EP0687290A1

EP0687290A1 - Floor-cleaning agents

Info

Publication number: EP0687290A1
Application number: EP94909043A
Authority: EP
Inventors: Heinz-Dieter Soldanski; Marlies Kalibe; Juergen Noglich
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-03-05
Filing date: 1994-02-25
Publication date: 1995-12-20
Anticipated expiration: 2014-02-25
Also published as: WO1994020595A1; CZ286846B6; HU9502589D0; CZ213295A3; ATE158341T1; DK0687290T3; CA2157570A1; EP0687290B1; SK110295A3; HUT72022A; PL310530A1; SK280885B6; ES2107195T3; HU218506B; DE59404098D1; GR3025103T3; PL177230B1; DE4306899A1

Abstract

The invention concerns aqueous agents containing a non-anionic surfactant, an anionic surfactant and an alkali-soluble polymeric polycarboxylate, at least 25 % of the non-ionic surfactant consisting of alkylpolyglycoside. The agent is suitable for use, after dilution, for the cleaning and care of floors of any kind. It has a particularly good storage stability and gives a protective film which is highly transparent.

Description

Floor cleaning center 1

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 agents usually contain heavy metal salts, usually in an emulsified form, waxes or film-forming polymers and crosslinking agents, which together form self-glossy or polishable films on the treated surfaces after drying. 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, for example, in British Patent 1,552,992 and German Patent Application 35,33531. These agents, which are also referred to as wiping agents, contain, in addition to film-forming polymers, sufficient amounts of surfactants, in particular nonionic and anionic surfactants , so that care and cleaning with these agents are possible at the same time. There are certain difficulties with these agents if particular emphasis is given to low foaming in the application and for this reason larger amounts of low-foam non-ionic surfactants are used in the agents. The appropriately set agents are often not stable to segregation in the cold and have less good residue behavior when used on smooth floors, with occasional increased re-soiling of the films. To achieve an improvement here without impairing the otherwise good properties of known agents was one of the objects of the present invention.

The invention relates to an aqueous agent for cleaning floors which contains nonionic surfactant, anionic surfactant and alkali-soluble polymeric polycarboxylate, at least 25% by weight of the nonionic surfactants contained in these agents consisting of alkyl polyglycosides.

The new agents have excellent cleaning properties and, after drying on the floor surface, provide very uniform films with extraordinarily high transparency and very low tendency to re-soiling. Particularly noteworthy is the high stability against segregation when stored in the cold, which exists even if, in view of the particular low foam, very low-foam nonionic surfactants with relatively low water solubility are used and / or the agents have very high surfactant concentrations.

The surfactants contained in the compositions are based on a mixture of non-ionic and anionic surfactants. The nonionic surfactants make up at least 50% by weight of the total surfactant content in the agents according to the invention; their proportion is preferably between 65 and 95% by weight. 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 C8 " ^c 20" ^A ^ ^kono l ^e ' ^{such as Z} - ^B - ^with coconut or tallow fatty alcohols, oleyl alcohol, oxo alcohols or secondary alcohols of this chain length should be mentioned first and foremost. 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 nonionic surfactants are mono- and diethanolamides 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 adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylene diamine polypropylene glycol and with alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic residue . Of the aforementioned nonionic surfactants, the addition products of 3 to 10 moles of ethylene oxide with long-chain primary alcohols with 10 to 16 carbon atoms from the group of the oxo alcohols and the natural fatty alcohols are preferred in the agents according to the invention, the fatty alcohol ethoxylates being very particularly preferred.

In addition to the above-mentioned nonionic surfactants, the agents according to the invention always also contain alkyl polyglycosides as nonionic surfactants. These are surfactants of the general formula I.

R-0 (-G) _n I

in which R is a long-chain alkyl radical having 8 to 22 carbon atoms, G is a glycosidically bonded radical of a monosaccharide and n is a value between 1 and 10. 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.

A synthesis which is important today on an industrial scale consists essentially in the acid-catalyzed condensation of monosaccharides of the aldose type (HO-G) with long-chain alcohols (R-OH) which contain 8 to 22, preferably 8 to 18, C atoms . When water escapes, alkyl glycosides of the formula I are formed

-0 (-G) _n

the value of n can be varied within wide limits by the choice of reaction conditions. Alkylglycosides of the formula I with n = 1 to 10; Compounds with values for n between 1 and 6, in particular 1 to 2, are preferred. In products in which n is greater than 1, n naturally represents a statistical mean.

In the preparation of the alkyl glycosides, it is also possible to start from oligosaccharides or polysaccharides, which in the course of the acid-catalyzed reaction are then first polymerized to lower fragments by hydrolysis and / or alcoholysis before the alkyl glycosides of the formula I form. Mixtures of different reducing monosaccharides or polysaccharides which contain different monosaccharide units can also be used as starting materials, where, if n is greater than 1, appropriately mixed alkylglycoside molecules can be formed.

The following monosaccharides are preferably suitable as starting materials: glucose, mannose, galactose, arabinose, apiose, lyxose, gallose, old rose, idose, ribose, xylose and talose as well as the oligosaccharides and polysaccharides composed of these monosaccharides, for example maltose, lactose , Maltotriose, hemicellulose, starch, partial hydrolysates of starch and sugar syrup. In the context of the invention, however, alkyl glycosides are preferred which are composed of the same monosaccharide units. Special alkyl glycosides in which the rest (-G) is derived from glucose are also preferred. For these compounds, also known as alkyl glucosides, glucose, maltose, starch and other oligomers of glucose are used accordingly as starting materials.

In the preparation described above, the alkyl part R is derived from long-chain, optionally unsaturated, preferably primary alcohols, which may be branched but preferably are not branched. Examples are the synthetic oxo alcohols with 9 to 15 carbon atoms and the fatty alcohols with 8 - 22 carbon atoms obtained from natural fatty acids. The fatty alcohols with 8 to 18 carbon atoms and the oxo alcohols with 11 to 15 carbon atoms are preferred, but in particular the fatty alcohols with 8 to 10 carbon atoms or with 12 to 14 carbon atoms.

In addition to the actual alkyl glycosides of formula I, industrially manufactured products generally also contain certain proportions of free alcohol R-OH and non-acetalized saccharides, optionally in oligomerized form. In most cases, these technical impurities do not interfere with the intended use. If alcohol mixtures are used in the manufacture of the alkyl glycosides, for example alcohols based on natural fats, the alkyl glycosides are of course also mixtures with a correspondingly greater meaning of R in formula I.

In the context of the present invention, those alkyl polyglycosides are preferably used whose glycoside part consists of 1 to 2 glucose units and whose alkyl part is derived from fatty alcohols having 8 to 10 C atoms. The alkyl polyglycosides in the agents according to the invention make up at least 25% by weight of the total of nonionic surfactants present. In the limit, alkyl polyglycosides alone can be included as nonionic surfactants. A content of 40% by weight to 80% by weight of alkyl polyglycosides, based on the total of nonionic surfactants, is particularly preferred. The agents according to the invention primarily contain synthetic anionic surfactants as anionic surfactants. These are primarily 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 sulfate-type surfactants are the sulfuric acid monoesters of long-chain primary alcohols of natural or synthetic origin, ie. H. of fatty alcohols such as B. coconut fatty alcohols, oleyl alcohol, lauryl, myristyl, palmmityl or stearyl alcohol, or the Cιo-C2θ ~ 0xoalcohols or secondary alcohols of this chain length. The sulfuric acid monoesters of the long-chain primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide (E0) are also suitable. Sulfated fatty acid alkanolamides, sulfated fatty acid onoglycerides and long-chain sulfosuccinic acid esters are also suitable. The anionic surfactants are preferably used as alkali salts, in particular sodium salts, but ammonium salts or the salts of alkanolamines having 2 to 6 carbon atoms can also be used. Particularly preferred anionic surfactants in the context of the present inventions are the fatty alcohol sulfates and the fatty alcohol ether sulfates, for example Ci2 Ci8 ~ coconut alcohol sulfate Na and Ci2 / Ci4 coconut alcohol + 2E0 sulfate.

In addition to the nonionic and anionic surfactants mentioned, the Agents according to the invention also contain smaller amounts of other surfactants, in particular amphoteric surfactants and soaps, if this is expedient to achieve special effects and the other good properties of the agents 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 total content of surfactants in the agents according to the invention is preferably between 4 and 25% by weight, in particular between 8 and 16% by weight, based on the total agent in the undiluted state.

The content of alkali-soluble poly polycarboxylate is essential for the care properties of the agents. These carboxylates can be resin-like compounds, for example copolymers of styrene and maleic anhydride, which can be partially saponified and, if appropriate, also partially esterified or amidated. However, preference is given to soluble polymer compounds which have a minimum film-forming temperature between 0 and 70 ° C. and which are generally copolymers of at least 3 different monomers, the polycarboxylates not being cross-linked.

As the most important component, the polymers preferably used contain an acrylate copolymer of 1 to 30 parts by weight, based on copolymer, of monomers containing carboxylic acid groups, 30 to 70 parts by weight of monomers which form homopolymers with glass transition temperatures below 20 ° C., preferably esters of acrylic acid with Ci-Cβ- alcohols and / or methacrylic acid with C4-C8-alcohols, and form 30 to 70 parts by weight of comonomers which form homopolymers having glass temperatures above room temperature, vor¬ preferably methacrylic acid esters of C _j -CSS-alcohols or styrene . As comonomers containing acid groups, ethylenically unsaturated carboxylic acids can be used; acrylic acid and methacrylic acid are primarily suitable.

Comonomers with glass transition temperatures below 20 ° C, that is glass transition temperatures below room temperature (based in each case on homopolymers of a monomer) are esters of acrylic acid with C 1 -C 6 alcohols and esters of methacrylic acid with C 4 -C 8 alcohols. For example, the methyl, ethyl, propyl, butyl or 2-ethylhexyl ester of acrylic acid as well as the butyl, hexyl or 2-ethylhexyl ester of methacrylic acid can be used here. Comonomers whose homopolymers have glass transition temperatures above room temperature are esters of methacrylic acid with C1-C3 alcohols, such as, for example, methyl methacrylate or ethyl methacrylate. A particularly important co onomer whose hoopolymer has a glass transition temperature above room temperature is styrene.

Copolymers of acrylic acid and / or methacrylic acid with styrene, acrylic acid esters and / or methacrylic acid esters are preferably used. The copolymers of acrylic acid or methacrylic acid with different acrylic and / or methacrylic acid esters and / or styrene are particularly preferred, for example terpolymers of methyl acrylate, acrylic acid ester, methacrylic acid and styrene. The respective ratios of comonomers whose homopolymers have glass transition temperatures below room temperature and monomers whose homopolymers have glass transition temperatures above room temperature must be set so that the film formation temperature of the polymer dispersion is in the range between 0 and 70 ° C. The general knowledge of polymer chemistry applies. The film formation temperatures mentioned relate to the plasticizer-free system, i. H. on the polymers without further additives. Examples of such polymers are the products Pri al 1531 (Rohm and Haas), NeoCryl XK-39 and NeoCryl BT-26 (ICI).

In any case, the polycarboxylates used, if they are not already water-soluble as such, should be able to be converted into a soluble form with the aid of alkalis. In particular, NaOH, KOH and non-volatile amines, such as, for example, alkanolamines, come in as alkalis Question. Aqueous ammonia is preferred, with the aid of which the desired clarification of the polycarboxylates can be carried out particularly safely without the risk of overbasing. The finished compositions should preferably have a pH between about 7 and about 11 in the undiluted state; the ranges with pH values between 8 and 9, but also between 10 and 10.5 are particularly preferred.

The amount of polymeric polycarboxylates in the agents according to the invention is preferably selected so that the weight ratio between polycarboxylate and the total content of surfactants is between 1: 6 and 2: 3, in particular between 1: 4 and 1: 2. If a mixture of several polymeric polycarboxyates is used, these values apply to the total polycarboxylate content.

In addition to the above-described mandatory ingredients and water and, if appropriate, alkalizing agents, the agents according to the invention can contain further auxiliaries and additives, as are customary in such agents. It is a prerequisite, of course, that the positive properties of the agents are not impaired thereby. Examples of such additives are organic, completely water-miscible solvents which are used to increase the performance and, if appropriate, to improve the wetting capacity. Lower alcohols having 2 or 3 carbon atoms are preferably used, 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 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 agents are used in such a way that a solution of the agent is first prepared by dilution with water, in which the content of non-volatile constituents is between about 0.2 and about 1 g / l. Depending on the concentration of the original agent, this concentration is reached by dilution between about 1: 1000 and about 1:50. The diluted solution is then applied to the surface to be cleaned with the aid of an absorbent object, 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 cleaning agent solution can dry out to form an evenly protective film. Because of this application method, such agents are also referred to as wiping agents. The agent according to the invention is distinguished by an optimal cleaning action against a multitude of soiling and at the same time forms a resistant film which forms an excellent protection against re-soiling. The film is completely transparent and allows the color and structure of the treated surfaces to appear largely unchanged without additional gloss. When the agent is used again, the film dissolves and thereby facilitates the cleaning process. There is no annoying film addition.

The agent according to the invention is particularly low-foaming even when it is used in higher concentration or undiluted for the local removal of stains. Even in high concentration, it has excellent storage stability at the usual storage temperatures, but especially in the cold. The agent is preferably suitable for cleaning floors and provides excellent results on stone, sealed parquet, tiles, linoleum and plastic floors, but it is also suitable for cleaning other hard surfaces, even for glass . Use on high-gloss floor coverings is particularly advantageous because the film formed does not reduce the gloss due to its high transparency.

The preparation of the agent in its various embodiments presents no difficulties. Usually, the polymeric polycarboxylate is first dissolved in water, if appropriate with the addition of the alkalizing agents, and the surfactants are then mixed in at the desired concentration. Finally, the additives follow.

In the following, some details are given regarding a preferred frame formulation of the agent according to the invention. It contains: 1 to 10, preferably 2 to 6 wt .-% fatty alcohol ethoxylate (3 to 10 E0).

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 group

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 between 0 and 70 ° C,

0 to 10, preferably 0.2 to 5% by weight of water-miscible organic

Solvents and

0 to 5, preferably 0.01 to 2% by weight of further auxiliaries and additives.

Examples

By mixing the individual constituents in water, the compositions No. 1 to 3 according to the invention specified in Table 1 and the compositions No. 4 to 10 not according to the invention were prepared. The figures for the ingredients mean% by weight; the rest 100% by weight is water. 3 g of these agents were each diluted to one liter and used in this form to test the cleaning ability and the re-soiling behavior. The transparency of the residue remaining after drying was checked with a 3-fold stronger concentration of the agents; The cold stability was tested on the undiluted agents. The test results are also shown in Table 1.

The procedure for the tests was as follows:

1. Testing the cleanliness

The cleaning effect of the wiping care products was determined with the aid of a Gardner washability and abrasion test device, as described in the quality standards of the Industrial Association of Cleaning and Care Products e. V. is described (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. 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 of 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 = covering light gray, medium soiled

4 = gray covering, heavily soiled

5 = covering intensely gray, very heavily soiled.

3. Checking the transparency of residues

A black, high-gloss tile (15 x 15 cm) was immersed in the test solution for 10 seconds and then set up perpendicularly to dry. After drying completely, the gloss was determined with the aid of a reflection measuring device (Dr. Lange, measuring angle 20 °) and compared with the initial value determined before the dipping process. Table 1 shows the differences between the two measured values as a decrease in gloss.

4. Testing the cold stability

Undiluted cleaning agents were stored in transparent glass bottles at +3 ° C for 24 hours. After this time the appearance of the samples was assessed visually:

+ = Product unchanged clear

- = product clouded or flocculated.

It is clear from the test results listed in Table 1 that the compositions according to the invention have particular advantages in terms of low-temperature stability and transparency of residues while having very good properties overall. Table 1

Examples

3 4 5 6 7 8 9 10

Ci2 / 14 fatty alcohol sulfate Na 2 1.5 3 2 2 2 8 8 6 6 Ci2 / i4 fatty alcohol + 4 EO 4 3 4 10 10 4 4 6 6 Ci2 / i4 fatty alcohol + 6 EO 3 C _β / io-alkyl polyglucoside ( 1.6 glucose) 6 7 6 6 _ _ _ _ _ copolymer of methacrylic acid, Bu- 5 4 5 - 4 - 5 - 5 - tylacrylate and methyl methacrylate with NH 0H clarified (pH 8.5) ethanol 5 5 5 5 5 5 5 5 5 Perfume + + + + + + + + + +

Cleaning capacity according to Gardner) (1) 45 43 46 32 34 29 43 33 38 32

Resoiling behavior (2) 2-3 2-3 2 4 2-3 4-5 2 3-4 2-3 4

Residue transparency (3) -2 -3 -3 -2 -12 -7 -10 -5 -10 -5

Cold stability (4) + + + + - - - - -

Claims

1. Aqueous floor cleaning agent containing nonionic surfactant, anionic surfactant and alkali-soluble polymeric polycarboxylate, characterized in that at least 25% by weight of the proportion of nonionic surfactants contained consists of alkyl polyglycosides.

2. Floor cleaning agent according to claim 1, in which the proportion of non-ionic surfactants in the total content of the surfactants is at least 50% by weight, preferably between 65 and 95% by weight.

3 floor cleaning agent according to one of claims 1 or 2, wherein the alkali-soluble poly ere polycarboxylate has a minimum film forming temperature between 0 and 70 ° C.

4. Floor cleaning agent according to one of claims 1 to 3, in which the weight ratio between polymer and the total content of surfactants is between 1: 6 and 2: 3, preferably between 1: 4 and 1: 2.

5. Floor cleaning agent according to one of claims 1 to 4, in which the total surfactant content is between 4 and 25%, preferably between 8 and 16% by weight, based on the weight of the finished agent.

6. Floor cleaning agent according to one of claims 1 to 5, containing

1 to 10, preferably 2 to 6% by weight of fatty alcohol ethoylate (3 to 10 E0), 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 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 between 0 and 70 ° C,

0 to 10, preferably 0.2 to 5% by weight of water-miscible organic solvents and

0 to 5, preferably 0.01 to 2 wt .-% of further auxiliary and

Additives.

7. Floor cleaning agent according to one of claims 1 to 6, in which the alkyl polyglycoside used is one having an alkyl chain consisting of 8 to 12 carbon atoms and a polyglycoside part consisting of 1 to 2 glucose units.

8. Use of an agent according to one of claims 1 to 7 in the thinned state for simultaneous cleaning and care of hard surfaces, in particular floors.

9. A method of cleaning and maintenance of floors, in which an agent according to one of claims 1 to 7 is first diluted with water to a nonvolatile content of 0.2 to 1 g / 1 and then the floor with the aid of an absorbent article is wiped with this dilute solution of the agent.