the compositions according to the invention. In extreme cases, alkyl polyglycosides may be the only nonionic surfactants present. A content of 40%
by weight to 80~ by weight of alkyl polyglycosides, based on the total of nonionic surfactants, is particularly preferred.
The compositions according to the invention mainly contain synthetic anionic surfactants as the anionic surfactants. The synthetic anionic surfactants in question are, above all, those of the sulfonate and sulfate type.
Surfactants of the sulfonate type include alkyl benzene sulfonates with a C915 alkyl radical and olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and also the disulfonates obtained, for example~ from Cl2-l8 monoolefins with a terminal or inter-Wo 94/20595 7 PCT/EP94/00530 nal double bond by sulfonation with gaseous sulfurtrioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonates obtainable from C1zl8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by addi-tion of bisulfites onto olefins and also the esters of ~-sulfofatty acids, for example the ~-sulfonated methyl or ethyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids.
Suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural or synthetic origin, i.e. of fatty alcohols such as, for example, cocofatty alcohols, oleyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol or stearyl alcohol, or Cl020 oxoalcohols or secondary al-cohols with the same chain length. The sulfuric acid monoesters of aliphatic long-chain primary alcohols ethoxylated with 1 to 6 moles of ethylene oxide (EO) or ethoxylated secondary alcohols are also suitable.
Sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides and long-chain sulfosuccinic acid esters are also suitable. The anionic surfactants are prefer-ably used in the form of alkali metal salts, more par-ticularly sodium salts, although ammonium salts or the salts of alkanolamines containing 2 to 6 carbon atoms may also be used. Particularly preferred anionic surfactants for the purposes of the invention are fatty alcohol sulfates and fatty alcohol ether sulfates, for example C1~Cl8 cocoalcohol sulfate Na and C12~14 cocoalcohol + 2 EO
sulfate.
In addition to the nonionic and anionic surfactants mentioned, the compositions according to the invention may also contain relatively small quantities of other surfactants, more particularly amphoteric surfactants, Wo 94/20595 8 PCT/EP94/00530 and soaps if this is appropriate for obtaining special effects and does not affect the other favorable proper-ties of the compositions. The soaps are the water-soluble salts of long-chain fatty acids preferably containing 12 to 18 carbon atoms, for example cocofatty acid sodium salt and tallow fatty acid sodium salt. The amphoteric surfactants are long-chain compounds of which the hydrophilic component consists of a cationic charged center (normally a tertiary amino group or a quaternary ammonium group) and an anionically charged center (norm-ally a carboxylate group or a sulfonate group). Examples of such surfactants are N-cocoalkyl-N,N-dimethylaminoaCe-tate and N-dodecyl-N,N-dimethyl-3-aminopropane sulfonate.
The total surfactant content of the compositions according to the invention is preferably between 4 and 25% by weight and more preferably between 8 and 16% by weight, based on the composition as a whole in its undiluted form.
The presence of alkali-soluble polymeric polycar-boxylate is cruclal to the care properties of the com-positions. These carboxylates may be resin-like com-pounds, for example copolymers of styrene and maleic anhydride which may be partly saponified and, optionally, even partly esterified or amidated. However, preferred polymeric polycarboxylates are soluble polymer compounds which have a minimum film forming temperature of 0 to 70C and which are generally copolymers of at least three different monomers, the polycarboxylates not being crosslinked with metals.
The polymers preferably used contain as their most important constituent an acrylate copolymer of 1 to 30 parts by weight, based on copolymer, of monomers contain-ing carboxylic acid groups, 30 to 70 parts by weight of monomers which form homopolymers having glass tempera-tures below 20C, preferably esters of acrylic acid with Cl8 alcohols and/or of methacrylic acid with C4-8 alcohols, and 30 to 70 parts by weight of comonomers which form homopolymers having glass temperatures above room temper-ature, preferably methacrylates of C13 alcohols or styrene.
The comonomers containing acid groups may be ethy-lenically unsaturated carboxylic acids, acrylic acid and methacrylic acid being particularly suitable.
Comonomers having glass temperatures below 20C, i.e. glass temperatures below room temperature (based on homopolymers of a monomer) include esters of acrylic acid with Cl8 alcohols and esters of methacrylic acid with C4-8 alcohols. Thus, the methyl, ethyl, propyl, butyl or 2-ethylhexyl ester of acrylic acid and also the butyl, hexyl or 2-ethylhexyl ester of methacrylic acid may be used. Comonomers of which the homopolymers have glass temperatures above room temperature are esters of meth-acrylic acid with Cl3 alcohols, for example methyl methacrylate or ethyl methacrylate. A particularly important comonomer of which the homopolymer has a glass temperature above room temperature is styrene.
Copolymers of acrylic acid and/or methacrylic acid with styrene, acrylates and/or methacrylates are prefer-ably used. The copolymers of acrylic acid or methacrylic acid with various acrylates and/or methacrylates and/or styrene, for example terpolymers of methyl acrylate, ethyl acrylate, methacrylic acid and styrene, are parti-cularly preferred. The particular ratios of comonomers, of which the homopolymers have glass temperature below room temperature, to monomers of which the homopolymers have glass temperatures above room temperature should be adjusted in such a way that the film forming temperature of the polymer dispersion is in the range from 0 to 70OC.
General knowledge of polymer chemistry may be applied in this regard. The film forming temperatures mentioned ~O 94/2059S 10 PCT/EP94/00530 apply to the plasticizer-free system, i.e. to the poly-mers with no other additives. Examples of such polymers are the products Primal 1531 (Rohm and Haas), NeoCryl XK-39 and NeoCryl BT-26 (ICI).
At all events, the polycarboxylates used, unless they are already water-soluble as such, should be con-verted into a soluble form with the aid of alkalis.
Suitable alkalis are, in particular, NaOH, KOH and non-volatile amines, for example alkanolamines. It is preferred to use aqueous ammonia with which the polycar-boxylates can be safely clarified as required without any risk of over-alkalization. In their undiluted form, the final compositions should preferably have a pH value of about 7 to about 11, pH values of 8 to g and also 10 to 10.5 being particularly preferred.
The quantity of polymeric polycarboxylates in the compositions according to the invention is preferably selected so that the ratio by weight of polycarboxylate to total surfactant content is from 1:6 to 2:3 and, more particularly, from 1:4 to 1:2. If a mixture of several polymeric polycarboxylates is used, these figures apply to the total polycarboxylate content.
In addition to the compulsory ingredients described above and water and, optionally, alkalizing agents, the compositions according to the invention may contain other auxiliaries and additives of the type typically present in such compositions. The only proviso in this regard is of course that the positive properties of the composi-tions should not be adversely affected by these other auxiliaries and additives. Examples of such additives are organic, completely water-miscible solvents which may be used to increase performance and, optionally, to improve wetting power. Lower alcohols containing 2 or 3 carbon atoms are preferred, being used in quantities of not more than 10% by weight and preferably in quantities -of from about 0.2 to 5% by weight, based on the total weight of the undiluted composition. Examples of other additives are perfume oils, dyes, viscosity regulators and preservatives. These substances are normally present in quantities of not more than 5% by weight and preferab-ly in quantities of 0.01 to 2% by weight.
The compositions are used by initially preparing a solution of the composition, in which the content of non-volatile components is between about 0.2 and about 1 g/l, by dilution with water. Depending on the concentration of the original composition, this concentration is achieved by dilution in a ratio of about 1:1000 to about 1:50. The dilute solution is then applied to the surface to be cleaned with an absorbent article, for example with lS a cloth or a sponge, and then partly removed from the surface with the soil. After this treatment, the surface is not rinsed so that the remaining cleaning solution can dry to form a uniform protective film. It is due to this method of application that the compositions in question are also known as wiping compositions. The composition according to the invention is distinguished by an optimal cleaning effect on a number of soil types and, at the same time, forms a resistant film which affords excellent protection against resoiling. The film is completely transparent so that the color and texture of the treated surfaces appear largely unchanged without an additional gloss effect. When the composition is re-applied, the film dissolves and thus facilitates the cleaning process.
Troublesome film addition does not occur.
The composition according to the invention is particularly low foaming, even when it is used in rela-tively high concentrations or in undiluted form for the local removal of stains. Even in high concentrations, it shows excellent stability in storage at typical storage temperatures, but especially at low temperatures. The Wo 94/20595 12 PCT/EP94/00530 composition is particularly suitable for the care and cleaning and floors and gives excellent results on stone, sealed parquet, tiles, linoleum and plastic floors, although it may also be used for cleaning other hard surfaces, even glass. It can be applied with particular advantage to high-shine floor coverings because the film formed does not affect the shine by virtue of its high transparency.
The production of the composition in its various forms does not involve any difficulties. Normally, the polymeric polycarboxylate is first dissolved in water, optionally with addition of the alkalizing agent, and the surfactants are subsequently added in the required concentration. Finally, the additives are introduced.
Particulars of a preferred formulation for the composition according to the invention are given in the following. It contains:
1 to 10, preferably 2 to 6% by weight of fatty alcohol ethoxylate (3 to 10 E), 1 to 10, preferably 4 to 8% by weight of fatty alcohol polyglucoside, 0.5 to 4, preferably 1 to 3% by weight of anionic surfactant from the 2S group consisting of fatty alcohol sulfate, fatty alcohol ether sulfate and mixtures thereof, 30 1 to 8, preferably 3 to 5% by weight of alkali-soluble polymeric polycarboxylate with a minimum film forming temperature of 0 to 70C, 2I575 7~
~O 94/20595 13 PCT/EP94/00530 0 to 10, preferably 0.2 to 5% by weight of water-mis-cible organic solvents and 0 to 5, preferably 0.01 to 2% by weight of other auxi-liaries and additives.
Fxample~
Compositions 1 to 3 according to the invention and comparison compositions 4 to 10 as set out in Table 1 were prepared by mixing the individual components in water. The figures alongside the ingredients represent % by weight, the balance to 100% by weight being water.
Quantities of 3 g of the compositions were diluted to 1 liter and were used in this form to test cleaning power and resoiling behavior. The transparency of the residue remaining after drying was tested with a three times higher concentration of the compositions. Low-tempera-ture stability was tested on the undiluted compositions.
The test results are also set out in Table 1.
The individual tests were carried out as follows:
1. Testinq of cleaning ~ower The cleaning effect of the wiping compositions was determined using a Gardner washability and scouring tester as described in the quality standards of the Industrieverband Putz- und Pflegemittel e.V. (Sei-fen-ole-Fette-wachse~ 108, pages 526 to 528 (1982)).
In this method, a white PVC film is provided with a test soil of soot and grease and machine-wiped under standardized conditions with a sponge soaked with the cleaning composition. Cleaning performance is measured by photoelectric determination of reflec-tance (in %).
2. Testing of resoiling behavior For this test, a white PVC covering (75 x 21 cm) was divided into three equal sections of 25 x 21 cm.
Quantities of 1.2 ml of the solution to be tested were wiped over each of the sections using a cotton cloth. This wiping operation was repeated 9 times after drying. Resoiling behavior was then tested after drying in a special drum in which the PVC
covering was placed and then moved around for 30 minutes at 25 r.p.m. with 36 g of a special soiling mixture. The test soil had the following composi-tion:
3 g of sieved vacuum cleaner dirt (RFC of the Waschereiforschung, Krefeld) 3 g of burnt sea sand 15 g of plastic granules (Durethan WKV 30, a product of Bayer AG, Leverkusen) 15 g steel balls 6 - 7 mm in diameter.
After the soiling treatment, the test covering was removed from the drum, tapped and visually evaluated by three people. Evaluation was based on the following scale:
1 = covering very light, hardly soiled 2 = covering light, moderately soiled 3 = covering light grey, medium-soiled 4 = covering grey, heavily soiled 5 = covering dark grey, very heavily soiled.
3. Testinq of residue transparency A black, high-gloss tile (15 x 15 cm) was immersed in the test solution for 10 seconds and then placed in an upright position to dry. After complete drying, gloss was measured with a reflection meter (Dr. Lange, measuring angle 20) and compared with e_ the starting value determined before immersion. The differences between the two measured values are shown in Table 1 as the reduction in gloss.
4. Testing of low-temperature stability Undiluted cleaning compositions were stored for 24 hours at +3C in transparent glass bottles. There-after, the appearance of the samples was visually evaluated:
+ = product still clear - = product clouded or flocculated.
The test results set out in Table 1 show that the compositions according to the invention show particular advantages in regard to low-temperature stability and residue transparency for very good overall properties.
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This invention relates to an aqueous composition which may be used in diluted form for the cleaning and care of hard surfaces, more particularly floors.
Many new processes and compositions for the cleaning and care of floors have been developed over recent years and decades, not least because of the development of new materials for floor coverings. In practice, the choice of the composition is largely determined by whether cleaning or preservation of the surface is the priority.
Thus, compositions which produce more or less hard and resistant films are mainly used for the care and preser-vation of surfaces. To this end, the compositions contain - generally in emulsified form - waxes or film-forming polymers and crosslinking agents, generally heavy metal salts, which together form self-shine or polishable films on the treated surfaces after drying. Long-lasting protection of the surfaces can be obtained in this way, severe mechanical stressing also being effectively toler-ated depending on the quality of the film. However, the removal of such films, as necessitated for example by soiling or damage, is only possible under extreme condi-tions. By contrast, compositions which are mainly in-tended for cleaning have high contents of surfactants, often together with alkaline substances, organic solvents or abrasives. In many cases, soil and old films can be thoroughly removed with such compositions although the surfaces thus cleaned are generally then exposed to resoiling without protection unless they are subsequently subjected to a preserving treatment.
Since, in many cases, cleaning and care of the floor surface are desirable in equal measure, compositions with which cleaning and preservation are possible in a single 2157~ 70 operation have also been developed in addition to the compositions mentioned above. Examples of such composi-tions can be found, for example, in GB-PS 1,528,592 and in German patent application 35 33 531. These composi-tions, which are also known as floor wiping compositions,contain sufficient quantities of surfactants, more particularly nonionic and anionic surfactants, in addi-tion to film-forming polymers so that the compositions may be used equally for care and cleaning. Certain difficulties arise with the compositions in question where emphasis is placed on particularly low foaming in application and, for this reason, relatively large quantities of low foaming nonionic surfactants are used in the compositions. The correspondingly formulated compositions are often not stable to separation at low temperatures and show poor residue behavior when used on to smooth floors, fairly significant resoiling of the films occasionally being observed as well. Providing an improvement in this regard without affecting the other favorable properties of known compositions was one of the problems addressed by the present invention.
The present invention relates to an aqueous floor-cleaning composition containing nonionic surfactant, anionic surfactant and alkali-soluble polymeric polycar-boxylate, at least 25% by weight of the nonionic surfac-tants present in this composition consisting of alkyl polyglycosides.
The new composition has excellent cleaning power and, after drying on the floor surface, forms very uniform films which show extremely high transparency and only a very slight tendency towards resoiling. A feature particularly worth noting is the high stability of the composition to separation during storage at low tempera-tures, even when very low-foaming nonionic surfactants with relatively poor solubility in water are used in the interests of particularly low foaming and/or the composi-tion has very high surfactant concentrations.
The surfactants present in the composition are based on a mixture of nonionic and anionic surfactants. The nonionic surfactants make up at least 50% by weight of the total surfactant content of the composition according to the invention. Their percentage content is preferably between 65 and 95% by weight.
In principle, suitable nonionic surfactants for the compositions according to the invention are any types of nonionic surfactants providing they meet the low foaming requirement. Corresponding nonionic surfactants are, above all, the adducts of 3 to 20 moles of ethylene oxide (EO) with primary C820 alcohols, for example with coco-fatty alcohol or tallow fatty alcohol, oleyl alcohol, oxoalcohols or secondary alcohols with the same chain length. Other suitable nonionic surfactants are the corresponding ethoxylation products of other long-chain compounds, for example fatty acids and fatty acid amides containing 12 to 18 carbon atoms and alkylphenols con-taining 8 to 16 carbon atoms in the alkyl moiety. In all these products, the ethylene oxide may be partly replaced by propylene oxide (Po). Other suitable nonionic surfac-tants are mono- and diethanolamides of fatty acids and long-chain amine oxides or sulfoxides, for example the compound N-cocoalkyl-N,N-dimethylamine oxide. Other nonionic surfactants which may be used in accordance with the invention are the water-soluble adducts - containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups - of ethylene oxide with polypropylene glycol, alkylenediamine polypropylene glycol and with alkyl polypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain performs a hydrophobic func-tion. Of the nonionic surfactants mentioned above, the adducts of 3 to 10 moles of ethylene oxide with long-chain primary alcohols containing 10 to 16 carbon atoms from the group of oxoalcohols and natural fatty alcohols are preferably present in the compositions according to the invention, the fatty alcohol ethoxylates being most particularly preferred.
In addition to the nonionic surfactants mentioned above, the compositions according to the invention also always contain alkyl polyglycosides as nonionic surfac-tants. Alkyl polyglycosides are surfactants correspond-ing to general formula I:
R~O(~G)n in which R is a long-chain alkyl radical containing 8 to 22 carbon atoms, G is a monosaccharide residue attached by a glycoside bond and n has a value of 1 to 10.
Alkyl polyglycosides have been known as surface-active substances for more than 50 years and can be produced by various methods, cf. European patent applica-tion 362 671 where literature on earlier processes is also cited.
A synthesis of industrial relevance essentially comprises the acid-catalyzed condensation of monosac-2S charides of the aldose (HO-G) type with long-chain alcohols (R-OH) containing 8 to 22 and preferably 8 to 18 carbon atoms. Alkyl glycosides corresponding to formula I:
R~O(~G)n in which the value of n can be varied within wide limits through the choice of the reaction conditions, are formed with elimination of water. Alkyl glycosides of formula I where n = 1 to 10 may be used in accordance with the invention. Compounds with values for n of 1 to 6 and, more particularly, 1 to 2 are preferred. In products where n is greater than 1, n is of course a statistical mean value.
Alkyl glycosides can also be produced from oligosac-charides or polysaccharides which, in the course of theacid-catalyzed reaction, are first depolymerized to lower fragments by hydrolysis and/or alcoholysis before the alkyl glycosides of formula I are formed. Mixtures of various reducing monosaccharides or polysaccharides containing various monosaccharide units may also be used as starting materials, in which case alkyl glycoside molecules of correspondingly mixed composition can be formed where n is greater than 1.
The following monosaccharides are preferred starting materials: glucose, mannose, galactose, arabinose, apiose, lyxose, gallose, altrose, idose, ribose, xylose and talose and the oligo- and polysaccharides composed of these monosaccharides, for example maltose, lactose, maltotriose, hemicellulose, starch, partial hydrolyzates of starch and sugar sirup. However, alkyl glycosides synthesized from the same monosaccharide units are pre-ferred for the purposes of the invention. Alkyl glyco-sides in which the residue (-G) is derived from glucose are particularly preferred. For these compounds which are also known as alkyl glucosides, glucose, maltose, starch and other oligomers of glucose are correspondingly used as starting materials.
In the above-described production process, the alkyl moiety R is derived from long-chain, optionally unsatura-ted, preferably primary alcohols which may be branched,but are preferably not branched. Examples are the synthetic oxoalcohols containing 9 to lS carbon atoms and the fatty alcohols containing 8 to 22 carbon atoms obtained from natural fatty acids. Fatty alcohols containing 8 to 18 carbon atoms and oxoalcohols contain-` 2157S70 ing 11 to 15 carbon atoms are preferred, fatty alcoholscontaining 8 to 10 carbon atoms or 12 to 14 carbon atoms being particularly preferred.
In addition to the actual alkyl glycosides corre-sponding to formula I, industrially produced productsgenerally also contain certain amounts of free alcohol R-OH and non-acetalized saccharides, optionally in oligo-merized form. In most cases, these technical impurities do not interfere with the intended application. If the alkyl glycosides are produced from alcohol mixtures, for example from alcohols based on natural fats, the alkyl glycosides are of course also mixtures with a correspond-ingly broad meaning of R in formula I.
Alkyl polyglycosides of which the glycoside com-ponent consists of l to 2 glucose units and of which thealkyl component is derived from fatty alcohols containing 8 to 10 carbon atoms are preferably used in accordance with the present invention. The alkyl polyglycosides make up at least 25% by weight of the total nonionic surfactant content of the compositions according to the invention. In extreme cases, alkyl polyglycosides may be the only nonionic surfactants present. A content of 40%
by weight to 80~ by weight of alkyl polyglycosides, based on the total of nonionic surfactants, is particularly preferred.
The compositions according to the invention mainly contain synthetic anionic surfactants as the anionic surfactants. The synthetic anionic surfactants in question are, above all, those of the sulfonate and sulfate type.
Surfactants of the sulfonate type include alkyl benzene sulfonates with a C915 alkyl radical and olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and also the disulfonates obtained, for example~ from Cl2-l8 monoolefins with a terminal or inter-Wo 94/20595 7 PCT/EP94/00530 nal double bond by sulfonation with gaseous sulfurtrioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonates obtainable from C1zl8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by addi-tion of bisulfites onto olefins and also the esters of ~-sulfofatty acids, for example the ~-sulfonated methyl or ethyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids.
Suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural or synthetic origin, i.e. of fatty alcohols such as, for example, cocofatty alcohols, oleyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol or stearyl alcohol, or Cl020 oxoalcohols or secondary al-cohols with the same chain length. The sulfuric acid monoesters of aliphatic long-chain primary alcohols ethoxylated with 1 to 6 moles of ethylene oxide (EO) or ethoxylated secondary alcohols are also suitable.
Sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides and long-chain sulfosuccinic acid esters are also suitable. The anionic surfactants are prefer-ably used in the form of alkali metal salts, more par-ticularly sodium salts, although ammonium salts or the salts of alkanolamines containing 2 to 6 carbon atoms may also be used. Particularly preferred anionic surfactants for the purposes of the invention are fatty alcohol sulfates and fatty alcohol ether sulfates, for example C1~Cl8 cocoalcohol sulfate Na and C12~14 cocoalcohol + 2 EO
sulfate.
In addition to the nonionic and anionic surfactants mentioned, the compositions according to the invention may also contain relatively small quantities of other surfactants, more particularly amphoteric surfactants, Wo 94/20595 8 PCT/EP94/00530 and soaps if this is appropriate for obtaining special effects and does not affect the other favorable proper-ties of the compositions. The soaps are the water-soluble salts of long-chain fatty acids preferably containing 12 to 18 carbon atoms, for example cocofatty acid sodium salt and tallow fatty acid sodium salt. The amphoteric surfactants are long-chain compounds of which the hydrophilic component consists of a cationic charged center (normally a tertiary amino group or a quaternary ammonium group) and an anionically charged center (norm-ally a carboxylate group or a sulfonate group). Examples of such surfactants are N-cocoalkyl-N,N-dimethylaminoaCe-tate and N-dodecyl-N,N-dimethyl-3-aminopropane sulfonate.
The total surfactant content of the compositions according to the invention is preferably between 4 and 25% by weight and more preferably between 8 and 16% by weight, based on the composition as a whole in its undiluted form.
The presence of alkali-soluble polymeric polycar-boxylate is cruclal to the care properties of the com-positions. These carboxylates may be resin-like com-pounds, for example copolymers of styrene and maleic anhydride which may be partly saponified and, optionally, even partly esterified or amidated. However, preferred polymeric polycarboxylates are soluble polymer compounds which have a minimum film forming temperature of 0 to 70C and which are generally copolymers of at least three different monomers, the polycarboxylates not being crosslinked with metals.
The polymers preferably used contain as their most important constituent an acrylate copolymer of 1 to 30 parts by weight, based on copolymer, of monomers contain-ing carboxylic acid groups, 30 to 70 parts by weight of monomers which form homopolymers having glass tempera-tures below 20C, preferably esters of acrylic acid with Cl8 alcohols and/or of methacrylic acid with C4-8 alcohols, and 30 to 70 parts by weight of comonomers which form homopolymers having glass temperatures above room temper-ature, preferably methacrylates of C13 alcohols or styrene.
The comonomers containing acid groups may be ethy-lenically unsaturated carboxylic acids, acrylic acid and methacrylic acid being particularly suitable.
Comonomers having glass temperatures below 20C, i.e. glass temperatures below room temperature (based on homopolymers of a monomer) include esters of acrylic acid with Cl8 alcohols and esters of methacrylic acid with C4-8 alcohols. Thus, the methyl, ethyl, propyl, butyl or 2-ethylhexyl ester of acrylic acid and also the butyl, hexyl or 2-ethylhexyl ester of methacrylic acid may be used. Comonomers of which the homopolymers have glass temperatures above room temperature are esters of meth-acrylic acid with Cl3 alcohols, for example methyl methacrylate or ethyl methacrylate. A particularly important comonomer of which the homopolymer has a glass temperature above room temperature is styrene.
Copolymers of acrylic acid and/or methacrylic acid with styrene, acrylates and/or methacrylates are prefer-ably used. The copolymers of acrylic acid or methacrylic acid with various acrylates and/or methacrylates and/or styrene, for example terpolymers of methyl acrylate, ethyl acrylate, methacrylic acid and styrene, are parti-cularly preferred. The particular ratios of comonomers, of which the homopolymers have glass temperature below room temperature, to monomers of which the homopolymers have glass temperatures above room temperature should be adjusted in such a way that the film forming temperature of the polymer dispersion is in the range from 0 to 70OC.
General knowledge of polymer chemistry may be applied in this regard. The film forming temperatures mentioned ~O 94/2059S 10 PCT/EP94/00530 apply to the plasticizer-free system, i.e. to the poly-mers with no other additives. Examples of such polymers are the products Primal 1531 (Rohm and Haas), NeoCryl XK-39 and NeoCryl BT-26 (ICI).
At all events, the polycarboxylates used, unless they are already water-soluble as such, should be con-verted into a soluble form with the aid of alkalis.
Suitable alkalis are, in particular, NaOH, KOH and non-volatile amines, for example alkanolamines. It is preferred to use aqueous ammonia with which the polycar-boxylates can be safely clarified as required without any risk of over-alkalization. In their undiluted form, the final compositions should preferably have a pH value of about 7 to about 11, pH values of 8 to g and also 10 to 10.5 being particularly preferred.
The quantity of polymeric polycarboxylates in the compositions according to the invention is preferably selected so that the ratio by weight of polycarboxylate to total surfactant content is from 1:6 to 2:3 and, more particularly, from 1:4 to 1:2. If a mixture of several polymeric polycarboxylates is used, these figures apply to the total polycarboxylate content.
In addition to the compulsory ingredients described above and water and, optionally, alkalizing agents, the compositions according to the invention may contain other auxiliaries and additives of the type typically present in such compositions. The only proviso in this regard is of course that the positive properties of the composi-tions should not be adversely affected by these other auxiliaries and additives. Examples of such additives are organic, completely water-miscible solvents which may be used to increase performance and, optionally, to improve wetting power. Lower alcohols containing 2 or 3 carbon atoms are preferred, being used in quantities of not more than 10% by weight and preferably in quantities -of from about 0.2 to 5% by weight, based on the total weight of the undiluted composition. Examples of other additives are perfume oils, dyes, viscosity regulators and preservatives. These substances are normally present in quantities of not more than 5% by weight and preferab-ly in quantities of 0.01 to 2% by weight.
The compositions are used by initially preparing a solution of the composition, in which the content of non-volatile components is between about 0.2 and about 1 g/l, by dilution with water. Depending on the concentration of the original composition, this concentration is achieved by dilution in a ratio of about 1:1000 to about 1:50. The dilute solution is then applied to the surface to be cleaned with an absorbent article, for example with lS a cloth or a sponge, and then partly removed from the surface with the soil. After this treatment, the surface is not rinsed so that the remaining cleaning solution can dry to form a uniform protective film. It is due to this method of application that the compositions in question are also known as wiping compositions. The composition according to the invention is distinguished by an optimal cleaning effect on a number of soil types and, at the same time, forms a resistant film which affords excellent protection against resoiling. The film is completely transparent so that the color and texture of the treated surfaces appear largely unchanged without an additional gloss effect. When the composition is re-applied, the film dissolves and thus facilitates the cleaning process.
Troublesome film addition does not occur.
The composition according to the invention is particularly low foaming, even when it is used in rela-tively high concentrations or in undiluted form for the local removal of stains. Even in high concentrations, it shows excellent stability in storage at typical storage temperatures, but especially at low temperatures. The Wo 94/20595 12 PCT/EP94/00530 composition is particularly suitable for the care and cleaning and floors and gives excellent results on stone, sealed parquet, tiles, linoleum and plastic floors, although it may also be used for cleaning other hard surfaces, even glass. It can be applied with particular advantage to high-shine floor coverings because the film formed does not affect the shine by virtue of its high transparency.
The production of the composition in its various forms does not involve any difficulties. Normally, the polymeric polycarboxylate is first dissolved in water, optionally with addition of the alkalizing agent, and the surfactants are subsequently added in the required concentration. Finally, the additives are introduced.
Particulars of a preferred formulation for the composition according to the invention are given in the following. It contains:
1 to 10, preferably 2 to 6% by weight of fatty alcohol ethoxylate (3 to 10 E), 1 to 10, preferably 4 to 8% by weight of fatty alcohol polyglucoside, 0.5 to 4, preferably 1 to 3% by weight of anionic surfactant from the 2S group consisting of fatty alcohol sulfate, fatty alcohol ether sulfate and mixtures thereof, 30 1 to 8, preferably 3 to 5% by weight of alkali-soluble polymeric polycarboxylate with a minimum film forming temperature of 0 to 70C, 2I575 7~
~O 94/20595 13 PCT/EP94/00530 0 to 10, preferably 0.2 to 5% by weight of water-mis-cible organic solvents and 0 to 5, preferably 0.01 to 2% by weight of other auxi-liaries and additives.
Fxample~
Compositions 1 to 3 according to the invention and comparison compositions 4 to 10 as set out in Table 1 were prepared by mixing the individual components in water. The figures alongside the ingredients represent % by weight, the balance to 100% by weight being water.
Quantities of 3 g of the compositions were diluted to 1 liter and were used in this form to test cleaning power and resoiling behavior. The transparency of the residue remaining after drying was tested with a three times higher concentration of the compositions. Low-tempera-ture stability was tested on the undiluted compositions.
The test results are also set out in Table 1.
The individual tests were carried out as follows:
1. Testinq of cleaning ~ower The cleaning effect of the wiping compositions was determined using a Gardner washability and scouring tester as described in the quality standards of the Industrieverband Putz- und Pflegemittel e.V. (Sei-fen-ole-Fette-wachse~ 108, pages 526 to 528 (1982)).
In this method, a white PVC film is provided with a test soil of soot and grease and machine-wiped under standardized conditions with a sponge soaked with the cleaning composition. Cleaning performance is measured by photoelectric determination of reflec-tance (in %).
2. Testing of resoiling behavior For this test, a white PVC covering (75 x 21 cm) was divided into three equal sections of 25 x 21 cm.
Quantities of 1.2 ml of the solution to be tested were wiped over each of the sections using a cotton cloth. This wiping operation was repeated 9 times after drying. Resoiling behavior was then tested after drying in a special drum in which the PVC
covering was placed and then moved around for 30 minutes at 25 r.p.m. with 36 g of a special soiling mixture. The test soil had the following composi-tion:
3 g of sieved vacuum cleaner dirt (RFC of the Waschereiforschung, Krefeld) 3 g of burnt sea sand 15 g of plastic granules (Durethan WKV 30, a product of Bayer AG, Leverkusen) 15 g steel balls 6 - 7 mm in diameter.
After the soiling treatment, the test covering was removed from the drum, tapped and visually evaluated by three people. Evaluation was based on the following scale:
1 = covering very light, hardly soiled 2 = covering light, moderately soiled 3 = covering light grey, medium-soiled 4 = covering grey, heavily soiled 5 = covering dark grey, very heavily soiled.
3. Testinq of residue transparency A black, high-gloss tile (15 x 15 cm) was immersed in the test solution for 10 seconds and then placed in an upright position to dry. After complete drying, gloss was measured with a reflection meter (Dr. Lange, measuring angle 20) and compared with e_ the starting value determined before immersion. The differences between the two measured values are shown in Table 1 as the reduction in gloss.
4. Testing of low-temperature stability Undiluted cleaning compositions were stored for 24 hours at +3C in transparent glass bottles. There-after, the appearance of the samples was visually evaluated:
+ = product still clear - = product clouded or flocculated.
The test results set out in Table 1 show that the compositions according to the invention show particular advantages in regard to low-temperature stability and residue transparency for very good overall properties.
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Claims (9)
1. An aqueous floor cleaning composition containing nonionic surfactant, anionic surfactant and at least 1%
by weight of alkali-soluble polymeric polycarboxylate, characterized in that at least 25% by weight of the nonionic surfactant component consists of alkyl polygly-cosides.
by weight of alkali-soluble polymeric polycarboxylate, characterized in that at least 25% by weight of the nonionic surfactant component consists of alkyl polygly-cosides.
2. A floor cleaning composition as claimed in claim 1, in which the nonionic surfactants make up at least 50% by weight and preferably 65 to 95% by weight of the total surfactant content.
3. A floor cleaning composition as claimed in claim 1 or 2, in which the alkali-soluble polymeric polycar-boxylate has a minimum film forming temperature of 0 to 70°C.
4. A floor cleaning composition as claimed in any of claims 1 to 3, in which the ratio by weight of polymer to total surfactant content is from 1:6 to 2:3 and preferably from 1:4 to 1:2.
5. A floor cleaning composition as claimed in any of claims 1 to 4, in which the total surfactant content is between 4 and 25% by weight and preferably between 8 and 16% by weight, based on the weight of the composition as a whole.
6. A floor cleaning composition as claimed in any of claims 1 to 5 containing 1 to 10, preferably 2 to 6% by weight of fatty alcohol ethoxylate (3 to 10 E), 1 to 10, preferably 4 to 8% by weight of fatty alkyl polyglucoside, 0.5 to 4, preferably 1 to 3% by weight of anionic surfactant from the group consisting of fatty alcohol sulfate, fatty alcohol ether sulfate and mixtures thereof, 1 to 8, preferably 3 to 5% by weight of alkali-soluble polymeric polycarboxylate with a minimum film forming temperature of 0 to 70°C, 0 to 10, preferably 0.2 to 5% by weight of water-mis-cible organic solvents and 0 to 5, preferably 0.01 to 2% by weight of other auxi-liaries and additives.
7. A floor cleaning composition as claimed in any of claims 1 to 6, in which the alkyl polyglycoside used has an alkyl chain of 8 to 12 carbon atoms and a polyglyco-side component consisting of 1 to 2 glucose units.
8. The use of the composition claimed in any of claims 1 to 7 in diluted form for the simultaneous cleaning and care of hard surfaces, more particularly floors.
9. A process for the cleaning and care of floors, in which a composition according to any of claims 1 to 7 is diluted with water to a content of non-volatile constitu-ents of 0.2 to 1 g/l and the floor is subsequently wiped with this dilute solution of the composition using an absorbent article.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4306899.5 | 1993-03-05 | ||
| DE4306899A DE4306899A1 (en) | 1993-03-05 | 1993-03-05 | Floor cleaning products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2157570A1 true CA2157570A1 (en) | 1994-09-15 |
Family
ID=6482006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002157570A Abandoned CA2157570A1 (en) | 1993-03-05 | 1994-02-25 | A floor cleaning composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0687290B1 (en) |
| AT (1) | ATE158341T1 (en) |
| CA (1) | CA2157570A1 (en) |
| CZ (1) | CZ286846B6 (en) |
| DE (2) | DE4306899A1 (en) |
| DK (1) | DK0687290T3 (en) |
| ES (1) | ES2107195T3 (en) |
| GR (1) | GR3025103T3 (en) |
| HU (1) | HU218506B (en) |
| PL (1) | PL177230B1 (en) |
| SK (1) | SK280885B6 (en) |
| WO (1) | WO1994020595A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4335046A1 (en) * | 1993-10-14 | 1995-04-20 | Henkel Kgaa | Aqueous floor cleaning agent |
| DE19501145A1 (en) * | 1995-01-17 | 1996-07-18 | Huels Chemische Werke Ag | Use of alkyl polyglycosides as a friction reducer |
| DE19714424A1 (en) * | 1997-04-08 | 1998-10-15 | Beiersdorf Ag | Cosmetic and dermatological detergent compositions containing acrylate copolymers, alkylglucosides and alcohols |
| DE19717950A1 (en) * | 1997-04-29 | 1998-11-05 | Henkel Kgaa | Mixtures of surfactants |
| DE19908563C2 (en) * | 1999-02-27 | 2002-11-14 | Cognis Deutschland Gmbh | Detergent for hard surfaces |
| WO2009024747A2 (en) * | 2007-08-17 | 2009-02-26 | Reckitt Benckiser Inc. | Environmentally acceptable hard surface treatment compositions |
| DE102013210273A1 (en) * | 2013-06-03 | 2014-12-04 | Henkel Ag & Co. Kgaa | Washing, cleaning or pretreatment agent with increased cleaning power IV |
| AU2018266305B2 (en) * | 2017-05-11 | 2024-03-21 | Ecolab Usa Inc. | Compositions and method for floor cleaning or restoration |
| JP2024507407A (en) * | 2020-12-04 | 2024-02-19 | ベーアーエスエフ・エスエー | No-scrubbing cleaning composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8310529D0 (en) * | 1983-04-19 | 1983-05-25 | Unilever Plc | General-purpose cleaning composition |
| DE3533531A1 (en) * | 1985-09-20 | 1987-04-02 | Henkel Kgaa | CLEANER FOR HARD SURFACES |
| GB9027416D0 (en) * | 1990-12-18 | 1991-02-06 | Unilever Plc | Detergent composition |
| DE4116807A1 (en) * | 1991-05-23 | 1992-11-26 | Henkel Kgaa | CONCENTRATED AQUEOUS LIQUID DETERGENT |
| DE4216410A1 (en) * | 1992-05-18 | 1993-11-25 | Henkel Kgaa | Floor cleaning process |
-
1993
- 1993-03-05 DE DE4306899A patent/DE4306899A1/en not_active Withdrawn
-
1994
- 1994-02-22 SK SK1102-95A patent/SK280885B6/en unknown
- 1994-02-25 PL PL94310530A patent/PL177230B1/en unknown
- 1994-02-25 AT AT94909043T patent/ATE158341T1/en not_active IP Right Cessation
- 1994-02-25 DE DE59404098T patent/DE59404098D1/en not_active Expired - Fee Related
- 1994-02-25 HU HU9502589A patent/HU218506B/en not_active IP Right Cessation
- 1994-02-25 CZ CZ19952132A patent/CZ286846B6/en not_active IP Right Cessation
- 1994-02-25 ES ES94909043T patent/ES2107195T3/en not_active Expired - Lifetime
- 1994-02-25 DK DK94909043.5T patent/DK0687290T3/en active
- 1994-02-25 EP EP94909043A patent/EP0687290B1/en not_active Expired - Lifetime
- 1994-02-25 WO PCT/EP1994/000530 patent/WO1994020595A1/en active IP Right Grant
- 1994-02-25 CA CA002157570A patent/CA2157570A1/en not_active Abandoned
-
1997
- 1997-10-20 GR GR970402745T patent/GR3025103T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SK110295A3 (en) | 1997-07-09 |
| HUT72022A (en) | 1996-03-28 |
| CZ213295A3 (en) | 1996-01-17 |
| EP0687290B1 (en) | 1997-09-17 |
| ATE158341T1 (en) | 1997-10-15 |
| WO1994020595A1 (en) | 1994-09-15 |
| EP0687290A1 (en) | 1995-12-20 |
| HU218506B (en) | 2000-09-28 |
| DE59404098D1 (en) | 1997-10-23 |
| PL310530A1 (en) | 1995-12-27 |
| CZ286846B6 (en) | 2000-07-12 |
| ES2107195T3 (en) | 1997-11-16 |
| GR3025103T3 (en) | 1998-01-30 |
| DE4306899A1 (en) | 1994-09-08 |
| PL177230B1 (en) | 1999-10-29 |
| HU9502589D0 (en) | 1995-10-30 |
| DK0687290T3 (en) | 1998-05-04 |
| SK280885B6 (en) | 2000-09-12 |
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|---|---|---|---|
| EEER | Examination request | ||
| FZDC | Discontinued application reinstated | ||
| FZDE | Discontinued |