EP0723578A1

EP0723578A1 - Aqueous floor cleaning agent

Info

Publication number: EP0723578A1
Application number: EP94928862A
Authority: EP
Inventors: Heinz-Dieter Soldanski; Daniela Poethkow
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-10-14
Filing date: 1994-10-05
Publication date: 1996-07-31
Also published as: WO1995010589A1; DE4335046A1; JPH09503804A; US5753604A

Abstract

The cleaning agent takes the form of an aqueous dispersion and contains a tenside, a film-forming polymer and a softener, in which the film-forming polymer is a mixture of two polymers of different molecular weights, the higher one of which is not soluble in water at a pH of 12, whereas the lower one is water-soluble at a pH of 9. After dilution, the agents are used for the cleaning and care of floorings of all kinds. They are distinguished by good cleaning action, even shine and good soiling resistance.

Description

"Aqueous Floor Cleaner"

The present invention relates to an aqueous agent which can be used in the diluted state for cleaning and maintaining hard surfaces, in particular floors.

Numerous new processes and agents have been developed for cleaning and maintaining floors in recent years and decades, not least due to the development of new materials for floor coverings. In practice, the selection of the agents is essentially determined by whether cleaning or preservation of the surface is to be achieved as a matter of priority. For the care and preservation of surfaces, primarily those agents are used which produce more or less hard, resistant films. For this purpose, the compositions usually contain, in emulsified form, waxes or film-forming polymers and crosslinking agents, as a rule heavy metal salts which, after drying, form self-glossy or polishable films on the treated surfaces. In this way, long-lasting preservation of the surfaces can be achieved, with strong mechanical stresses being well tolerated, depending on the quality of the film. However, removal of such films is only possible under extreme conditions if it becomes necessary, for example because of dirt or damage. In contrast, agents whose main focus is on cleaning contain high levels of surfactants, often together with alkaline substances, organic solvents or abrasives. In many cases a thorough removal of dirt and old coverings is possible with these agents, but the surfaces cleaned in this way are then usually exposed to re-soiling without protection, unless a preservation treatment is connected.

Since in many cases cleaning and maintenance of the floor surface are equally desirable, in addition to these agents, those have also been developed which can be used for cleaning and preservation in one operation are. Examples of such agents can be found in British Patent 1,528,592, in German Patent Application DE 35 33 531 and in the older, as yet unpublished German Patent Application P 4306899. These agents, which are also referred to as wiping agents, contain sufficient alkali-soluble film-forming polymers Amounts of surfactants, especially ionic and anionic surfactants, so that care and cleaning with these agents are possible at the same time. It is remarkable, however, that even if these agents are used several times, the floor is not given an additional shine. Especially with heavily used floors, both a high cleaning performance and a clear build-up of gloss are often desired. At the same time, re-soiling on the treated floors should remain as low as possible. One of the objects of the present invention was to create a means which combines all of these properties.

The invention relates to an aqueous floor cleaning agent in the form of a dispersion which contains surfactant, film-forming polymer and plasticizer and, if appropriate, further constituents customary in wiping care products and which is characterized in that it is both a high molecular weight polymer which has a pH of 12 is not water-soluble, and also contains a low molecular weight polymer which is water-soluble at a pH of 9.

The new agent has excellent cleaning properties and gives the floor surface a very uniform, clear shine after drying, which increases with repeated use. Nevertheless, the tendency towards re-soiling of the floors cleaned in this way is extraordinarily low. It is particularly noteworthy that the glossy film is obtained without the use of heavy metal salts as the crosslinking component.

Characteristic of the new agents is the simultaneous presence of two different polymers, one of which is high molecular weight and insoluble even in strong alkali, while the second polymer has a relatively low molecular weight and is clearly water-soluble even at a pH of 9 or lower is. Of course, one or the other type of polymer can also contain several chemically different types. Both in the high molecular weight as The low molecular weight polymer is also a homopolymer or, preferably, a copolymer which consists at least partly of esters of acrylic acid or methacrylic acid. The high molecular weight polymer is preferably selected from the group of the polyacrylates and the acrylate-styrene copolymers and contains, if at all, only small amounts of carboxyl groups. The low molecular weight polymers are preferably copolymers of acrylic acid or methacrylic acid with esters of acrylic acid, methacrylic acid or with styrene. The molecular weight of the high molecular weight polymer is usually between about 5 × 10 ⁵ and 2.5 × 10 ⁶ , preferably between 1.0 × 10 ⁶ and 2.0 × 10 ⁶ . The molecular weight of the low molecular weight polymer is usually not more than about 100,000, preferably between 30,000 and 80,000. Polymers of the two types are commercially available and are usually offered in the form of aqueous dispersions with a solids content between about 30 and 50% by weight and about neutral to weakly acidic pH. Of the high molecular weight polymers suitable for the agents according to the invention are those which are not water-soluble even at a pH of 12. To test this property, 5 parts by weight of the polymer or a correspondingly larger amount of its aqueous dispersion are made up to 100 parts by weight with distilled water and, while stirring at room temperature, with 10% sodium hydroxide solution to a pH of 12.0 set. With this treatment, the polymer must not go into solution within 10 minutes. In contrast, of the low molecular weight polymers, only those types are suitable for the agents according to the invention which are clear in solution from 5% dispersion in water after addition of aqueous ammonia to a pH of 9.0 within 10 minutes at room temperature go.

Examples of some commercially available types of the high molecular polymer are the products Primal NT-2624, Pri al NT-2819, Pri al NT-2611 from Rohm & Haas, the products Neocryl AS 8-B and Neocryl AS 19 from Zeneca, the product Ubatol U 4138 from Stapol, the product Poligen ES 9666 X from BASF and the product D 40 - 3 A from Morton International. The high molecular weight polymers should preferably have minimal film temperature between 40 and 80 ° C. Examples of suitable low-molecular commercial products are the Primal E 1531 polymers from Rohm & Haas and Neocryl XK 39 from Zeneca. The total content of the abovementioned polymers in the agents according to the invention is preferably 3 to 15% by weight and in particular 5 to 12% by weight. The weight ratio of high molecular weight to low molecular weight polymer is preferably 1: 4 to 4: 1, in particular 1: 1 to 3: 1.

In addition to the combination of at least two polymers of different molecular weights, the agents according to the invention contain at least one surfactant and one plasticizer. The surfactant content is preferably between 1 and 6% by weight, in particular 1.5 to 3% by weight, based on the total weight of the composition. The proportion of plasticizer is preferably 0.3 to 5% by weight, preferably 0.6 to 3% by weight, also based on the weight of the finished agent.

The surfactants contained are preferably nonionic or anionic surfactants. In principle, all types of nonionic surfactants are suitable as nonionic surfactants for the agents according to the invention, provided that they meet the requirements regarding low foam. The addition products of 3 to 20 moles of ethylene oxide (E0) with primary Cs-C2 () alcohols, such as, for example, B. on coconut or tallow alcohols, oleyl alcohol, oxo alcohols or secondary alcohols of this chain length. The corresponding ethoxylation products of other long-chain compounds are also suitable, for example the fatty acids and the fatty acid amides with 12 to 18 C atoms and the alkylphenols with 8 to 16 C atoms in the alkyl part. In all of these products, propylene oxide (PO) can also be added instead of part of the ethylene oxide. Also suitable as non-ionic surfactants are mono- and diethanol ide of fatty acids and long-chain amine oxides or sulfoxides, for example the compound N-cocoalkyl-N, N-dimethylamine oxide. Also to be mentioned are the water-soluble addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide onto polypropylene glycol, alkylene diamine polypropylene glycol and onto alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic residue. Of the aforementioned nonionic surfactants, the agents according to the invention the addition products of 3 to 10 mol of ethylene oxide onto long-chain primary alcohols having 10 to 16 carbon atoms from the group of the oxo alcohols and in particular natural fatty alcohols are preferred.

A very particularly preferred class of nonionic surfactants are the alkyl polyglycosides for the agents according to the invention. These are surfactants of the general formula I.

R-0 (-G) _n (I)

in which R is a long-chain alkyl radical with 8 to 22 carbon atoms, G is a glycosidically bound radical of a monosaccharide and n is a value between 1 and 10. When these surfactants are used, extraordinarily high cleaning performance is achieved in the compositions according to the invention even with small amounts of surfactant and at the same time very little tendency to re-soiling. The agents according to the invention therefore preferably contain alkyl polyglycosides as a predominant part of the total amount of the surfactants contained; It is particularly preferred to use exclusively alkyl polyglycosides as surfactants in the agents according to the invention.

Alkyl polyglycosides have been known as surface-active substances for more than 50 years and can be produced in various ways. In this context, reference should only be made to European patent application 362 671, which also cites literature on older processes. In the context of the invention, alkyl glycosides in which the rest (-G) is derived from glucose are preferred. The alkyl part R is preferably derived from long-chain, optionally unsaturated, preferably primary alcohols, which can be branched, but are preferably not branched. Examples are the synthetic oxo alcohols with 9 to 15 C atoms and the fatty alcohols obtained from natural fatty acids with 8 to 22 C atoms. In the context of the present invention, those alkyl polyglycosides are preferably used whose glycoside part consists of 1 to 2 glycose units and whose alkyl part is derived from fatty alcohols having 8 to 10 carbon atoms.

The agents according to the invention can primarily contain synthetic anionic surfactants as anionic surfactants. It is above all those of the sulfonate and sulfate type.

As surfactants of the sulfonate type come alkylbenzenesulfonates with a C9-C15 alkyl radical and olefin sulfonates, i.e. H. Mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C12-C18-M0-noolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, are considered. Also suitable are the alkanesulfonates which are obtainable from Ci2-Ci8-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of α-sulfo fatty acids, e.g. B. the α-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel 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, ie of fatty alcohols, such as, for example, B. coconut fatty alcohols, oleyl alcohol, lauryl, myristyl, palmmityl or stearyl alcohol, or the Cιo- 2θ "O ^χoa l '^<0 * ¹⁰ l ^en or secondary alcohols of this chain length. Also the sulfuric acid monoester with 1 to 6 moles Ethylene oxide (EO) ethoxylated aliphatic long-chain primary alcohols or ethoxylated secondary alcohols are suitable. Sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides and long-chain sulfosuccinic acid esters are also suitable. The anionic surfactants are preferably used as alkali metal salts, in particular sodium salts, but ammonium salts can also be used or the salts of alkanolamines with 2 to 6 carbon atoms are used. Particularly preferred anionic surfactants in the context of the present invention are the fatty alcohol sulfates and the fatty alcohol ether sulfates, for example Ci2 Ci8 ~ ocosal alcohol sulfate Na and Ci2 / Ci4 coconut alcohol + 2E0- Sulfate Na.

Anionic surfactants are preferably used in combination with nonionic surfactants. A particularly preferred combination consists of fatty alcohol sulfate and fatty alcohol ethoxylates with 3 to 6 ethylene oxide units.

In addition to the nonionic and anionic surfactants mentioned, the agents according to the invention can also contain smaller amounts of other surfactants, in particular contain other surfactants and soaps if this is expedient to achieve special effects and the other good properties of the compositions are not thereby impaired. The soaps are the water-soluble salts of long-chain fatty acids with preferably 12 to 18 carbon atoms, for example coconut fatty acid sodium salt and tallow fatty acid sodium salt. The amphoteric surfactants are long-chain compounds whose hydrophilic part consists of a cationically charged center (usually a tertiary amino or a quaternary ammonium group) and an anionically charged center (usually a carboxylate or a sulfonate group). Examples of such surfactants are N-coco-alkyl-N, N-dimethylaminoacetate and N-dodecyl-N, N-dimethyl-3-aminopropanesulfonate.

The plasticizers contained in the agents according to the invention can be both temporary and permanent plasticizers. Usually a mixture of both types is used. On the one hand, the plasticizers have the task of facilitating the formation of the polymer film when the cleaning agent dries and at the same time to prevent the film from becoming brittle after drying. Temporary plasticizers are those which have a marked volatility at room temperature, so that they evaporate from the care agent films after a certain time, while permanent plasticizers are non-volatile and remain in the films. Examples of suitable temporary plasticizers are ethers of monoethylene glycol, diethylene glycol and triethylene glycol and of dipropylene glycol and tripropylene glycol, and likewise the acetates of these ethers, provided that they are sufficiently water-soluble and can be accepted in terms of smell. Examples of suitable permanent plasticizers are tributoxyethyl phosphate, mono- and dialkyl esters of phthalic acid, 2,2,4-trimethyl-l, 3-pentanediol mono- or diisobutyrate and 2-methylpyrrolidine.

In addition to the abovementioned proportions, the agents according to the invention can contain further ingredients customary in wiping care agents. It is a prerequisite, of course, that this does not impair the positive properties of the agents. Waxes should be mentioned primarily, with the help of which the caring properties of the agents can be further modified. Both natural and synthetic waxes are suitable. see origin, for example carnauba wax and candellaw wax or polyethylene wax and montan ester wax. Montanester waxes with dropping points between 75 and 90 ° C and acid numbers from 15 to 40 are preferred. The polyethylene waxes preferably have dropping points between 100 and 140 ° C. In the agents according to the invention, the waxes preferably make up no more than 5% by weight, in particular 0.1 to 2% by weight are used.

Organic, completely water-miscible solvents, which are used to increase the performance and, if appropriate, to improve the wetting capacity, may be mentioned as examples of further customary additives. Lower alcohols having 2 or 3 carbon atoms are preferred, amounts not exceeding 10% by weight, preferably between about 0.2 and 5% by weight, based on the total weight of the undiluted agent. Examples of other additives are perfume oils, dyes, viscosity regulators, agents for adjusting the pH and preservatives. These substances are usually used in amounts of not more than 5% by weight, preferably between 0.01 and 2% by weight.

The pH of the compositions is preferably between 7 and 11, in particular between 8 and 10, but in individual cases values outside these ranges, for example in the weakly acidic range, can also be selected if this is expedient for special reasons. pH values in the alkaline range are set by adding customary alkalis, for example KOH, NaOH, Na2C03, NH3 and alkanolamines, preferably by adding ammonia and / or NaOH.

The agent is usually used in such a way that a preparation of the agent is prepared first by dilution with water, in which the content of non-volatile constituents is between about 1 and about 4 g / 1. Depending on the concentration of the original agent, this concentration is achieved by dilution between about 1: 200 and about 1:15. The diluted preparation is then applied to the surface to be cleaned with the aid of an absorbent article, for example with the aid of a wipe or a sponge, and z. T. removed with the dirt from the surface again. After this treatment, the surface not rinsed off, so that the remaining detergent solution can dry out to an evenly protective film. Because of this application method, agents of this type are also referred to as wiping agents. The agent according to the invention is distinguished by an exceptional cleaning action against a multitude of soiling and at the same time forms a resistant film which forms excellent protection against re-soiling. The film also gives floors subject to heavy wear an additional gloss, which increases when the agent is used several times. The agent is preferably suitable for the care cleaning of floors and delivers excellent results on stones, sealed parquet, tiles, linoleum and plastic floors. The nourishing properties of the product are particularly effective on matt surfaces, which are given an additional shine when the product is used.

The preparation of the agent in its various embodiments presents no difficulties. Usually, the low molecular weight polymer is first dissolved in water, if appropriate with the addition of alkalizing agent, then the surfactants are mixed in at the desired concentration before the high molecular weight polymer is introduced, usually in the form of a prefabricated dispersion. Plasticizers and other additives are usually entered last.

Examples

By mixing the individual components in water, the agents 1 to 7 according to the invention given in Table 1 and the agents 8 to 14 not according to the invention were prepared. The pH of the agents was brought to 9.0 uniformly with ammonia. Figures for the ingredients in Table 1 mean percent by weight; the remainder to 100% by weight is water. 25 g of these agents were each diluted to 1 1 with water and used in this form to test the cleaning ability, the gloss formation and the re-soiling behavior. The test results are also listed in Table 1.

The tests were carried out as follows:

1. Checking the cleanliness

The cleaning effect of the wiping care products was determined with the help of a Gardner washability and abrasion tester, as described in the quality standards of the Industrial Association for Cleaning and Care Products e. V. (Seifen-Öle-Fette-Wwachs, 108, pages 526 to 528 (1982)). In this method, a white PVC film is soiled with soot and grease and, under standardized conditions, is wiped by machine with a sponge soaked in the cleaning agent. The cleaning performance is measured by photoelectric determination of the reflectance (in%).

2. Gloss qebunq

The test was carried out on an anthracite-colored terrazzo stone with light inclusions, which had a surface of 15 x 30 cm. 3 ml of the test solution were added to the stone and evenly distributed with a damp and well wrung out cotton cloth. The process was carried out a total of 20 times, each time with a new cloth, the time interval between two jobs being at least 1 hour, so that the surface could dry constantly in any case. The gloss was then determined using a reflectometer (Dr. Lange company, measuring angle 60 °) and compared with the initial value of the untreated stone. In the table are the differences between the two measured values are reproduced as an increase in the gloss, the measured values being determined as mean values from measurements at 6 different points. With the means according to the invention, the measured values did not vary by more than one unit around the average value.

3. Check the re-soiling behavior

Here, a white PVC covering (75 x 21 cm) was divided into three equal sections of 25 x 21 cm. 1.2 ml of the solution to be tested was distributed on each of these partial areas with its own cotton cloth. This wiping process was repeated nine times after drying. The soiling behavior was then checked after drying in a special drum in which the PVC covering was placed and moved with 36 g of a special soiling mixture for 30 minutes at 25 revolutions per minute. The test dirt had the following composition:

3 g sieved vacuum cleaner dirt (RFC from laundry research, Krefeld)

3 g of burnt sea sand

15 g plastic granules Durethan WKV 30 (Bayer, Leverkusen)

15 g steel balls 6 - 7 mm in diameter

After the soiling process, the test sheet was removed from the drum, tapped off and visually inspected by three people. The evaluation was based on the following grid:

1 = very light topping, hardly soiled

2 = covering light, moderately soiled

3 = slightly gray covering, medium degree of protection

4 = gray covering, heavily soiled

5 = covering intensely gray, very heavily soiled.

It is clear from the test results listed in Table 1 that the agents according to the invention both have good cleaning properties and bring about a clear increase in gloss, while the re-soiling behavior is low. Table 1

B e i s p i e l e

8 9 10 11 12 13 14

not alkali-soluble 4 3 4 8 6 3 8 - - - 6 9 9 12 acrylic-styrene copolymer (Primal NT 2624), molecular weight over 500000 alkali-soluble 2 6 8 4 3 6 4 6 9 12 -. . _

Acrylate copolymer (Primal E 1531), molecular weight below 100,000

C ₈ -Cιn-alkyl- 2.1 2.1 2.1 2.1 - - - 2.1 2.1 2.1 2.1 2.1 7 2.1 polygiucoside (1.6 glucose)

Ci2-Ci4-fatty alcohol sulfate Na

Ci2-Ci4 fatty alcohol + 4 E0

Cι? -Ci4 fatty alcohol + 6 E0

10 11 12 13 14

Tributoxyethyl- 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 phosphate

Diethylene glycol 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 monomethyl ether

Perfume, preservative + + + + + + + + + + + + + + cross-linking agent

1.Cleaning 61 60 61 58 59 58 59 64 60 67 40 40 54 39

2nd increase in gloss +12 +19 +19 +23 +18 +19 +22 +6 +9 +4 +16 +20 ± 0 +25 on terrazzo

3. Restart 2 2 2 2 2 2 2 2 2 2 2 2 5 2 dirt behavior

Claims

claims

1. Aqueous floor cleaning agent in the form of a dispersion containing surfactant, film-forming polymer and plasticizer, characterized in that it is both a high molecular weight polymer which is insoluble in water at a pH of 12 and a low molecular weight polymer which is soluble in a pH Value of 9 is water soluble.

2. Floor cleaning agent according to claim 1, wherein the molecular weight of the high molecular weight polymer between 5. 10 * 5 and 2.5. 10-5 lies.

3. Floor cleaning agent according to one of claims 1 or 2, wherein the molecular weight of the low molecular weight polymer does not exceed 100,000, preferably between 30,000 and 80,000.

4. Floor cleaning agent according to one of claims 1 to 3, wherein the high molecular weight polymer is selected from the group of polyacrylates, acrylate-styrene copolymers and mixtures thereof.

5. Floor cleaning agent according to one of claims 1 to 4, wherein the high molecular weight polymer has a minimum film-forming temperature between 40 and 80 ° C.

6. Floor cleaning agent according to one of claims 1 to 5, in which the low molecular weight polymer is selected from the group of the Copolymeri¬ sate of acrylic acid or methacrylic acid with esters of acrylic acid, methacrylic acid and / or with styrene.

7. Floor cleaning agent according to one of claims 1 to 6, containing a total of 4 to 15 wt .-%, preferably 6 to 10 wt .-%, based on the total weight of the agent, of polymers, the weight ratio of high molecular weight to low molecular weight polymer 1: 4 to

Is 4: 1.

8. Floor cleaning agent according to one of claims 1 to 7, containing 0.3 to 5 wt .-%, preferably 0.6 to 3 wt .-% of plasticizer.

9. Floor cleaning agent according to one of claims 1 to 8, containing 1 to 6 wt .-%, preferably 1.5 to 3 wt .-% of surfactant.

10. Floor cleaning agent according to one of claims 1 to 9, in which the surfactant contained consists predominantly, preferably completely, of alkyl polyglycoside.