JP2002543240A - Cleaning agents for hard surfaces - Google Patents

Abstract

  (57) [Summary] The present invention relates to (a) a cationic surfactant, (b) an alkyl and / or alkenyl oligoglycoside, and (c) a sulfate and / or sulfonate interface containing 4 to 10 carbon atoms in the hydrophobic residue. A detergent for hard surfaces containing an activator, the detergent having a pH in the range of 1-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates generally to cleaning and disinfecting compositions, and more particularly to advantageous compositions containing a combination of selected cationic, non-ionic and anionic surfactants. The use of the mixtures for the preparation of preparations having a high viscosity as well as cleaning compositions.

BACKGROUND OF THE INVENTION Hitherto, flush toilets have been cleaned using solid toilet blocks that are suspended in a water bath or fixed below the edge of a flush toilet tub. Its function is to clean the surface of the flush tub during the flushing process, in particular to mask unpleasant odors by releasing fragrances. In particular, flushing agents for flush toilets are also referred to in the literature as fragrance blocks, especially in view of their ability to release fragrances. Usually, surfactants, builders, inorganic salts, and, of course, fragrances and dyes are used in their preparation. Several such formulations are known from the prior art literature. For example, US Pat. No. 4,534,879 (Procter & Gamble)
A solid cleaning composition containing C _9-15 alkyl sulfate, alkyl benzene sulfonate and an inorganic salt as surfactant components is described. EP 0 265 979 A1 (Akzo) describes a concentrated aqueous detergent comprising a mixture of a cationic surfactant and an amine oxide together with a short-chain arylsulfonate. European Patent Application Publication EP00149779A1 (Henkel) describes a toilet block containing alkylbenzenesulfonates and alkylsulfates, as well as fatty alcohols or alkylphenol ethoxylates. German patent DE 4337032 C2 (Henkel) relates to a toilet block containing alkyl sulfates, alkyl ether sulfates and alkyl glucosides. EP 0 268 967 A1 (Henkel) describes a toilet block containing sodium lauryl sulfate and a fatty acid monoethanolamide. The described toilet blocks are usually manufactured by injection molding, compression molding, extrusion or granulation processes, but are expensive to machine and often require normal high temperature (injection molding / extrusion). The undesirable loss of fragrance under the action of the method is problematic. Another disadvantage is that refill units, which are widely used for environmental reasons, can only be used after complete consumption of the block.
Although desirable, it is not possible, for example, to refill as required for a stronger release of the active ingredient, or more specifically for a stronger release of the fragrance.

[0003] DE 197 15 872 A1 (Henkel) describes a flush toilet cleaner in gel form having pseudoplastic properties. Since the technology involved is simple, this detergent can be produced relatively inexpensively, and the difficulty in production is greatly reduced. Also, the individual refillability problem can be solved by such a pseudoplastic compound. This known gel-form toilet cleanser contains polysaccharides (more specifically xanthan gum) to establish its pseudoplastic properties, and as surfactants alkyl polyglycosides (essential components) and anions Contains a non-ionic and / or non-ionic co-surfactant (optional component). However, this gel form of the cleaning agent is special during the formation of the gel in order to ensure on the one hand that no air bubbles are formed and on the other hand that the other components are evenly distributed in the gel. It must be manufactured while taking precautionary measures.

[0004] The complex problem to be solved by the present invention therefore allows, on the one hand, an easy application, on the other hand, to prevent premature spillage even on inclined surfaces in order to guarantee as long a contact time as possible. It was to provide a novel cleaning composition for hard surfaces, having a viscosity, preferably a flush toilet cleaner in gel form. further,
This composition has improved cleaning performance, is bactericidal and will retain an advantageous viscosity without the use of conventional thickeners. The composition also exhibits good initial foaming behavior, allows for the incorporation of various fragrance oils even in large amounts, and finally will have a long useful life. That is, the flush toilet could be flushed many times before the cleaning composition is completely consumed (number of flushes).

DISCLOSURE OF THE INVENTION The present invention relates to (a) a cationic surfactant, preferably an esterquat and / or tetraalkylammonium compound, (b) an alkyl and / or alkenyl oligoglycoside, and (c) A cleaning composition for hard surfaces, comprising a sulfate and / or a sulfonate surfactant containing from 4 to 10 carbon atoms in the hydrophobic part, wherein the pH value is in the range from 1 to 5. Composition.

[0006] Surprisingly, the compositions of the present invention not only have excellent cleaning performance and bactericidal action, but are also much higher than normal compositions even without thickeners It was found to have viscosity and exhibit pseudoplastic behavior. That is, the composition of the present invention comprises
Not only is it distinguished by easy application and excellent outflow behavior, but it also has a high foaming capacity, allows the introduction of various fragrances even in relatively large amounts, and, due to its gel-like consistency, For example, "administration" can be performed for a long time with high reliability even from a container in a water tank of a flush toilet. Further, the aqueous composition can be wholly or partially free of water and can be compressed into blocks.

(Best Mode for Carrying Out the Invention)Esterquat The “esterquat” constituting the component (a1) is generally a quaternary.
Solution as a Cationic Surfactant of Triethanolamine Esters
Is done. These are known compounds that can be obtained by relevant methods in manufacturing organic chemistry.
Can be. See, for example, International Patent Application Publication No. WO 91/01295 (Henkel).
According to this document, triethanolamine is converted by fatty acids in the presence of hypophosphorous acid.
The reaction mixture is partially esterified, air is passed through the reaction mixture and then the whole is
Quaternize with sulfate or ethylene oxide. In addition, appropriate dispersion
Quaternary triethanolamine ester in the presence of an agent (preferably a fatty alcohol)
A process for the production of solid esterquats with grading is described in German Patent DE 43 08 794.
It is known from C1 (Henkel). For a review of this subject, see, for example, Puchta et al.
ens.Surf.Det.,30, 186 (1993)], the block (M.Brock) [Tens.Surf.Det., 30 , 394 (1993)] by R. Lagerman et al. [J. Am. Oil Chem. Soc.,71 , 97 (1994)] and I. Shapiro [Cosm. Toil.109, 77 (1994)]
Published by

The quaternized fatty acid triethanolamine ester salt is represented by the following formula (I):

Embedded image [Wherein, R¹CO is an acyl group containing from 6 to 22 carbon atoms;^TwoAnd R ^Three Are, independently of one another, hydrogen or R¹Same as CO, R^FourIs 1 to
An alkyl group containing 4 carbon atoms or (CH_TwoCH_TwoO)_qH group, m, n and
And p are both 0 or a number from 1 to 12, and q is a number from 1 to 12.
, X is a halide, alkyl sulfate or alkyl phosphate]
.

A representative example of an esterquat that can be used in accordance with the present invention is capron
Acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, iso
Stearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behen
Acids, erucic acids, and industrial mixtures thereof (e.g., pressurized water
(Obtained in decomposition). Industrial C_6/10Use fatty acids
Preferably. Fatty acids and triethanol to produce quaternized esters
The amine may be used in a molar ratio of 1.1: 1 to 3: 1. Features of Esterquat
Considering the properties, a ratio of 1.2: 1 to 2.2: 1 is preferable, and 1.5: 1 to 1.9: 1.
Has been found to be particularly advantageous. Preferred esterquats are 1.5 to
Technical mixture of mono, di and triesters having an average degree of esterification of 1.9
And industrial C_6/10Derived from upper rectified fatty acids. In terms of performance, R¹CO
Is an acyl group containing 6 to 10 carbon atoms;^TwoIs R¹Same as CO, R ^Three Is hydrogen and R^FourIs a methyl group, m, n and p are 0, and X is methyl
The quaternized fatty acid triethanolamine ether of the formula (I) which is a sulfate
Steal salts have been found to be particularly advantageous.

In addition to quaternized fatty acid triethanolamine ester salts, other suitable ester quats are quaternized ester salts of fatty acids of the formula (II) below with diethanolalkylamine. :

Embedded image Wherein R ¹ CO is an acyl group containing 6 to 22 carbon atoms, R ² is hydrogen or the same as R ¹ CO, and R ⁴ and R ⁵ are each independently And 1
An alkyl group containing 4 carbon atoms, m and n are both 0 or a number from 1 to 12, and X is a halide, alkyl sulfate or alkyl phosphate].

Finally, another group of suitable ester quats are the quaternized ester salts of fatty acids of the formula (III) with 1,2-dihydroxypropyldialkylamines:

Embedded image Wherein R ¹ CO is an acyl group containing 6 to 22 carbon atoms, R ² is hydrogen or the same as R ¹ CO, and R ⁴ , R ⁶ and R ⁷ are Independent of each other,
An alkyl group containing from 1 to 4 carbon atoms, m and n are both 0 or a number from 1 to 12, and X is a halide, alkyl sulfate or alkyl phosphate].

As regards the choice of the preferred fatty acids and the optimal degree of esterification, the examples given for formula (I) also apply to the esterquats of formulas (II) and (III).

Another group of suitable cationic surfactants suitable as the tetraalkylammonium compound component (a2) are preferably the tetraalkylammonium compounds of the formula (IV):

Embedded image Wherein R ⁸ is a linear or branched alkyl and / or alkenyl group containing 6 to 22 carbon atoms or a benzyl group, and R ⁹ and R ¹⁰ are each independently R ⁸ The same or an alkyl group containing 1 to 22 carbon atoms, R ¹¹ is an optionally hydroxy-substituted alkyl group containing 1 to 4 carbon atoms, and X is a halide, alkyl sulfate Or an alkyl phosphate].

Representative examples are cetyltrimethylammonium chloride, dimethyldistearylammonium chloride and benzyldistearylammonium bromide.

The alkyl and / or alkenyl oligoglycoside constituting the alkyl and / or alkenyl oligoglycoside component (b) is represented by the following formula:
Known nonionic surfactants represented by (V):

Embedded image Wherein R ¹² is an alkyl and / or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms, and p is a number of 1 to 10 is there].

These can be obtained by the relevant methods of manufacturing organic chemistry. European Patent Application Publication No. EP0301298A1 and International Patent Application Publication No. WO90 / 03977,
It is a representative of the detailed literature available for this subject. Alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses containing 5 or 6 carbon atoms, preferably glucose. That is, preferred alkyl and / or alkenyl oligoglycosides are alkyl and / or alkenyl oligoglucosides. The index p in the general formula (V) indicates the degree of oligomerization (DP), that is, the distribution of mono- and oligoglycosides, and is a number from 1 to 10. While the p of a compound must always be an integer, and will particularly take on values from 1 to 6, the value p of an alkyl oligoglycoside is a quantity measured and calculated by analysis and is a fraction. Is common. It is preferred to use alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization of from 1.1 to 3.0. Alkyl and / or alkenyl oligoglycosides having a degree of oligomerization of less than 1.7, more specifically 1.2 to 1.4, are preferred from an application point of view.
Alkyl or alkenyl group R ¹² is 4 to 11, preferably can be derived from primary alcohols having 8 to 10 carbon atoms. Representative examples are butanol,
Capron alcohol, caprylic alcohol, capric alcohol, undecyl alcohol, and industrial mixtures thereof, such as obtained in the hydrogenation of industrial fatty acid methyl esters or in the hydrogenation of aldehydes from the oxo synthesis of Roelen ]. C ₈ alkyl oligoglucosides (DP = 1 to 3) having a chain length of -C ₁₀ [obtained as the first fraction in the separation of technical C _8-18 coconut oil fatty alcohol by distillation, less than 6% by weight as an impurity may also contain a C ₁₂ alcohol, and alkyl oligoglucosides based on technical C _9/11 oxoalcohols (DP = 1 to 3) is preferable. The alkyl or alkenyl group R ¹² is 12-22, preferably also be derived from primary alcohols having 12 to 14 carbon atoms. Representative examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petrocerinyl alcohol, aralkyl alcohol, gadreyl alcohol,
Behenyl alcohol, ercil alcohol, brassyl alcohol, and
These are industrial mixtures (which can be obtained as described above). DP = 1 ~
Alkyl _{oligoglucosides} based on hydrogenated C12 / ₁₄ coconut oil fatty alcohols of 3 are preferred.

Sulfate and / or sulfonate surfactant Sulfate or sulfonate surfactant is a solubilizing agent. A representative example is a short-chain arylsulfonate (component c1) represented by the following formula (VI):

Embedded image [Wherein, R ¹³ is a linear or branched alkyl group containing 1 to 4 carbon atoms, R ¹⁴ is hydrogen or a methyl group, Ph is a phenyl group, Y is an alkali metal And / or alkaline earth metals, ammonium, alkylammonium, alkanolammonium or glucumammonium].

Representative examples are toluenesulfonate, xylenesulfonate, cumenesulfonate and mixtures thereof in the form of the sodium salt.

A representative example is also a short-chain alkyl sulfate (component c2), preferably represented by the following formula (VII):

Embedded image Wherein R ¹⁵ is a linear or branched alkyl group containing 6 to 10, preferably 8 carbon atoms, Y is an alkali metal and / or an alkaline earth metal,
Ammonium, alkyl ammonium, alkanol ammonium or gluc ammonium].

Representative examples are the alkali metal salts of octyl sulfate and 2-ethylhexyl sulfate.

Industrial Applicability In order to establish an acidic pH value, the composition according to the invention may comprise an inorganic acid such as hydrochloric acid or phosphoric acid, or an organic acid such as formic acid, adipic acid, tartaric acid or preferably citric acid. Can be contained. The amount used depends on the desired pH value, which should specifically be in the range 1.5-3.

In one preferred embodiment of the invention, the composition comprises the following components: (a) 1 to 10% by weight, preferably 2 to 5% by weight, of a cationic surfactant; (b 1) 1 to 10% by weight, preferably 1.5 to 4.5% by weight of alkyl and / or alkenyl oligoglycosides, and (c) 0.1 to 2% by weight, preferably 0.5 to 1.5% by weight Sulfate and / or
Or sulfonate surfactants, provided that these amounts add up to 100% by weight with water and other optional auxiliaries and additives.

Finally, the present invention relates to a method for preparing a hard surface cleaning composition (preferably a flush toilet cleaner in gel form) comprising: (a) a cationic surfactant; And / or alkenyl oligoglycosides, and (c) sulfate and / or sulfonate surfactants containing from 4 to 10 carbon atoms in the hydrophobic moiety.

Auxiliaries and additives The cleaning composition in gel form according to the invention comprises co-surfactants, lime dissolving agents, builders,
It may further contain an aromatic substance, an aromatic substance solubilizer, a solvent, a microorganism inhibitor, a preservative, a dye, a pH adjuster, and the like.

[0025] Suitable co-surfactants are nonionic, anionic and / or amphoteric or zwitterionic surfactants, usually from about 1 to 5% by weight of the composition, preferably 2% 〜3% by weight. Representative examples of anionic surfactants include soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates,
Alkyl ether sulfonate, glycerol ether sulfonate, α-methyl ester sulfonate, sulfo fatty acid, alkyl sulfate, fatty alcohol ether sulfate, glycerol ether sulfate, hydroxy mixed ether sulfate, monoglyceride (ether) sulfate, fatty acid amide
(Ether) sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates,
Fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl glutamates and acyl aspartates, such as alkyl oligoglucoside sulfates, protein fatty acid condensates (more specifically, wheat-based plant products) and alkyl (ether) It is a phosphate. When these anionic surfactants contain polyglycol ether chains, they can have the usual homolog distribution, but preferably have a narrow homolog distribution.

Representative examples of nonionic surfactants include fatty alcohol polyglycol ether,
Alkyl phenol polyglycol ether, fatty acid polyglycol ester,
Fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, (hydroxy) mixed ethers and mixed formals, optionally partially oxidized glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolysates ( In particular, plant products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have the usual homolog distribution, but preferably have a narrow homolog distribution.

Representative examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

The above-mentioned surfactants are all known compounds. Information on the structure and preparation of these compounds can be found in the relevant review books. For example, Falbe (J.Falbe
) “Surfactants in Consumer Products” [Sprin
ger Verlag, Berlin, 1987, p.54-124] or Falbe ed., "Katalysatoren, Te
nside und Mineraloeladditive (catalysts, surfactants and mineral oil additives) "[Thieme
Verlag, Stuttgart, 1978, p.123-217]. Preference is given to using alcohol ethoxylates, hydroxy mixed ethers, fatty acid methyl ester ethoxylates, amine oxides and / or betaines as cosurfactants.

Preferred lime dissolving agents are acids which dissolve lime, for example citric acid, formic acid, acetic acid, lactic acid or water-soluble salts thereof, which are 1 to 12% by weight, preferably 2% by weight, based on the composition. It can be used in amounts of up to 7% by weight.

Another optional ingredient of the composition of the present invention is a builder. This is preferably a water-soluble builder, because it has less tendency to form insoluble residues on hard surfaces. Suitable liquid water-soluble builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids (eg, the neutral reactive sodium salt of 1-hydroxyethane-1,1-diphosphonate), which are
It can be present in an amount of 0.5-5% by weight, preferably 1-2% by weight. Suitable solid or water-insoluble builders are, in particular, microcrystalline zeolites containing synthetic and bound water, for example detergent quality zeolite NaA. However, NaX zeolite and mixtures of NaA and NaX are also suitable. The zeolites can be used in the form of a spray-dried powder or in the form of an undried stabilized suspension which is still watery from the time of its manufacture. When the zeolite is used in the form of a suspension, the suspension may contain as stabilizer a small amount of a nonionic surfactant, for example 1 to 3% by weight, based on zeolite, of ethoxylated isotridecanol or Ethoxylated _C12-18 fatty alcohols containing 2 to 5 ethylene oxide groups can be included. Suitable zeolites have an average particle size (C
volume distribution as measured by the oulter Counter method), preferably 18 to
It contains 22% by weight, more preferably 20-22% by weight of bound water.

Suitable substitutes or partial substitutes for zeolites have the general formula: NaMSi _x O _{2x + 1.}
yH in ₂ O [wherein, M is sodium or hydrogen, x is a number from 1.9 to 4, y
Is a number from 0 to 20; preferred values of x are 2, 3 or 4]. Such crystalline layered silicates are described, for example, in European Patent Application Publication EP 0164514 A1. Particularly preferred are β- and γ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O, and β-sodium disilicate can be obtained, for example, by the method described in International Patent Application Publication No. WO 91/08171. The composition according to the invention preferably contains from 10 to 60% by weight of zeolite and / or crystalline sheet silicate as solid builder, a mixture of zeolite and crystalline sheet silicate in any proportion being particularly advantageous. It is. In one particularly preferred embodiment, the composition contains from 20 to 50% by weight of zeolite and / or crystalline sheet silicate. Particularly preferred detergents contain up to 40% by weight of zeolite, more particularly up to 35% by weight, based on the water-free active substance.

Another suitable component of the present detergent is a water-soluble amorphous silicate, which is preferably used in combination with zeolites and / or crystalline sheet silicates.
Particularly preferred detergents are those having a Na ₂ O: SiO ₂ molar ratio (modulus) of 1: 1 to 1 in particular.
: 4.5, preferably 1: 2 to 1: 3.5 sodium silicate detergent. The content of amorphous sodium silicate of the composition is preferably up to 15% by weight, more preferably up to 2-8% by weight.

[0033] Phosphates (eg, tripolyphosphate, pyrophosphate and orthophosphate) can also be present in the composition in small amounts. The phosphate content of the composition is preferably up to 15% by weight, more specifically from 0 to 10% by weight.

In addition, the composition can contain layered silicates of natural and synthetic origin. The corresponding layered silicates are described, for example, in German Patent Application Publication DE 233489.
9B1, European Patent Application Publication EP0026529A1 and German Patent Application Publication D
It is known from E3526405A1. Their suitability for use is not limited to a particular composition or structural formula. However, smectite is preferred, and bentonite is particularly preferred. Suitable phyllosilicate belonging to the group of water-swellable smectite, for example, is a silicate represented by the following general _{formula: (OH) 4 Si 8-} y Al y (Mg x Al 4-x) O ₂₀ Montmorillonite (OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ Hectorite (OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite [where x Is 0-4, y is 0-2, and z is 0-6.

Further, a small amount of iron can be introduced into the crystal lattice of the layered silicate represented by the above formula. Because of its ion exchange properties, the sheet silicate can also contain hydrogen, alkali metal and alkaline earth metal ions, more specifically Na ⁺ and Ca2 ⁺ . The amount of water of hydration is usually in the range of 8-20% by weight and depends on the degree of swelling and the processing method. Suitable layered silicates are described, for example, in US Pat.
3,966,629, US 4,062,647, European Patent Application Publication EP002652.
9A1 and EP0028432A1. It is preferable to use a layered silicate from which strongly colored iron ions and calcium ions have been substantially removed by an alkali treatment.

Useful organic builders are, for example, polycarboxylic acids, preferably used in the form of the sodium salt, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotri acids Acetic acid (NTA) and mixtures thereof (when their use is environmentally safe). Preferred salts are the salts of polycarboxylic acids, for example, citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid having a relative molecular weight of from 800 to 150,000 (based on the acid). Suitable copolymer polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. 50-9
Copolymers of acrylic acid and maleic acid containing 0% by weight of acrylic acid and 50 to 10% by weight of maleic acid are particularly suitable. Their relative molecular weight (based on free acid) is usually in the range of 5,000 to 200,000, preferably
Within the range of 0000 to 120,000, more preferably 50,000 to 10
It is in the range of 0.000. The use of a polymeric polycarboxylate is not absolutely essential. However, when polymeric polycarboxylates are used, biodegradable polymers such as acrylic acid and maleic acid or salts thereof and vinyl alcohol or vinyl alcohol derivatives as monomers, or acrylic acid and 2-alkylallyl sulfonic acid or Detergents containing these salts and terpolymers containing sugar derivatives as monomers are preferred. Terpolymers obtained in accordance with the teachings of DE-A-422 21 381 A1 and DE 43 07 772 A1 are particularly preferred.

Another suitable builder is polyacetal, which is a polyol carboxylic acid containing at least 3 hydroxyl groups and 5 to 7 carbon atoms, as described for example in EP 0 280 223 A1. It can be obtained by reacting a dialdehyde. Preferred polyacetals are derived from dialdehydes (eg, glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof) and polyol carboxylic acids (eg, gluconic acid and / or glucoheptonic acid). The citrate group is particularly preferred. The builder may be present in the composition of the present invention in an amount of 0-5% by weight.

The hygiene effect can be enhanced by adding a microorganism inhibitor. Suitable microbial inhibitors are, in particular, mixtures of isothiazolines, sodium benzoate and / or salicylic acid. Other examples are substances which act specifically on Gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorohexidine [1,6-di- (4-chlorophenylbiguanide)-. Hexane] or TC
And C (3,4,4'-trichlorocarbanilide). Many fragrances and essential oils also have antimicrobial properties. Representative examples are the active substances eugenol, menthol and thymol (in clove), mint and thyme oil. An important natural microbial inhibitor is farnesol (3,7,11-trimethyl-2,6), a terpene alcohol present in linden flower oil and having a German lily of the valley-like aroma.
, 10-dodecatrien-1-ol). Glycerol monolaurate has also been used successfully as an antibacterial agent. The content of microbial inhibitors depends largely on the effectiveness of the particular compound and can be up to 5% by weight. The microbial inhibitor is preferably present in an amount of 0-10% by weight, more specifically in an amount of 0.01-7% by weight.

The optional fragrance is a fragrance known from the prior art. Mixtures of natural and synthetic fragrances are mentioned by way of example. Natural aromatic substances include flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anis, cilantro, caraway,
Juniper, pericarp (bergamot, lemon, orange), roots (flavour, angelica, celery, cardamom, costas, iris, calmus), trees (pine, sandalwood, yusouboku, cedarwood, rosewood), barbs and grass (taragon, lemon) Extracts of grass, sage, thyme), needles and branches (spruce, fir, pine, low pine), resin and balsam (galbanum, elemi, benzoin, myrrh, frankincense, opopanax). Animal raw materials such as musk and beaver can also be used. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of ester-type aromatic compounds include benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, and ethylmethylphenylglycinate. , Allylcyclohexyl propionate, styralyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether; aldehydes include, for example, linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and Borgeonal is included.
Examples of suitable ketones are ionone, α-isomethylionone and methylseryl ketone. Suitable alcohols are anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. Hydrocarbons mainly include terpenes and balsams. However, it is preferred to use a mixture of different aroma compounds, which together produce a pleasant aroma. Other suitable aromatic oils are relatively low volatility essential oils (
Most of these are used as aroma components). Examples are sage oil,
Chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime flower oil,
Juniper fruit oil, vetiver oil, oribanum oil, galbanum oil, labranum oil and labendin oil. The following are preferably used individually or in the form of a mixture: bergamot oil, dihydromyrcenol, rial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, Benzyl acetone, cyclamenaldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice
Citrus oil, mandarin oil, orange oil, allyl amyl glycolate, cyclovertal, lavendine oil, salvia oil, β-damascorn, geranium oil bourbon, cyclohexyl salicylate, Beltfix Keuer (V
ertofix Coeur), Iso-E-Super, Fixolide N
P, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl
(irotyl) and floramat. The dose of the aroma substance is determined by the desired aroma intensity and is in the range of 0 to 15% by weight.

Aroma solubilizing agents which may be present in the compositions of the present invention include polyol fatty acid esters, for example coconut oil fatty acid esterified glycerol alkoxylated with 7 moles of ethylene oxide (Cetiol HE ^R , Henkel KGaA) and / or 40
Or hydrogenated castor oil alkoxylated with 60 moles of ethylene oxide (E
umulgin ^R HRE 40 or 60, Henkel KGaA) and / or 2-hydroxy-fatty alcohol ethoxylate (Eumulgin ^R L, Henkel KGaA) are included. The amount of the fragrance solubilizer in the composition of the present invention is usually 0 to 10% by weight, preferably 1 to 7% by weight.

Solvents that may be present in the compositions of the present invention, more specifically for dyes and fragrance oils, include, for example, alkanolamines, polyols such as ethylene glycol, propylene glycol, 1,2- Glycerol and other monohydric and polyhydric alcohols, as well as alkyl benzene sulphonates (containing 1 to 3 carbon atoms in the alkyl moiety) are included. The group of lower alcohols is particularly preferred, and ethanol is most particularly preferred. The content of the solvent depends on the type and amount of the constituent to be dissolved, and is usually in the range of 0.5 to 5% by weight.

A water-soluble dye is preferably present for coloring the product or for coloring the liquid circulating around the container. In a preferred embodiment, the content of water-soluble dye is not more than 1% by weight and is intended to improve the appearance of the product. When additional color signals are needed during the wash, the content of water-soluble dye can be increased to 5% by weight.

EXAMPLES Various flush toilet cleaners were prepared and their cleaning performance and their viscosities to the IPP standard (soil 78/19, undiluted application) (Brookfield RVT viscometer, 20
° C, spindle 1, 10 rpm) (Seifen-Oele-Fette-Wachse, 112 , 371, 1988)
Was tested. Table 1 shows the results. Examples 1 to 6 correspond to the present invention, and Comparative Examples C1 to C1.
C3 is intended for comparison. All amounts represent% by weight.

[0044]

[Table 1]

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inagna Hanke Federal Republic of Germany Day-47269 Deusbruck, Angermunder Strasse No. 66 (72) Inventor Jörg Kale Federal Republic of Germany Day-42799 Reichlingen, Am Trepchen No. 8 F term (reference) 4H003 AB19 AB27 AC05 AE06 AE10 DA05 DA06 EB07 EB08 EB21 EB22 EB41 ED02 FA28 FA30 FA34

Claims (10)

[Claims] 1. A cationic surfactant, (b) an alkyl and / or alkenyl oligoglycoside, and (c) a sulfate and / or sulfonate surfactant containing from 4 to 10 carbon atoms in the hydrophobic moiety. CLAIMS 1. A cleaning composition for hard surfaces, comprising: a pH value in the range of 1-5. 2. Component (a1) represented by the following formula (I): Wherein, R ¹ CO is an acyl group containing 6 to 22 carbon atoms, R ² and R ³ are independently of one another, identical to or is R ¹ CO is hydrogen, R ⁴ Is 1-4
An alkyl group containing ₂ carbon atoms or a (CH ₂ CH ₂ O) _q H group, m, n and p are both 0 or a number from 1 to 12, and q is a number from 1 to 12 And
X is a halide, an alkyl sulfate or an alkyl phosphate.] The composition according to claim 1, which contains an ester quat represented by the following formula: 3. Component (a1) represented by the following formula (II): Wherein R ¹ CO is an acyl group containing 6 to 22 carbon atoms, R ² is hydrogen or the same as R ¹ CO, and R ⁴ and R ⁵ are each independently And 1
An alkyl group containing 4 carbon atoms, m and n are both 0 or a number from 1 to 12, and X is a halide, an alkyl sulfate or an alkyl phosphate. The composition according to claim 1, comprising at. 4. Component (a1) represented by the following formula (III): Wherein R ¹ CO is an acyl group containing 6 to 22 carbon atoms, R ² is hydrogen or the same as R ¹ CO, and R ⁴ , R ⁶ and R ⁷ are Independent of each other,
An alkyl group containing 1 to 4 carbon atoms, m and n are both 0 or a number from 1 to 12, and X is a halide, an alkyl sulfate or an alkyl phosphate. The composition according to claim 1, comprising an esterquat. 5. Component (a2) represented by the following formula (IV): Wherein R ⁸ is a linear or branched alkyl and / or alkenyl group containing 6 to 22 carbon atoms or a benzyl group, and R ⁹ and R ¹⁰ are each independently R ⁸ The same or an alkyl group containing 1 to 22 carbon atoms, R ¹¹ is an optionally hydroxy-substituted alkyl group containing 1 to 4 carbon atoms, and X is a halide, alkyl sulfate Or an alkyl phosphate]. The composition according to any one of claims 1 to 4, comprising a tetraalkylammonium compound represented by the formula: 6. Component (b) represented by the following formula (V): Wherein R ¹² is an alkyl and / or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms, and p is a number of 1 to 10 The composition according to any one of claims 1 to 5, comprising an alkyl and alkenyl oligoglycoside represented by the formula: 7. Component (c1) represented by the following formula (VI): [Wherein, R ¹³ is a linear or branched alkyl group containing 1 to 4 carbon atoms, R ¹⁴ is hydrogen or a methyl group, Ph is a phenyl group, Y is an alkali metal And / or an alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucumammonium].
7. The composition according to any one of 6. 8. Component (c2) represented by the following formula (VII): Wherein R ¹⁵ is a linear or branched alkyl group containing 6 to 10, preferably 8 carbon atoms, Y is an alkali metal and / or an alkaline earth metal,
Ammonium, alkylammonium, alkanolammonium or glucumammonium].
8. The composition according to any one of items 7. 9. (a) 1 to 10% by weight of a cationic surfactant, (b) 1 to 10% by weight of an alkyl and / or alkenyl oligoglycoside,
And (c) 0.1 to 2% by weight of a sulfate and / or sulfonate surfactant,
A composition according to any of the preceding claims, characterized in that it comprises 100% by weight of water and optionally other auxiliaries and additives. 10. A method for preparing a cleaning composition for hard surfaces, comprising: (a) a cationic surfactant, (b) an alkyl and / or alkenyl oligoglycoside, and (c) a hydrophobic moiety. Use of a mixture having a pH of 1 to 5, comprising a sulfate and / or a sulfonate surfactant containing 10 carbon atoms.