EP0743975B1 - Hard surface cleaning agent - Google Patents

Abstract

PCT No. PCT/EP95/00357 Sec. 371 Date Oct. 10, 1996 Sec. 102(e) Date Oct. 10, 1996 PCT Filed Feb. 1, 1995 PCT Pub. No. WO95/21905 PCT Pub. Date Aug. 17, 1995A water-containing cleaning composition having a pH value of 3.0 to 6.5 containing 0.1% to 50% by weight of at least one alkyl glycoside corresponding to formula (I):R1-O-[G]xwherein R1 is a branched or linear, saturated or unsaturated alkyl group containing 6 to 11 carbon atoms, G is a glycose or xylose unit and x is a number of 1 to 10, 0. 1 % to 30% by weight of at least one fatty alcohol ether corresponding to formula (II) <IMAGE> (II) in which R2 is an alkyl radical containing 6 to 12 carbon atoms, m is a number of 0.5 to 3.0 and n is a number of 4.0 to 12.0, based on the weight of the composition, and which is free from hydrotropes based on organic acids.

Description

The invention relates to cleaning agents for hard surfaces. As such are all non-textile that occur in the household and commercial sector Surfaces, with the exception of dishes.

The term all-purpose cleaner has come up for this type of cleaning agent naturalized. All-purpose cleaners have been known for a long time. It is about essentially aqueous surfactant solutions of various kinds with or without the addition of builders and with or without the addition of water-soluble ones Solvents or solubilizers. The consumer hires such all-purpose cleaners meet the requirement of all types of im Household soiling to be effective. Conventional weakly alkaline or neutral all-purpose cleaners meet this requirement as far as possible with regard to oily, greasy and dusty soiling. Beyond that, the consumer also expects that above all calcareous contamination occurring in the bathroom, but also in the kitchen area are easily removable; to meet this need the production of acidic all-purpose cleaners is ideal. In practice it has However, it has been shown that the provision of all-purpose acidic cleaners does not done in a trivial way by acidifying conventional all-purpose cleaners can, since in this case there are often problems with regard to assembly, Cold stability and / or storage stability, especially with regard to possibly contained perfume oils occur. Often there is also one not inconsiderable amount of hydrotropes necessary to all components to solve. However, it would be desirable to do without hydrotropes because they generally do not contribute to cleaning performance.

International patent application W086 / 2943 discloses acidic cleaning agents, the anionic surfactants and - to adjust the viscosity - Contain monoglycosides.

The object of the present invention is to provide acidic, easy-to-assemble, cold and storage-stable cleaning agents with good cleaning power for hard surfaces, so-called general-purpose cleaners, which also show the above-mentioned requirement profile without the use of hydrotropes. The object was achieved by combining a C ₆ -C ₁₁ alkyl glycoside with a specific fatty alcohol ether.

• 0,1 bis 50 Gew.-%, vorzugsweise 1,0 bis 10 Gew.-%, mindestens eines Alkylglycosids der Formel I, R¹-O-[G]_x, wobei R¹ eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 6 bis 11 C-Atomen, vorzugsweise 8 bis 10 C-Atomen, G einen Glycoserest, vorzugsweise einen Glucose- oder Xyloserest bedeutet, und x für Zahlen von 1 bis 10, vorzugsweise von 1,1 bis 3,0 steht,
• 0,1 bis 30 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, mindestens eines Fettalkoholethers der Formel II,
  
  wobei R² einen Alkylrest mit 6 bis 12 C-Atomen, m eine Zahl von 0,5 bis 3,0 und n eine Zahl von 4,0 bis 12,0 bedeuten.
  und das frei ist von Hydrotropen basierend auf organischen Säuren.

The invention relates to a water-containing cleaning agent with a pH of 3.0 to 6.5, preferably 3.5 to 5.5, containing

• 0.1 to 50% by weight, preferably 1.0 to 10% by weight, of at least one alkyl glycoside of the formula I, R ¹ -O- [G] _x , where R ^{1 is} a branched or straight-chain, saturated or unsaturated alkyl group with 6 to 11 carbon atoms, preferably 8 to 10 carbon atoms, G is a glycose residue, preferably a glucose or xylose residue, and x represents numbers from 1 to 10, preferably from 1.1 to 3.0,
• 0.1 to 30% by weight, preferably 0.5 to 10% by weight, of at least one fatty alcohol ether of the formula II,
  
  where R ^{2 is} an alkyl radical having 6 to 12 carbon atoms, m is a number from 0.5 to 3.0 and n is a number from 4.0 to 12.0.
  and that is free of hydrotropes based on organic acids.

EP-A-0 202 638 describes cleaning concentrates of C _8-12 alkyl glycoside, an adduct of EO and PO or butylene oxide on a C _6-16 alcohol, water and a combination of solubilizers (hydrotropes) based on organic acids for strongly alkaline cleaning formulations .

In particular, in the formula (II) m stands for a number from 1.0 to 2.0 and n for a number from 6.0 to 11.0.

Alkyl glycosides are known substances, which according to the relevant Preparative organic chemistry processes can be obtained. Representing the extensive literature here is on the writings EP-A1-0 301 298 and W090 / 3977 referenced. The alkyl glycosides can of aldoses or ketoses with 5 or 6 carbon atoms, preferably of Derive glucose and xylose. The preferred alkyl glycosides are thus Alkyl glucosides and xylosides.

The index number x in the general formula (I) gives the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides on and stands for a number between 1 and 10. While x in a given connection must always be an integer, especially the values x = 1 to 6 can assume, the value x is analytical for a particular alkylglycoside determined calculated size, mostly a fractional number represents. Alkyl glycosides with an average degree of oligomerization are preferred x used from 1.1 to 3.0. For application technology In view of such alkylglycosides are preferred, their degree of oligomerization is less than 2.0 and is in particular between 1.2 and 1.6.

The alkyl radical R ¹ can be derived from primary alcohols having 6 to 11, preferably 8 to 10, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol or undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl glucosides and alkylxylosides of chain length C ₈ -C ₁₀ (DP = 1.1 to 3) are preferred, the fatty alcohol portion of which is obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a portion of less than 15 , preferably less than 6 wt .-% C ₁₂ alcohol may be contaminated.

According to formula (II), the fatty alcohol ethers are addition products of propylene oxide and ethylene oxide onto primary alcohols having 6 to 12 carbon atoms, that is to say e.g. B. on hexanol, octanol, decanol, dodecanol or a C ₈ -C ₁₀ pre-fatty alcohol.

The numbers m and n in the formula (II) are average degrees of propoxylation or ethoxylation and can also assume fractional numerical values as quantities to be determined analytically. The average degree of propoxylation m is 0.5 to 3.0, preferably 1.0 to 2.0 and in particular 1.1 to 1.5; the average degree of ethoxylation n is 4.0 to 12.0, preferably 7.0 to 11.0 and in particular 8.0 to 10.0. The C ₆ -C ₁₀ alcohol is preferably first propoxylated and then the ethoxylation is carried out, ie the ethylene glycol units are preferably located at the end of the molecule.

The production of these substances and their use in detergents and cleaning agents is already in German Offenlegungsschrift DE 36 43 895 have been described.

The cleaning agents according to the invention can optionally include additional ones nonionic surfactants in amounts of 0.1 to 10 wt .-%, preferably 0.1 to 2.0 wt .-%, based on the total agent, z. B. fatty acid polyhydroxyamides, for example glucamides, and the conventional ones Ethoxylates of fatty alcohols, alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 10 to 22 carbon atoms, preferably 12 up to 18 carbon atoms. The degree of ethoxylation of these compounds is usually between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reaction with ethylene oxide will. The ethanolamide derivatives of alkanoic acids are preferred 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The most suitable Compounds include the lauric, myristic and palmitic monoethanolamides.

Furthermore, the cleaning agents according to the invention can contain customary anionic surfactants as additional surfactant components in amounts of 0.1 to 10% by weight, preferably 01 to 2.0% by weight, based on the total agent. Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, sulfofatty acid disalts, sulfofatty acid alkyl ester salts, alkanesulfonates, isethionates, taurides, sarcosinates, ether carboxylates and / or alkylbenzenesulfonates with linear C ₉ -C ₁₅ -alkyl groups on the benzene nucleus. The useful surfactants of the sulfate type include in particular primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation; The derivatives of linear alcohols with in particular 8 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.

In addition, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates are used as anionic surfactant components. Such ether sulfates preferably contain 2 to 30, in particular 4 to 20, ethylene glycol groups per molecule.

Suitable anionic surfactants of the sulfonate type include those by Implementation of fatty acid esters with sulfur trioxide and subsequent neutralization available sulfoesters, especially those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms Sulfonation products, as well as the sulfofatty acid disalts derived from them. The alkanesulfonates that can be used are substances those by sulfoxidation of hydrocarbons, which are preferred Contain 10 to 20 carbon atoms can be obtained. This usually results Products with a statistical distribution of sulfonic acid substituents that if desired can be separated in a known manner. As cations in all cases of the anionic surfactants mentioned, especially those the group of alkali ions and ammonium or alkyl or. Hydroxyalkyl substituted Ammonium ions into consideration.

However, the cleaning agents according to the invention achieve the stated object even without the optional anionic surfactants, therefore on their use can also be dispensed with if necessary.

In principle, a mixture of any organic or inorganic acid with its respective salt can be used to adjust the pH according to the invention from 3.0 to 6.5, preferably 3.5 to 5.5 and in particular 4.0 to 4.5 , e.g. B. phosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid, formic acid; however, a mono-, di- or tricarboxylic acid having 2 to 6 carbon atoms is preferably used. Lactic acid, tartaric acid, malic acid, glycolic acid, glyoxylic acid, succinic acid, adipic acid, glutaric acid, but especially citric acid are preferred. The mixture of acid and salt is present in amounts of 0.1 to 15% by weight, preferably 1.0 to 5.0% by weight, based on the total agent, depending on which is in the range according to the invention pH is now ultimately desired. As salts are e.g. As ammonium and C ₂ -C ₄ mono- and dialkanolammonium salts to name, but preferred are the alkali metal salts. A mixture of acid and corresponding alkali metal salt is obtained in the simplest case by presenting the acid and with an alkali metal hydroxide, e.g. B. NaOH, partially neutralized.

Of course, combinations of different acids can also be used their respective salts can be used.

The pH value at an application concentration of 10 g detergent per 1 solution is usually 4.0 to 6.0. The invention Cleaning agents are generally aqueous preparations, in addition However, water-miscible organic solvents can be used be, e.g. B. methanol, ethanol, propanol, isopropanol and mixtures thereof.

Other additives usually contained in cleaning agents are Viscosity regulator, e.g. B. synthetic polymers such as e.g. Homopolymers and copolymers acrylic acid, polyethylene glycol, biosynthetic polymers such as e.g. Xanthan gum; Preservatives, e.g. Glutaraldehyde; Dyes, opacifiers and perfume oils.

The agents according to the invention can be prepared by simple mixing of the individual components, as such or, if appropriate, in aqueous Solution may be available.

With regard to not mandatory, but usually in cleaning agents However, perfume oils contained show that the surfactant combination according to the invention from alkyl glycosides of the formula I and fatty alcohol ethers of Formula II brings about a significant improvement in the incorporation of perfume oils; i.e. the perfume oils are easier to incorporate and also lead to better storage-stable formulations than this with conventional cleaning agents the case is.

The hydrotropes used in conventional cleaning agents, for example short-chain (C ₂ -C ₆ ) alcohols, e.g. B. butylene glycol; Cumene sulfonate and butyl glucoside can optionally be added to the cleaning agents according to the invention; however, the cleaning agents according to the invention also achieve the objects without hydrotropes.

The agents according to the invention are particularly suitable for cleaning hard ones Surfaces such as Enamel, glass, PVC, linoleum or ceramic tiles, especially in the bathroom or kitchen area, where calcareous contaminants are to be found. Acid sensitive materials such as B. marble, should but can not be cleaned with the agents of the invention.

Examples

By mixing the components, compositions E1 and E2 according to the invention and comparative compositions V1 to V4 not according to the invention were produced. (Figures in% by weight) E1 E2 V1 V2 V3 V4 C ₈ -C ₁₀ APG 3.5 3.5 - - 3.5 3.5 C ₁₂ -C ₁₆ APG - - 3.5 3.5 - - C ₈ -C ₁₀ -FA x 1.2 PO x 6 EO 1.5 1.5 1.5 1.5 - - C _12-14 -FA x 7 EO - - - - 1.5 1.5 Citric acid (anhydrous) 6.0 6.0 6.0 6.0 6.0 6.0 NaOH to adjust to pH: 4.3 4.3 4.3 4.3 4.3 4.3 Ethanol (hydrotrope) - 1.0 - 1.0 - 1.0 Xanthan gum 0.2 0.2 0.2 0.2 0.2 0.2 Perfume oil 0.9 0.9 0.9 0.9 0.9 0.9 Rest of water Appearance of the product at room temperature clear clear cloudy cloudy clear clear Appearance of the product after storage at 40 ° C / 1 week clear clear cloudy cloudy C ₈ -C ₁₀ APG: C ₈ -C ₁₀ alkyl 1,6-glucoside (DP = 1.6) C ₁₂ -C ₁₆ APG: C ₁₂ -C ₁₆ alkyl 1,4-glucoside (DP = 1.4) FA: fatty alcohol PO: propylene oxide EO: ethylene oxide C ₈ -C ₁₀ -FA x 1.2 PO x 6 EO: C ₈ -C ₁₀ fatty alcohol, which was first propoxylated 1.2 times and then ethoxylated 6 times

The examples according to the invention show both with and without hydrotrope clear products, even after storage at 40 ° C and subsequent cooling stay clear to normal ambient temperature (20 - 25 ° C).

In contrast, the comparative examples V1 and V2 are already after production cloudy products. The comparative examples V3 and V4 are immediately after Production clear, but cloudy after storage.

Claims (12)

1. A water-containing cleaning formulation with a pH value of 3.0 to 6.5 containing

   0.1 to 50% by weight of at least one alkyl glycoside corresponding to formula I R¹-O-[G]_x, where R¹ is a branched or linear, saturated or unsaturated alkyl group containing 6 to 11 carbon atoms, G is a glycose unit and x is a number of 1 to 10,

   0.1 to 30% by weight of at least one fatty alcohol ether corresponding to formula II:

   

   in which R² is an alkyl radical containing 6 to 12 carbon atoms, m is a number of 0.5 to 3.0 and n is a number of 4.0 to 12.0,
   and which is free from hydrotropes based on organic acids.
2. A water-containing cleaning formulation as claimed in claim 1, characterized in that it has a pH value of 3.5 to 5.5.
3. A formulation as claimed in claim 1 or 2, characterized in that it contains 1 to 10% by weight of at least one alkyl glycoside corresponding to formula I R¹-O-[G]_x.
4. A formulation as claimed in any of claims 1 to 3, characterized in that R¹ is a linear or branched, saturated or unsaturated alkyl group containing 8 to 10 carbon atoms.
5. A formulation as claimed in any of claims 1 to 4, characterized in that G is a glucose or xylose unit.
6. A formulation as claimed in any of claims 1 to 5, characterized in that x is a number of 1.1 to 3.0.
7. A formulation as claimed in any of claims 1 to 6, characterized in that it contains 0.5 to 10% by weight of a fatty alcohol ether corresponding to formula (II).
8. A formulation as claimed in any of claims 1 to 7, characterized in that, in formula (II), m is a number of 1.0 to 2.0 and n is a number of 6.0 to 11.0.
9. A formulation as claimed in claims 1 to 8, characterized in that the pH value of 3.0 to 6.5 is adjusted with a mixture of 0.1 1 to 15% by weight, based on the formulation as a whole, of an organic mono-, di- or tricarboxylic acid containing 2 to 6 carbon atoms and an alkali metal salt thereof.
10. A formulation as claimed in claim 9, characterized in that the pH value of 3.5 to 5.5 is adjusted with a mixture of 1.0 to 5% by weight, based on the formulation as a whole, of an organic, mono-, di- or tricarboxylic acid containing 2 to 6 carbon atoms and an alkali metal salt thereof.
11. A formulation as claimed in claim 10, characterized in that the organic mono-, di- or tricarboxylic acid containing 2 to 6 carbon atoms is selected from the group consisting of citric acid, lactic acid, tartaric acid, malic acid, glycolic acid, glyoxylic acid, succinic acid, adipic acid and glutaric acid.
12. A formulation as claimed in claim 1 1, characterized in that the organic mono-, di- or tricarboxylic acid containing 2 to 6 carbon atoms is citric acid.