DE4311159A1 - Use of liquid concentrates for cleaning hard surfaces - Google Patents

Description

Liquid all-purpose cleaners for household and domestic use Businesses have been firmly established over the past decade because they are simple and easy to use. Most are the means as preferably aqueous concentrates in the trade. They leave already as such, d. H. undiluted, on a damp absorbent Apply cloth of any texture or a sponge with which the hard surfaces of metal, lacquered wood, plastic, ceramic Products, such as porcelain, tiles, tiles and the like, wiped off and thereby remove dust, grease and stains. It will desired that this surface treatment in turn no cleaning Mittelflecken and strips leaves and no after-treatment, at For example, with a soaked in clear water, so damp cloth, requires.

Such general purpose liquid detergents are generally made concentrated solutions of various anionic surfactant mixtures, but also mixtures from anionic and nonionic surfactants are known. You will u. a. in DE 27 09 690, DE 28 40 463, EP 71 411, DE 39 43 070 and DE 41 34 973 described.

From EP 70 074 combinations of alkyl polyglucosides and C ₁₂ -C ₁₄ - alkyl sulfates or alkyl ether sulfates are known, which foam increasingly. Their use as all-purpose cleaning agents could therefore not be discussed.

In the non-prepublished DE 42 10 365 are all-purpose cleaning medium, the predominantly nonionic surfactants addition gegebe optionally up to 25% of the total amount of surfactant anionic surfactants ent hold.  

Surprisingly, it has now been found that trate for hard surfaces comes to an unpredictable outstanding cleaning performance liquid detergent Konzen if one a) anionic and b) as nonionic surfactants small amounts of a) to alkylpolyglycosides of the formula ROZ _x with R = C ₈ - C ₁₄ , O = oxygen and x = 1-1.6, wherein Z represents a sugar unit, namely a glucose and / or preferably a xylose unit, and optionally additionally uses other known nonionic surfactants.

The cleaning performance of these concentrates reaches the level known, good, but only reluctantly used Alkylbenzolsulfonathaltiger Re zepturen with a cleaning-enhancing polymer content, as z. B. fall within the scope of DE 28 40 463.

The present invention thus relates to the use of liquid Konzen on the basis of aqueous solutions of anionic surfactants and nonio African surfactants, organic and / or inorganic builders, water-soluble solvents or solubilizers and other conventional components of such detergents as nonionic surfactant about 0.1 to 45 , preferably about 1.0 to 30 wt .-%, based on the total concentrate, of an alkyl glycoside of the formula ROZ _x with R = C ₈ - C ₁₈ , preferably C ₈ -C ₁₄ , O = oxygen and x = about 1- 2, preferably, about 1-1.6, wherein Z is a glucose and / or preferably a Xylo seeinheit included, for cleaning hard surfaces.

Among the usable alkyl glycosides compounds are here before on average less than two glucose or xylose units per alkyl radical, in particular those having about 1 to 1.6 glucose or xylene understood units. By "alkyl", not only but preferably the residues of those produced by hydrogenation of natural fatty acids Fatty alcohols that are completely or predominantly saturated, but also un saturated parts, understood. They indicate about 8 to 18, in particular substantially about 8 to 14 carbon atoms.  

The preparation of the alkyl polyglycosides is carried out either by direct order of glucose or xylose with the corresponding fatty alcohol or by a transacetalization of short-chain glycosides, preferably butylglyl coside, with the corresponding alcohol. The composition of the individual Products are shown in the following table:

Their proportion of the total mixture may be about 0.1 to 30, preferably about 1 to 28 wt .-% amount.

Suitable anionic surfactants are those of the sulfonate and / or sulfate type. Sulfonate surfactants are alkylbenzenesulfonates (C _9-15 -alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and then ßende alkaline or acidic hydrolysis of the sulfonation receives, wei ter alkanesulfonates, which are obtainable from alkanes by sulfochlorination or Sulfoxyda tion and subsequent hydrolysis or neutralization or by Bisul fitaddition to olefins, esters of α-sulfo fatty acids, eg. B. the α-sulfonic acids from hydrogenated alkyl esters of coconut, palm kernel or tallow. Preferably, however, the agents according to the invention are free from such anionic surfactants of petrochemical origin.

The sulfate-type surfactants preferably used for ecological reasons are the sulfuric acid monoesters of primary C ₁₂ -C ₁₈ , preferably C ₁₂ -C ₁₄ , alcohols and those of corresponding secondary alcohols. Furthermore eig nen sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides or sulfated reaction products of about 1-5 moles of ethylene oxide with primary or secondary fatty alcohols. In any case, derivatives of fatty acids are preferred since they are of natural origin and constitute renewable raw materials.

All anionic surfactants may in the form of their alkali, alkaline earth, in particular special magnesium and ammonium salts and as soluble salts organic Bases such as mono-, di- or triethanolamine. For cost reasons usually the sodium salts are preferred.

In addition to the alkyl polyglucosides and -xylosiden used in the invention can as further nonionic surfactants or alkyl polyglycol with an HLB value greater than 10, preferably 11, are added. Under Al kylrest of these alkyl polyglycol ethers are the alkyl chains of fatty alcohols natural or synthetic origin and oxo alcohols hen. These alkyl polyglycol ethers may be present in a ratio of about 0.1 to 5, preferably from about 0.5 to 3, based on a part of the inventions According to the named alkylpolyglucosides or -xylosides used. The total amount of nonionic surfactants is retained.

For the cleaning agent concentrates according to the invention can furthermore be used as Builders about 0.1 to 7, preferably about 0.5 to 3 wt .-%, bezo to the whole concentrate, alkaline in its entirety inorganic or organic compounds, as well as inorganic or orga niche complexing agents are used, preferably in the form of their Alka Li or amine salts, in particular the sodium and potassium salts are present. The builders include here also the alkali metal hydroxides.

Other useful inorganic substances which Mit Mit If necessary, can be added, for example, Bicarbo nate, carbonates, borates, silicates or polyphosphates such as pentasodium tri phosphate, pyrophosphates or orthophosphates. The latter phosphor However, ionic salts should be more useful for environmental reasons not be used.

To the organic complexing agents of the type of aminopolycarboxylic ge Hear, inter alia, the nitrilotriacetic acid, ethylenediaminetetraacetic acid  re, N-hydroxyethyl-ethylene diaminetriacetic acid. As polyphosphonic acids may be mentioned: methylene diphosphonic acids, 1-hydroxyethane-1,1-diphosphone acid, propane-1,1,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, Polyvinylphosphonic acid, copolymers of vinylphosphonic acid and Acrylic acid, ethane-1,2, dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy 1,2-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,2- diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino or Ethylamino-di- (methylenephosphonic acid) and ethylenediaminetetra (methylene acid).

As examples of N- or P-free and therefore preferred one or more tiger carboxylic acids or their salts as builders are often, though not exclusively, carboxyl group-containing compounds proposed. A large number of these carboxylic acids have a complex Forming calcium. These include z. Citric acid, wine acid, benzene hexacarboxylic acid, tetrahydrofurantetracarboxylic acid, gluconic acid glutaric, succinic, adipic, polyacrylic and copoly mers or mixtures thereof.

As household cleaners generally neutral to weak are set alkaline, d. H. their aqueous working solutions at An usually concentrations about 1-20, preferably about 5-15 g / l of water or aqueous solution has a pH in the range of 6.0-10.5, preferably 7.0-9.5, can regulate the pH an addition of small amounts of acidic and / or alkaline components, too as a buffer, be required.

Suitable acidic substances are customary inorganic or organic acids ren or acid salts, such as hydrochloric acid or sulfuric acid, Lactic acid, polycarboxylic acids, such as. As citric acid, tartaric acid, glutar acid, succinic acid, adipic acid or mixtures thereof and the like.

If the content of alkaline builders is not for regulation the pH value is sufficient, even alkaline-looking organic or inorganic compounds such as. For example, sodium hydroxide, alkanolamines, namely mono-, di- or triethanolamine or ammonia are added.  

In addition, one can known solubilizers, individually or as Mixture with each other, incorporate what except water-soluble organic Solvents such as in particular low molecular weight aliphatic alcohols with 1-4 carbon atoms also the so-called hydrotropes of Type of lower alkylarylsulfonates, for example toluene, xylene or Cumene sulfonates or short chain alkyl sulfates such as octyl sulfate or the short-chain homologues of other surfactants such as the alkyl glycosides with less than 8 carbon atoms in the alkyl radical, for example butylglucoside belong. The anionic representatives may also be in the form of their sodium and / or potassium and / or alkyl amino salts. As a solubilizer Furthermore, water-soluble organic solvents are usable, esp especially those with boiling points above 75 ° C such as the Ethers of identical or different polyhydric alcohols or the Partial ethers of polyhydric alcohols. These include, for example, or triethylene glycol polyglycerols and the ethylene glycol partial ethers, Propylene glycol, butylene glycol or glycerol with aliphatic, 1-6 Koh atoms in the molecule contained monohydric alcohols.

As a water-soluble or water-emulsifiable organic solvent Also come ketones, such as acetone, methyl ethyl ketone and aliphatic, cy cloaliphatic and aromatic hydrocarbons, and terpene alcohols consider.

The weight ratio of surfactant to solvent or solubilizer may be 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1.

To regulate the viscosity, if appropriate, an addition is recommended small amounts of higher polyglycol ethers having molecular weights up to about 600 or polyglycerol. Furthermore, it is recommended to regulate the viscosity an addition of electrolytes such. As to chlorides and / or sulfates of Sodium or magnesium and / or urea.

In addition, the claimed agents may be other customary ingredients Additives to dyes and fragrances preservatives and polymers Cleaning enhancers about according to DE 28 40 463 included.  

A frame formulation of the concentrates according to the invention can thus be total have approximately the following basic composition:

ingredients Weight% alkylpolyglycosides about 0.1 to 30, preferably about 1 to 28 Other surfactants about 2.0 to 20, preferably about 5 to 15 builders about 0.1 to 7, preferably about 0.5 to 3 Surfactants: solvents / solubilizers 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1 Dyes / fragrances / detergent booster small quantities preservative small quantities water Rest on each 100

tries

To prove the advantages of the cleaning agent according to the invention The known hard surface cleaners have been compared in terms of their cleaning capacity hired.

Testing the cleaning effect

To test the detergency, the test described below was used method that gives very reproducible results. The dirt off Solution of hard surfaces was after the detergency test, be written in soap oils-fats-waxes 112, 371 (1986).

The detergent to be tested was on an artificially soiled Given plastic surface. When using a detergent with 10 wt .-% surfactant content was as a test soiling a mixture of Vaseline®, fatty acid glycerine esters and pigments used. The test The area of 26 × 28 cm became uniform with the help of a surface doctor coated with 2 g of artificial soil. The test area was with  10 ml of the detergent solution coated. After ten wiping movements with a plastic sponge, the cleaned test area was under flow held by the water and the loose-fitting dirt removed. The Reini effect, d. H. the whiteness of the thus cleaned plastic surface was with a color difference measuring instrument Microcolor of Dr. Ing. Long measured. The white standard was the clean white plastic surface. Because when measuring the clean surface set to 100% and the soiled area is displayed with 0, the read values are at the cleaned plastic surfaces with the percentage cleaning ver like equate (% RV). In the following experiments are the given values RL rel. (%) the values obtained by this method for the cleaning power of the tested cleaning agents, based on the Cleaning performance of the comparative formulation according to DE 28 40 463 (RL = 100%). They each represent averages of triplicate determinations.

Examples

There were all purpose cleaner base formulations with different alkylpolygly cosiden tested. The active substance content of the concentrates was in each case 10% by weight.

As a comparison served a powerful commercial standard formulation tion, which falls within the scope of the patent DE 28 40 463 (RL = 100%):
8% by weight of alkylbenzenesulfonate, Na salt,
2% by weight adduct of C _12/14 alkyl epoxide + ethylene glycol + 10 mol ethylene oxide,
2% by weight of Na gluconate,
0.1% by weight of polyethylene glycol having a molecular weight of about 600,000 (Polyox WSR 205® from UCC)
Rest of water.

The cleaning performance of the Formu in the following examples Alierungen was on the cleaning performance o.a. standard formulations with this being set to 100%. The pH of the formulation Depending on requirements, it was either with caustic soda or with citric acid set to about 7.0.

recipes

Although the high cleaning performance of the standard is not achieved is, so it can with these detergents with optimal Umweltver a good cleaning performance can be achieved.

From the formulas 1-6 and 7-12 it can be seen that the cleaning performance of Alkylpolyxylosiden is even better than that of the corresponding Alkylpolyglucosides. It was not expected to get results comes close to the standard and an ecologically improved recipe based on renewable raw materials.

The abbreviations used in the tables have the following meaning:
FAES: C _12/14 fatty alcohol ether sulfate with approx. 2 EO, Na salt (Texapon® N),
FAS: C _12/14 fatty alcohol sulfate, Na salt,
APG-8: C ₈ alkyl polyglucoside (1.6 GE),
APG-10: C ₁₀ alkyl polyglucoside (1.6 GE),
APG-12: C ₁₂ alkyl polyglucoside (1.4 GE),
APG-14: C ₁₄ alkyl polyglucoside (1.4 GE),
APX-8: C ₈ alkylpolyoside (1.4 XE),
APX-10: C ₁₀ -Alkylpolyxylosid (1.4 XE);
APX-12: C ₁₂ alkyl polyoxyloside (1.4 XE),
APX-14: C ₁₄ -Alkylpolyxylosid (1.4 XE);
Polyox® WSR 205: Polyethylene glycol MG 600 000
GE = glucose units per alkyl radical
XE = xylose units per alkyl radical.

Claims (6)

1. Use of liquid concentrates based on aqueous solutions of an ionic surfactants and nonionic surfactants, organic and / or inorganic builders, water-soluble solvents or solubilizers and other conventional components of such detergents as nonionic surfactant about 0.1 to 45, preferably about 1 before , 0 to 30 wt .-%, based on the total concentrate, of an alkylpolyglycoside of the formula ROZ _x with R = C ₈ -C ₁₈ , preferably, C ₈ -C ₁₄ , O = oxygen and x = about 1 to 2, preferably about 1-1.6, wherein Z represents a glucose and / or preferably a xylose unit, for cleaning hard surfaces. 2. Use of agents according to claim 1, as anionic surfactants those of the sulfonate and / or sulfate type. 3. Use of agents according to claim 1 and 2, which are free of anio niche surfactants of petrochemical origin. 4. Use of agents according to claim 1 and 2, wherein the weight ratio of alkyl glycosides to anionic surfactants about 1:10 to is about 10: 1, preferably about 1: 7 to about 1: 1. 5. Use of agents according to claim 1 to 4, in addition to the alkylpoly Glykosiden still contain other nonionic surfactants, the Total amount of nonionic surfactants remains unchanged. 6. Use of agents according to claim 5, wherein the ratio of further nonionic surfactants to alkyl polyglycosides about 0.1 to 5: 1, preferably about 0.5 to 3: 1 and especially about 1: 1 is.