NO993761L - Liquid, aqueous detergent mixtures - Google Patents

Description

Technical subject area

The present invention relates to the cleaning of various surfaces such as hard surfaces, fabrics, clothes and the like.

Background

A wide variety of detergents has been described in detail in the industry. Typically, detergents can be divided into detergents for hard surfaces and detergents for laundries. Detergents of these two types are traditionally very different in terms of formulation and are sold as different products with different market concepts. These differences place demands on the customer, who must buy and use at least two different products. Furthermore, the compositions of the two types above, especially detergents for hard surfaces, can be divided into two subtypes.

In fact, there are many different types of detergents available for hard surfaces, such as detergents for bathrooms, kitchens and floors.

This variation in formulation is made necessary by the difference in nature between the dirt that can be found on large sinks and on various hard surfaces in kitchens and bathrooms. For example, kitchen dirt mainly includes cooking oils, while bathroom dirt mainly includes grease and soap scum, also lime deposits; dirt on the floor mainly consists of solid particles and the sink can have many different types of dirt/stains, including grease stains (e.g. olive oil, mayonnaise, vegetable oils), particulate stains and/or bleachable stains (e.g. tea, coffee) .

However, there is a trend towards the development of liquid aqueous detergent compositions with better performance in several respects, i.e. liquid aqueous multi-purpose detergents which can be used satisfactorily on different surfaces as well as in laundries to remove different types of dirt and stains. Such multipurpose mixtures are, for example, described in European Patent Application EP-A-598973.

This patent application describes truly liquid aqueous detergents comprising hydrogen peroxide with an entirely nonionic system, i.e. at least one nonionic compound with an HLB above 15, at least one nonionic compound with an HLB of from 13 to 15, at least one nonionic compound with an HLB of from 9 to 13 and at least one nonionic compound with an HLB less than 9. This patent application further describes the use of 2-alkyl alkanols as defoamers in said mixtures.

However, it has been found that such liquid aqueous mixtures consisting of hydrogen peroxide, a 2-alkyl alkanol and, as surfactant system, a specific nonionic system of at least four nonionic surfactants with different HLB values (hydrophilic lipophilic balance) as defined herein previously, does not satisfactorily meet customers' needs. Indeed, such compositions based on a fully nonionic surfactant system and comprising a high level of hydrophobic surfactants were found to perform poorly on certain types of stains in heavy wash applications. Although such hydrophobic nonionic surfactants have good degreasing properties and are particularly effective on greasy dirt of a hydrophobic nature, such as mineral oil and soap suds when used in hard surface cleaners, it has been found that when said hydrophobic nonionic surfactants are used in laundry - applications, bleachable stains are not bleached satisfactorily. The wetting ability of the stains on the fabrics is seriously affected by the hydrophobicity of the nonionic system of said mixtures, i.e. good contact is prevented between hydrogen peroxide and the stains on said fabric, and this results in a poor performance on bleachable stains. It has also been found that there is a problem associated with the use of such ingredients, i.e. hydrophobic, nonionic surfactants and 2-alkyl alkanols, in that they can cause the finished product to appear hazy, indicating insolubility and phase separation.

Other multipurpose cleaning compositions have been described similar to that described in EP-A-666 308. EP-A-666 308 describes compositions comprising hydrogen peroxide or a source thereof, a 2-alkyl alkanol, a hydrophobic surfactant with a HLB less than 14 and an anionic surfactant. However, there is still room for further improvement of such multipurpose liquid aqueous cleaners with respect to general washing performance on various types of stains, including for example bleachable stains and grease stains.

It is thus the aim of the present invention to produce a multi-purpose liquid, aqueous detergent mixture which provides improved bleaching performance and improved performance with respect to stains, especially grease stains, when used for washing applications, including pre-treatment of heavy laundry, and/or in various household applications (for example cleaning hard surfaces typically found in kitchens or bathrooms).

It is a further aim of the present invention to produce an improved liquid, aqueous detergent mixture which is also a clear mixture in a wide temperature range, i.e. up to 45°C.

It has now been found that these objectives can be effectively achieved by formulating a liquid aqueous detergent composition having a pH up to 7 and comprising a peroxygen bleach, at least one ethoxylated nonionic surfactant and at least one zwitterionic betaine surfactant having a weight ratio of the ethoxylated nonionic surfactant to the zwitterionic betaine surfactant of from 0.01 to 20. Indeed, it is by combining these ingredients in the appropriate ratios that a liquid, aqueous multi-purpose cleaner is produced which exhibits great flexibility to the dirt that it is supposed to remove.

It has now been found that such a mixture when used, for example in a washing application, especially in a pre-treatment, increases the removal of various types of stains which include grease stains such as lipstick, olive oil, mayonnaise, vegetable oil, sebum, make-up, and more surprisingly the bleaching effect, compared to the stain removal and bleaching performance provided by the same mixture with only one of these surfactants (ie, ethoxylated nonionic or zwitterionic betaine surfactant) at the same total surfactant level. Also, the compositions of the present invention significantly increase the removal of kitchen grime when used to clean hard surfaces, compared to the same compositions comprising only one of these surfactants (ie, ethoxylated nonionic or zwitterionic betaine surfactant) at the same total level of surfactants. In fact, the compositions of the present invention provide excellent stain removal performance on a wide variety of stains and soils and have excellent bleaching performance when used in any laundry application, i.e. as a washing powder or laundry additive, and especially when used in a pre-treatment of storvaBk, or even in other household applications such as cleaning hard surfaces.

It is also an advantage that the aqueous mixtures here are physically and chemically stable during long-term storage.

Yet another advantage of the mixtures according to the present invention is that they are able to work under varying conditions, i.e. in hard and soft water and unmixed or diluted. It is also advantageous that they provide satisfactory glossiness and surface safety when used as cleaning agents on hard surfaces and satisfactory fabric and color safety when used as detergents.

Summary of the invention

The present invention includes a liquid, aqueous mixture having a pH up to 7 and consisting of from 0.01 to 20% by weight of the total mixture of a peroxygen bleach, from 0.001 to 30% by weight of the total mixture of an ethoxylated, nonionic surfactant substance, from 0.001 to 20% by weight of a zwitterionic betaine surfactant and a weight ratio of the ethoxylated nonionic surfactant to the zwitterionic betaine surfactant of from 0.01 to 20, with the proviso that said mixture is free of an antimicrobial essential oil or an active compound or a mixture thereof.

The present invention further comprises processes for cleaning a surface, for example a substance or a hard surface, starting from a liquid, aqueous mixture as defined here. For example, the process for cleaning substances includes the steps of contacting said substances with the liquid, aqueous mixture here unmixed or diluted, and subsequent rinsing of said substances. In the preferred embodiment, when the fabrics are pretreated, the mixture is applied unmixed to the fabrics, and the fabrics are then washed in a normal wash cycle.

Detailed description of the invention

The liquid, aqueous cleaning mixture

The mixtures according to the present invention are liquid mixtures as opposed to a solid substance or a gas. As used herein, "liquid" includes "paste-like" mixtures. The liquid mixtures here are aqueous mixtures. The liquid mixtures according to the present invention have a pH of up to 7, preferably from 1 to 6, and preferably from 2 to 5. The formulation of the mixtures according to the present invention in the acidic pH range contributes to the chemical stability of the mixtures and to blan the products' performance in terms of stain removal. The pH of the mixture can be adjusted with any acidifying agent known to those skilled in the art. Examples of acidifying agents are organic acids such as citric acid and inorganic acids such as sulfuric acid.

As a first essential element, the mixtures according to the present invention contain a peroxygen bleach or a mixture thereof. The presence of the peroxygen bleaching agent really contributes to the excellent bleaching benefits of said compositions. Suitable peroxygen bleaches that can be used here are hydrogen peroxide, water-soluble sources of this and mixtures of these. As used herein, a peroxygen source means any compound that produces perhydroxyl ions when said compound is in contact with water.

Suitable sources of hydrogen peroxide for use herein include percarbonates, persilicates, persulfates such as monopersulfate, perborates, peroxyacids such as diperoxydodecanedioic acid (DP-DA), magnesium perphthalic acid, perlauric acid, perbenzoic and alkylperbenzoic acids, hydroperoxides, aliphatic and aromatic diacyl peroxides, and mixtures thereof. Preferred peroxygen bleaches here are hydrogen peroxide, hydroperoxide and/or diacyl peroxide. Hydrogen peroxide is the most preferred peroxygen bleach here.

Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene monohydroperoxide, tert-amyl hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide. Such hydroperoxides have the advantage of being particularly safe to fabrics and colors while providing excellent bleaching performance when used in any type of laundry application.

Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof. Suitable aromatic diacyl peroxides for use here are, for example, benzoyl peroxide. Such diacyl peroxides have the advantage of being particularly safe to fabrics and colors while providing excellent bleaching performance when used in any type of laundry operation.

The mixtures here constitute from 0.01 to 20% by weight of the total mixture of said peroxygen bleach or mixtures thereof, preferably from 1 to 15% and more preferably from 2 to 10%.

As another essential element, the compositions according to the present invention comprise an ethoxylated nonionic surfactant or a mixture thereof at a level of from 0.001 to 30% by weight of the total mixture. Preferably, the mixtures here consist of from 0.01 to 15% by weight of the total mixture of said ethoxylated, nonionic surfactant or mixtures thereof, more preferably from 0.5 to 10%, even more preferably from 1 to 9% and preferably from 1 to 6%.

Suitable ethoxylated nonionic surfactants here are ethoxylated nonionic surfactants according to the formula RO-(C2H40)nH where R is a C6 to C22 alkyl chain or a C6 to C28 alkylbenzene chain, and where n is from 0 to 20, preferably from 1 to 15, more preferably from 2 to 15 and preferably from 2 to 12. The preferred R chains for use herein are C 1 to C 22 alkyl chains.

Preferred ethoxylated nonionic surfactants conform to the above formula and have an HLB (hydrophilic-lipophilic balance) below 16, preferably below 15, and more preferably below 14. These ethoxylated nonionic surfactants have been found to have good fat-reducing properties.

Accordingly, suitable ethoxylated nonionic surfactants for use here are Dobanol<R>91-2.5 (HLB= 8.1; R is a mixture of C9 and C1 alkyl chains, n is 2.5), or Lutensol<R >T03 (HLB= 8; R is a C13 alkyl chain, n is 3), or Lutensol" A03 (HLB = 8; R is a mixture of C13 and C1S alkyl chains, n is 3), or Tergitol<R>25L3 (HLB=7, 7; R is in the range of C12 to C15 alkyl chain lengths), or Dobanol<H>23-3 (HLB = 8.1, - R is a mixture of C12 and C13 alkyl chains, n is 3), or Dobanol* 23-2 (HLB= 6, 2;R is a mixture of C12 and C13 alkyl chains, n is 2), or Dobanol<R>45-7 (HLB=11.6; R is a mixture of C14 and C15 alkyl chains, n is 7), Dobanol* 23-6 ,5(HLB= 11.9; R is a mixture of C12 and C13 alkyl chains, n is 7), or Dobanol<R>25-7 (HLB= 12; R is a mixture of C12 and C15 alkyl chains, n is 7) , or Dobanol <R>91-5 (HLB= 11.6; R is a mixture of C9 and Cu alkyl chains, n is 5), or Dobanol<R>91-6 (HLB= 12.5; R is a mixture of C9 and C1X alkyl chains, n is 6), or Dobanol" 91-8 (HLB= 13.7; R is a mixture of C9 and C1X alkyl chains, n is 8), Dobanol<R> 91-10 (HLB=14.2; R is a mixture of C9 to CX1 alkyl chains, n is 10) or mixtures thereof. Preferred here is Dobanol<R>91-2 ,5, or Lutensol<R>T03, or Lutensol<R>A03, or Tergitol<R>25L3, or Dobanol<R>23-3, or Dobanol<R>23- 2, or mixtures thereof. These Dobanol<R>surfactants are commercially available from SHELL. These Lutensol R surfactants are commercially available from BASF and these Tergitol R surfactants are commercially available from UNION CARBIDE.

Suitable chemical processes for preparing the ethoxylated nonionic surfactant for use herein include condensation of corresponding alcohols with alkylene oxide in desired conditions. Such processes are well known to professionals in the industry and have been described in detail by the industry.

The mixtures here can desirably include one of the ethoxylated nonionic surfactants or a mixture of the ethoxylated nonionic surfactants that have different HLBs (hydrophilic-lipophilic balance). In a preferred embodiment, the mixture here comprises an ethoxylated nonionic surfactant according to the formula above and with an HLB up to 10 (i.e. a so-called hydrophobic, ethoxylated nonionic surfactant, preferably below 10, and more preferably below 9, and an ethoxylated nonionic surfactant according to the formula above and with an HLB above 10 to 16 (i.e. a so-called hydrophilic ethoxylated nonionic surfactant), preferably from 11 to 14. In this preferred embodiment, the mixtures according to the present invention typically comprise from 0.01 to 15% by weight of the total mixture of said hydrophobic ethoxylated nonionic surfactant, preferably from 0.5 to 10% and from 0.01 to 15% by weight of said hydrophilic ethoxylated nonionic surfactant, preferably from 0.5 to 10%.

Such mixtures of ethoxylated nonionic surfactants with different HLBs may be desired as they allow optimal grease removal performance with a wider spectrum of greasy soils with different hydrophobic/hydrophilic properties.

As a third essential element, the compositions according to the present invention comprise a zwitterionic betaine surfactant or a mixture thereof at a level of from 0.001 to 20% by weight of the total mixture. Preferably, the mixtures herein comprise from 0.01 to 10% by weight of the total mixture of said zwitterionic betaine surfactant or mixtures thereof, more preferably from 0.5 to 8% and preferably from 1 to 5%.

Suitable zwitterionic betaine surfactants for use herein contain both a cationic hydrophilic group, ie a quaternary ammonium group, and an anionic group on the same molecule over a relatively wide range of pH values. The typical anionic hydrophilic groups are carboxylates and sulphonates, although other groups such as sulphates, phosphonates and the like can be used. A generic formula for the zwitterionic betaine surfactant for use herein is:

Where Rx is a hydrophobic group, R2 is hydrogen, Cx-C6alkyl, hydroxyalkyl or another substituted C1-C6alkyl group; R 3 is C 1 - C 6 alkyl, hydroxyalkyl or another substituted C 1 - C 6 alkyl group which also joins with R 2 to form ring structures with the N, or a C 1 - C 6 carboxylic acid group or a C 1 - C 6 sulfonate group; R 4 is a moiety connecting the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy-alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group.

Preferred hydrophobic groups Rx are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains which may contain linking groups such as amido groups and ester groups. More preferably, Rx is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more preferably from 10 to 16. These simple alkyl groups are preferred for reasons of cost and stability. However, the hydrophobic group ^ can also be an amido radical of the formula Ra-C(0)-NH-(C(Rb)2)m, where Ra is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18, and more preferably up to 16, Rb is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, and preferably 3, with no more than one hydroxy group in any (C(Rb) 2 ) moiety.

Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more

preferably methyl. Preferred R 3 is a C 1 -C 4 carboxylic acid group or a C 1 -Q sulfonate group, or a C 1 -C 3 alkyl and more preferably methyl. Preferred R 4 is (CH 2 ) where n is a number from 1 to 10, preferably from 1 to 6 and more preferably from 1 to 3.

Some common examples of betaine/sulfobetaine are described in US Patent No. 2,082,275, 2,702,279 and 2,255,082 which are incorporated herein by reference.

Examples of particularly suitable alkyldimethyl betaines include coconut dimethyl betaine, lauryl dimethyl betaine, decyldimethyl betaine, 2-(N-decyl-N,N-dimethyl-ammonia)acetate, 2-(N-coco N,N-dimethylammonium)acetate, myristyldimethyl- betaine, palmityldimethyl betaine, cetyldimethyl betaine, stearyl dimethyl betaine. For example, Coconut dimethyl betaine is commercially available from Seppic under the trade name Amonyl 265 ® . Lauryl betaine is commercially available from Al-bright fcWilson under the trade name Empigen BB/L ® .

Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine or acylamidopropylene-(hydropropylene)sulfobetaine of a C10-C14 fatty acid. For example, the latter is commercially available from Sherex Company under the trade name "Varion CAS ® sulfobetaine".

A further example of betaine is Lauryl-imino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA

Particularly preferred zwitterionic betaine surfactants for use herein are salt-free, i.e. the raw material for the zwitterionic betaine surfactant contains less than 5% by weight of salt, preferably less than 2%, more preferably less than 1% and most preferably from 0.01 to 0 .5%.

By "salts" is meant here any material which has as a basic unit, a pair of positive ions (or a positive molecular ion) and a negative ion (or a negative molecular ion) which contains one or more halogen atoms. Such salts include sodium chloride, potassium chloride, sodium bromide and the like.

Such salt-free zwitterionic betaine surfactants are obtained by conventional manufacturing processes such as reverse osmosis or fractional precipitation. For example, reverse osmosis is based on the principle of contact between the zwitterionic betaine surfactant (commercially available) with a polar solvent (it is understood that such a solvent is salt-free) separated by a semi-permeable membrane such as acetate-cellulose. Adequate pressure is applied to the system to allow the salts to migrate from the surfactant feedstock into the polar solvent phase. In this way, the zwitterionic betaine surfactant raw material is purified, i.e. the salts are subtracted from the raw material.

Advantageously, it has now been surprisingly found that the use of such salt-free zwitterionic betaine surfactants provides improved fabric and color safety when bleaching fabrics with a mixture containing a peroxygen bleach consisting of the same, compared to the use of the same zwitterionic betaine surfactant with larger amount of salts. Thus, the present invention in its broadest view also includes the use of a mixture consisting of a salt-free zwitterionic betaine surface-active substance and a peroxygen bleaching agent for bleaching substances whereby the color fastness (i.e. color damage/discoloration is reduced) and/or the safety of the fabric is improved.

The zwitterionic betaine surfactant herein has the ability to further enhance the stain removal performance achieved by the ethoxylated nonionic surfactant herein on grease stains, while providing improved bleaching effect of the liquid composition of the present invention containing a peroxygen bleach.

In fact, a significant interaction between these ingredients has been observed to obtain an optimal stain removal effect with varying stain types, from particulate to non-particulate dirt from hydrophobic to hydrophilic dirt in varying household applications and especially in applications for washing both hydrophilic and hydrophobic substances.

Optimum stain removal and bleaching performance is achieved when the ethoxylated nonionic and zwitterionic betaine surfactants are present in the composition according to the present invention comprising a peroxygen bleach (pH up to 7) in a weight ratio of the ethoxylated surfactant to the zwitterionic betaine surfactant of from 0.01 to 20, preferably from 0.1 to 15, more preferably from 0.5 to 5 and preferably from 0.8 to 3.

Excellent stain removal and bleaching performance can be advantageously achieved with the compositions herein with a low total level of surfactants. Typically, the mixtures herein comprise from 0.01 to 35% by weight of the total mixture of ethoxylated nonionic and zwitterionic betaine surfactants, preferably from 0.1 to 15%, more preferably from 0.5 to 10%, and even more preferably less than 10% and preferably from 1 to 8%.

In fact, the present invention is based on the discovery that the use of a zwitterionic betaine surfactant on top of the ethoxylated surfactant in appropriate proportions, in a liquid, aqueous mixture including a peroxygen bleach (pH up to 7), increases the bleaching performance and the removal of different types of stains, including grease stains (e.g. lipstick, olive oil, mayonnaise, vegetable oil, sebum, make-up), compared to the bleaching and stain removal performance achieved with the same mixture based on only one of these surfactants ( i.e. ethoxylated nonionic surfactant or zwitterionic betaine surfactant) at the same total surfactant level. For example, it is only at very high levels of nonionic surfactants compared to the dual level of ethoxylated nonionic surfactants and zwitterionic betaine surfactants present in the mixture that one observes a corresponding benefit with regard to fat cleansing. It is important that the stain removal and bleaching benefits are obtained with a liquid aqueous mixture which is a water-like, clear and translucent mixture.

The appearance of a mixture can be assessed via a turbidimetric analysis. For example, the translucency of the mixture can be assessed by measuring its absorption with a spectrophotometer at a wavelength of 800 nm.

The performance with regard to stain removal can be assessed with the following test methods on different types of stains.

A suitable test method for assessing the stain removal performance on a dirty fabric, for example under pre-treatment conditions, is the following: A mixture according to the present invention is applied unmixed to a fabric, preferably on the dirty part of the fabric, and is allowed to work for from 1 to 10 minutes, and said pre-treated fabric is then washed in accordance with normal washing conditions, at a temperature of from 30 to 70°C for from 10 to 100 minutes. The stain removal is then assessed by comparing side by side the soiled fabric pre-treated with the composition according to the present invention with those pre-treated with the reference, for example the same composition but consisting only of an alkylated nonionic surfactant or only a zwitterionic betaine surfactant as the only surfactant. A visual gradation can be used to indicate differences in panel units (psu) in a range from 0 to 4.

A suitable test method for assessing cleaning performance on a hard surface is the following: synthetic dirt representative of typical household kitchen dirt on hard surfaces can be used. The sample dirt is applied to an enamel-coated metal plate (cleaned with a detergent and then with alcohol) with a paint roller, and the plates are then baked at 130°C for 30 minutes. After 24 hours they can be used for the test. This sample is evaluated in a Gardner straight-line scrubber. The results are given as the number of strokes that a given mixture needs to clean a standard soiled plate. The lower the number of strokes required, the more effective the mixture used to clean the sample plates of the dirt referred to as smooth removal.

The bleaching performance can be assessed in the same way as the stain removal performance, but the stains used are bleachable stains such as coffee, tea and the like.

An advantage of the liquid aqueous mixture according to the present invention is that they are physically and chemically stable for long storage times.

Chemical stability of the mixtures here can be assessed by measuring the concentration of available oxygen (often abbreviated to Av02) at a given storage time after preparation of the mixtures. The concentration of available oxygen can be measured by chemical titration methods known in the industry, such as the iodometric method, the thiosulfatimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the selection of the most appropriate method are described for example in "Hydrogen Peroxide", W.C.Schumb, C.N.Satterfield <nd R.L.Wentworth, Reinhold Publishing Corporation, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int.Science 1970.

By "physically stable" is meant here that no phase separation occurs in the mixture after a period of 7 days at 50°C.

Optional ingredients

The mixtures herein may further include a variety of other optional ingredients such as chelators, builders, other surfactants, stabilizers, bleach activators, soil suspending agents, polyamine soil suspending polymers, polymeric soil release agents, radical scavengers, catalysts, color transfer agents, solvents , optical brighteners, perfumes, pigments and dyes.

In a preferred embodiment of the present invention, the ionic strength of the mixture is higher than lx 10"<4>M, preferably greater than 5x 10"<4>M, and more preferably greater than lx10"<3>M. In fact, it has been observed that formulating the compositions of the present invention with such a high ionic strength further contributes to their advantages, i.e., improved stain removal performance and improved bleaching performance. The higher the ionic strength, the better the stain removal and bleaching performance. In fact, it is speculated that under pH conditions in the present mixtures (acidic to neutral), especially when the pH of the mixture is higher than the pka value of the zwitterionic betaine surfactant present therein, said surfactant is in a dipolar form and that its packing is greatly affected by the ionic strength.

The ionic strength of the mixture can be increased by adding different ingredients such as chelates or mixtures of such.

Accordingly, the compositions of the present invention may include a chelate as a preferred optional ingredient. Suitable chelates may be any of those known to those skilled in the art such as those selected from the group comprising phosphonate chelates, amino-carboxylate chelates, other carboxylate chelates, poly-functional-substituted aromatic chelates, ethylenediamine N,N' - disuuric acid, or mixtures thereof.

A chelate may be desirable in the compositions according to the present invention as it allows one to increase the ionic strength of the compositions herein and thus their stain removing and bleaching performance on various surfaces. The presence of chelates can also help to reduce the loss of tensile strength in the fabrics and/or damage to the colours, especially when applied to pre-treat washing. In reality, the chelates inactivate the metal ions present on the surface of the fabrics and/or in the washing mixture (unmixed or diluted) which would otherwise contribute to the radical decomposition of the peroxygen bleach.

Suitable phosphonate chelates for use herein may include alkali metal ethane 1-hydroxy diphosphonate (HEDP), alkylene poly-(alkylenephosphonate), as well as aminophosphonate compounds, including aminoaminotri(methylene phosphonic acid) (ATPM), nitrilo trimethylenephosphonate (NTP) , ethylenediamine tetramethylenephosphonate, and diethylenetriamine pentamethylenephosphonate (DTPMP). The phosphonate compounds may be present either in their acidic form or as salts of various cations on some or all of the acidic functional groups. Preferred phosphonate chelates for use here are diethylenetriamine pentamethylenephosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelates are commercially available from Monsanto under the trade name DEQUEST

Polyfunctionally substituted aromatic chelates may also be useful in the compositions herein. See US Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are the dihydroxy-disulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred chelate for use herein which is biodegradable is ethylenediamine N,N'-diacetic acid, or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof. The ethylenediamine N,N'-dicarboxylic acids, particularly the (S,S) isomer, have been described in detail in US Patent 4,704,233, November 3, 1987, to Hartan and Perkins. The ethylenediamine N,N'-succinic acids are, for example, commercially available under the trade name ssEDDS ® from Palmer Research Laboratories.

Suitable aminocarboxylates for use herein include ethylene diamine tetraacetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA), N-hydroxyethyl ethylene diamine triacetates, nitrilotriacetates, ethylene diamine tetrapropionates, triethylene tetraamine hexaacetates, ethanol diglycines, propylene diamine tetraacetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium or substituted ammonium salt forms. Particularly suitable aminocarboxylates for use here are diethylene triamine pentaacetic acid, propylene diamine tetraacetic acid (PDTA) which is for example commercially available from BASF under the trade name TRILON FS ® , and methylglycine diacetic acid

(MGDA) .

Other carboxylate chelates which may be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.

Another chelate that can be used here has the formula:

where R 1 R 2 , R 3 , and R 4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NOj. -C(O)R', and -SO2R" where R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy , and R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of -H and alkyl.

Particularly preferred chelates for use herein are amino amino-tri(methylenephosphonic acid), diethylene-triamino-pentaacetic acid, diethylene triamine pentamethylenephosphonate, 1-hydroxyethane diphosphonate, ethylenediamine N,N'-diacetic acid, and mixtures thereof.

Typically, the mixtures according to the present invention comprise up to 5% by weight of a chelate, or mixtures thereof, preferably from 0.01 to 1.5% by weight and preferably from 0.01 to 0.5%.

The mixtures according to the present invention may further comprise other surfactants than those mentioned here previously, including other nonionic, anionic, cationic and/or amphoteric surfactants.

Typically, the compositions according to the present invention comprise from 0.01 to 30% by weight of the total composition of another surfactant on top of the zwitterionic betaine surfactant and the ethoxylated nonionic surfactant, preferably from 0.1 to 25% and more preferably from 0.5 to 20%.

Suitable nonionic surfactants which can be used herein include polyhydroxy fatty acid amides, or mixtures thereof according to the formula:

where R<1> is H, or Cx-C4alkyl, C1-C, hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R<2> is C5-C31hydrocarbyl, and Z is a polyhydroxy- hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkylated derivative thereof.

Preferably R<1> is Cx-C4alkyl, more preferably Cx or C2alkyl, and preferably methyl, R<2>is a straight-chain C7-C19alkyl or alkenyl, preferably a straight-chain C9-C18alkyl or alkenyl, more preferably a straight-chain CX1-C18alkyl or alkenyl, and most preferably a straight-chain C1X-C14 alkyl or alkenyl, or mixtures thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, corn syrup with a high dextrose content, high fructose corn syrup, and high maltose corn syrup can be used as well as the individual sugar types listed above. These corn syrups may provide a mixture of sugar components for Z. It is understood that it is in no way intended to exclude other suitable raw materials. Z will preferably be selected from the group consisting of -CH2-(CHOH)n- CH2OH, -CH-(CH2OH) - (CHOH)n_1-CHaOH, -CH2- (CHOH) 2- (CHOHR' ) (CHOH) - CH 2 OH, where n is a number from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and carboxylated derivatives thereof. Most preferred are glycityls where n is 4, especially CH2-(CHOH)4-CH2OH.

In the formula R2-C (0)-N(R1)-Z, R<1> can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy -cyethyl, or N-2-hydroxypropyl. R<2->C(0)-N< can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, caprisamide, palmitamide, talgamide and the like. Z can be 1-deoxyglusityl, 2-deoxyfructityl, 1-deoxymatityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl and the like.

Suitable surfactants of polyhydroxy fatty acid amides are commercially available under the trade name HOE<®>from Hoechst.

Methods for producing surfactants from polyhydroxy fatty acid amides are known in the industry. In general, they can be made by reacting an alkylamine with a reducing sugar in a reductive amination reaction to give a corresponding N-alkylpolyhydroxyamine, and then reacting this with an aliphatic fatty acid ester or triglyceride in a condensation/amidation step to give the product N-alkyl, N-polyhydroxy fatty acid amide. Processes for the preparation of compositions containing polyhydroxysulfuric acid amides are described, for example, in GB Patent Specification 809,060, published February 18, 1959 by Thomas Hedley &Co.,Ltd, US.patent 2,965,576, issued December 20, 1960 to E.R. Wilson, US .patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, US.patent 1,985,424, issued December 25,1934 to Piggott and WO 92/06070, all of which are incorporated herein by reference.

Suitable anionic surfactants that can be used herein include water-soluble salts or acids of the formula ROSOjM where R is preferably a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl with a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g. a cation of an alkali metal (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl, dimethyl, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidine cations and quaternary ammonium cations derived from alkyl amines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains with C12-C16 are preferred for lower washing temperatures (eg below about 50°C) and C16-C18 alkyl chains are preferred for higher washing temperatures (eg above about 50°C).

Other suitable anionic surfactants that can be used here are water-soluble salts or acids of the formula R0(A)mSO3M where R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group with a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12 -C18alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation such as , can be a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium etc), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are included herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidine and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine. Mixtures of these and the like. Exemplary surfactants are C12-C18alkyl polyethoxylate (1.0)sulfate, C12-C18E (1.0) M), C12-C18alkyl polyethoxylate (2.25) sulfate, C12-C1BE(2.25)M), C12-C18alkyl polyethoxylate (3 .0) sulfate C12-C18E(3.0), and C12-C18 alkyl polyethoxylate (4.0) sulfate C12-C18E(4.0)M), where M is suitably selected from sodium and potassium.

Other anionic surfactants useful for washing purposes can also be used here. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts) of soap, C9-C20 linear alkylbenzene sulfonates, Ca-C22 primary or secondary alkane sulfonates, C8-C24 olefin sulfonates, sulphonated carboxylic acids produced by sulphonation of the pyrolysis product of eitrates of alkaline earth metals, e.g. as described in British Patent specification No. 1,082,179 , C8-C24 alkyl polyglycol ether sulfates) containing up to 10 mol of ethylene oxide); alkyl ester sulfonates such as C14-C16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinate (especially saturated or unsaturated C6-C14 diesters), sulfates of alkyl polysaccharides such as the sulfates of alkyl polyglucoside (the nonionic non-sulfated compound described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those according to the formula RO (CH2CH20) kCH2COO- M+ where R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is soluble, salt-forming cations. Resin acids and hydrogenated resin acids are also suitable such as resin, hydrogenated resin and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A number of such surfactants are also generally described in US Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at column 23, line 58 to column 29, line 23 (here included as a reference).

Other suitable anionic surfactants that can be used here also include acyl sarcosinate or mixtures thereof, in acid and/or salt form, preferably long-chain acyl sarcosinates with the following formula:

where M is hydrogen or a cationic moiety and where R is an alkyl group with from 11 to 15 carbon atoms, preferably with from 11 to 13 carbon atoms. Preferred M is hydrogen and salts of alkali metals, especially sodium and potassium. Said surfactants of acyl sarcosinate are derived from natural fatty acids and the amino acid sarcosinate (N-methyl glycine). It is suitable for use as aqueous solutions of their salts or in their acidic form as powders. Being derivatives of natural fatty acids, said acyl sarcosinates break down quickly and quickly biologically and they have good compatibility with the skin.

accordingly, suitable long-chain acyl sarcosinates include C12 acyl sarcosinate (ie an acyl sarcosinate according to the formula above where M is hydrogen and R is an alkyl group of 11 carbon atoms) and C14 acyl sarcosinate

(ie an acyl sarcosinate according to the formula above where M is hydrogen and R is an alkyl group with 13 carbon atoms). C12acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied by Hampshire. C14acyl sarcosinate is commercially available for example, as Hamposyl M-30® supplied by Hampshire.

Suitable amphoteric surfactants for use here include amine oxides with the following formula RxR2R3NO where each of RI, R2 and R3 are independently saturated, substituted or unsubstituted, linear or branched hydrocarbon chains with from 1 to 30 carbon atoms. Preferred amine oxide surfactants for use according to the present invention are amine oxides with the following formula R1R2R3NO where RI is a hydrocarbon chain with from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and where R 2 and R 3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains with from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups. RI can be a saturated substituted or unsubstituted linear or branched hydrocarbon chain. Suitable amine oxides for use herein are, for example, naturally mixed C8-C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst.

The compositions in the present invention may comprise a radical scavenger or a mixture of such. Suitable radical scavengers for use herein include the well-known substituted mono- and dihydroxybenzenes and their analogues, alkyl and aryl carboxylates and mixtures thereof. Preferred such radical scavengers for use herein include di-tert-butyl hydroxytoluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl hydroxy anisole, benzoic acid, toluic acid, catechol, t-butyl catechol , benzylamine, 1,1,3-tri(2-methyl-4-hydroxy-5-t-butylphenyl)butane, n-propyl gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxytoluene. Such radical scavengers as N-propyl gallate may be commercially available from Nipa Laboratories under the trade name Nipanox<®>. Free radical scavengers, if used, are typically present herein in amounts ranging from 0 up to 10% by weight of the total composition and preferably from 0.001 to 0.5% by weight.

The presence of radical scavengers can contribute to a reduced loss of tensile strength in the fabric and/or minor color damage when the mixtures according to the present invention are used for any washing purpose, especially when pre-treating the laundry.

The mixtures according to the present invention may further comprise an antioxidant or mixtures thereof. Typically, the mixtures herein consist of up to 10% by weight of the total mixture of an antioxidant or mixtures thereof, preferably from 0.002 to 5%, more preferably from 0.005 to 2% and most preferably from 0.01 to 1%.

Suitable antioxidants which can be used herein include organic acids such as citric acid, ascorbic acid, tartaric acid, adipic acid and sorbic acid, or amines such as lecithin, or amino acids such as glutamine, methionine and cysteine, or esters such as ascorbyl palmitate, ascorbyl stearate and triethyl citrate or mixtures of these. Preferred antioxidants for use herein are citric acid, ascorbic acid, ascorbyl palmitate, lecithin or mixtures thereof.

As an optional ingredient, the compositions according to the present invention may include a bleach activator or mixtures thereof. By "bleach activator" is meant here a compound that reacts with hydrogen peroxide to form a peracid. The peracid formed in this way constitutes the activated bleaching agent. Suitable bleach activators for use herein include those belonging to the class of esters, amides, imides or anhydrides. Examples of suitable compounds of this type are described in British Patent GB 1,586,-769 and GB 2,143,231 and a method for their formation in a pearled form is described in European Published Patent Application EP-A-62,523. Suitable examples of such compounds which can be used here are tetraacetyl ethylenediamine (TAED), sodium 3,5,5 trimethyl-hexanoyl-oxybenzene sulphonate, diperoxy dodecanoic acid as described for example in US 4,818,425 and nonylamides of peroxyadipic acid as described for example in US 4,259,201 and n-nonanoyloxybenzenesulfonate (NOBS). Also suitable are N-acyl caprolactams selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecanoyl caprolactam, formyl caprolactam, acetyl caprolactam, pro -panoyl caprolactam, butanoyl caprolactam, pentanoyl caprolactam or mixtures thereof. A particular family of bleach activators of interest was described in EP 624,154, and particularly preferred in this family is acetyl triethyl citrate (ATC). Acetyl triethyl citrate has the advantage that it is environmentally friendly as it eventually breaks down into citric acid and alcohol. Furthermore, acetyl triethyl citrate has good hydrolytic stability in the product during storage, and it is an effective bleach activator. The mixtures according to the present invention can comprise from 0.01 to 20% by weight of the total mixture of said bleach activator, or mixtures of. these, preferably from 1 to 10%, and more preferably from 3 to 7%.

Cleaning processes

In the present invention, the liquid aqueous cleaning mixture according to the present invention must come into contact with the surface to be cleaned.

By "surfaces" is meant here any dead surface. These dead surfaces include, but are not limited to, hard surfaces typically found in houses such as kitchens, bathrooms or inside cars, e.g. tiles, walls, floors, chrome, glass, smooth vinyl, any plastic surface, plastic-treated wood, table tops, sinks, stove tops, plates, sanitary fixtures such as drains, shower systems, shower curtains, sinks, toilets and the like, as well as substances such as includes clothes, curtains, curtains, bed linen, bath towels, tablecloths, sleeping bags, tents, upholstered furniture and the like, and carpets. Dead surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.

Thus, the present invention also includes a process for cleaning a material such as the dead surface. In such a process, the mixture as defined here is in contact with the surface to be cleaned. This can be done either in a so-called "pretreatment method", where a mixture as defined here is added unmixed to said substance before the substance is rinsed, or washed and then rinsed, or in a "soaking method" where a mixture as defined here is first diluted in a aqueous bath and the fabrics are immersed and soaked before being rinsed, or in a "wash through method" where a mixture as defined here is added on top of a washing liquid formed by dissolving or dispersing a typical detergent. It is also important in both cases that the substances are rinsed after they have been in contact with said mixture before said mixture has completely dried out.

In fact, it has been found that evaporation of water helps to increase the concentration of free radicals on the surface of the substances, and consequently the speed of the chain reaction. It is also speculated whether an auto-oxidation occurs when water evaporates when the liquid mixtures are allowed to dry on the substances. Said auto-oxidation reaction generates peroxy radicals which can contribute to the breakdown of cellulose. Thus, by not allowing the liquid mixtures as described here to dry on the fabrics in a process for pre-treating soiled fabrics, you help to reduce the loss of tensile strength and/or the damage to the colors when you pre-treat the fabrics with liquid mixtures containing peroxygen bleaches.

In a pretreatment mode, the process comprises the steps of adding said liquid mixture in its unmixed form to said substances, or at least the soiled parts thereof, and then rinsing, or washing and then rinsing said substances. In this method, the unmixed mixtures can optionally be allowed to act on said substances for a period varying from 1 min. to 1 hour, before the fabrics are rinsed, or washed and then rinsed, provided that the mixture is not allowed to dry on said fabrics. For particularly difficult stains, it may be appropriate to further rub or brush said substances with a sponge or brush, or by rubbing two pieces of cloth against each other.

In another method, generally referred to as "soaking", the process comprises the steps of diluting said liquid mixture in its unmixed form in an aqueous bath to obtain a diluted mixture. The degree of dilution of the liquid mixture in an aqueous bath is typically up to 1:85, preferably up to 1:50 and more preferably about 1:25 (mixture:water). The fabrics are then contacted with the aqueous bath containing the aqueous mixture, and the fabrics are finally rinsed, or washed and then rinsed. Preferably, in this embodiment, the substances are immersed in the aqueous bath comprising the liquid mixture, and preferably, the substances are allowed to soak there for a period which can vary from 1 minute to 48 hours, preferably from 1 hour to 24 hours.

In yet another mode which may be considered a sub-embodiment of "soaking", generally referred to as "bleaching through washing", the liquid mixture is used as an additive to the washing. And in this embodiment, the aqueous bath is formed by dissolving or dispersing a conventional detergent in water. The liquid mixture in its unmixed form is brought into contact with the aqueous bath, and the substances come into contact with the aqueous bath containing the liquid mixture. Finally, the fabrics are rinsed.

In another embodiment, the present invention also includes a process for cleaning hard surfaces, such as dead surfaces. In such a process, the mixture as defined here is allowed to come into contact with the hard surface to be cleaned. The present invention thus comprises a process for cleaning a hard surface with a mixture as defined here, where said process comprises the steps of adding said mixture to said hard surface, preferably only the dirty parts thereof, and optionally rinsing said hard surface.

In the process for cleaning hard surfaces according to the present invention, the mixture as defined here can be applied to the surface to be cleaned in its unmixed form or in its diluted form typically up to 200 times its weight of water, preferably from 80 to 2 times its weight of water. And more preferably from 60 to 2 times.

When the compositions of the present invention are used as a cleaning agent for hard surfaces, the compositions are easy to rinse away and they provide a high gloss on the cleaned surface.

Depending on the intended final use, the mixtures here can be packaged in a variety of containers including conventional bottles, bottles equipped with "roll-on", sponge, brush or spray device.

The invention is further illustrated by the following examples.

Examples

The following mixtures were prepared by mixing the listed ingredients in the indicated proportions (% by weight unless otherwise specified).

HEDP is 1-hydroxyethane diphosphonate.

DTPMP is diethylene triamine pentamethylene phosphonate. Miratain H 2C-HA<®>is Lauryl-imino-dipropionate. Salt-free Betaine<*>is Lauryl dimethyl betaine with 0.3% sodium chloride by weight. This betaine is obtained by purification of commercially available Lauryl dimethyl betaine GENAGEN LAB ® (Hoechst) (which contains 7.5% by weight of sodium chloride).

Mixtures I to XVI show excellent performance in terms of general stain removal especially of grease stains such as lipstick, make-up, olive oil, mayonnaise, tallow and the like, and improved bleaching effect.

When used for pretreatment, any of the compounds I to XVI are applied unmixed to the stained part of the fabric and allowed to act there for 5 minutes. The fabric is then washed with a conventional detergent and rinsed.

When used in a "bleach through the wash" mode, any of the compositions I through XVI are contacted with a solution of a common detergent in water. The fabrics are then in contact with the aqueous bath containing the liquid detergent, and the fabric is then rinsed. They can also be used in a softening mode, where 100 ml of the liquid mixture is diluted with 10 liters of water. The substances are then in contact with this aqueous bath containing the mixture and are allowed to soak there for a period of 24 hours. The substances are possibly rinsed.

Blends I to XVI exhibit excellent general stain removal ability when used for cleaning hard surfaces, particularly grease stains along with kitchen grime.

Blends IX to XVI when used to wash colored laundry are safe to use both with regard to the laundry and the colors in any washing application and especially when pre-treating the laundry.

Claims (17)

1. A liquid aqueous mixture having a pH up to 7 and comprising from 0.01 to 20% by weight of the total mixture of a peroxygen bleach, from 0.001 to 30% by weight of the total mixture of an ethoxylated nonionic surfactant, from 0.001 to 20% by weight of a zwitterionic betaine surfactant with a weight ratio of the ethoxylated nonionic surfactant to the zwitterionic betaine surfactant of from 0.01 to 20, with the proviso that said mixture is free of an antimicrobial essential oil or an active of this or a mixture of these. 2. A mixture according to claim 1 where said mixture consists of from 0.01 to 15% by weight of the total mixture of said ethoxylated nonionic surfactant or mixtures thereof, more preferably from 0.5 to 10% and preferably from 1 to 6%. 3. A mixture according to any preceding claim wherein said mixture consists of from 0.01 to 10% by weight of the total mixture of said zwitterionic betaine surfactant or mixtures thereof, preferably from 0.5 to 8% and preferably from 1 to 5%. 4. A composition according to any preceding claim wherein said peroxygen bleach is hydrogen peroxide or a water-soluble source thereof, typically selected from the group consisting of percarbonates, persilicates, persulfates, perborates, peroxyacids, hydroperoxides, aromatic and aliphatic diacyl peroxides and mixtures thereof, preferred are hydrogen peroxide, tert-butyl hydroperoxide, cumyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene monohydroperoxide, tert-amyl peroxide, 2,5-dimethyl-hexane-2, 5-dihydroperoxide, dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, benzoyl peroxide or a mixture of these, and more preferably is hydrogen peroxide. 5. A mixture according to any one of the preceding claims comprising from 1 to 15% by weight of the total mixture of said peroxygen bleaches or mixtures thereof, preferably from 2 to 10%. 6. A composition according to any preceding claim wherein said zwitterionic betaine surfactant conforms to the formula: Where Ry is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain which may contain connecting groups such as amido groups, ester groups, preferably an alkyl group with from 1 to 24 carbon atoms, preferably from 8 to 18 and more preferably from 10 to 16, or an amido radical of the formula Ra-C(0)-NH-(C (Rb) 2) m, where Ra is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group with from 8 up to 20 carbon atoms, preferably up to 18, and more preferably up to 16, Rb is selected from the group comprising hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than a hydroxy group in any (C(Rb ) 2 ) moiety; R 2 is hydrogen, C 1 -C 8 alkyl, hydroxyalkyl or another substituted C 1 -C 6 alkyl group; R 3 is C 1 -C 8 alkyl, hydroxyalkyl or another substituted C 1 -C 6 alkyl group which can also be connected with R 2 to give ring structures with N, or a C 1 -C 8 carboxylic acid group or a C 1 -C 8 sulfonate group; R„ is a part that connects the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or poly alkoxy group with from 1 to 10 carbon atoms; and X is a carboxylate or sulfonate group. 7. A composition according to any preceding claim wherein said zwitterionic betaine surfactant contains less than 5% by weight salt, preferably less than 2%, more preferably less than 1% and most preferably from 0.01 to 0.5% . 8. A composition according to any preceding claim wherein said ethoxylated nonionic surfactant conforms to the formula RO-(C2 H4 0)n H, where R is a C6 to C22 alkyl chain or a C6 to C28 alkylbenzene chain, and where n is from 0 to and n is an integer from 0 to 20, preferably from 1 to 15, more preferably from 2 to 15 and preferably from 2 to 12. 9. A mixture according to any preceding claim wherein said mixture further comprises a chelate or a mixture thereof, typically up to 5% by weight of the total mixture, preferably from 0.01 to 1.5%. 10. A mixture according to claim 9 where said chelate is a phosphonate chelate, an aminocarboxylate chelate, another carboxylate chelate, a polyfunctionally substituted aromatic chelate, ethylenediamine N,N'' diacetic acid or mixtures thereof, and more preferably amino aminotri-(methylenephosphone) -acid), diethylene-triamino-pentaacetic acid, diethylenetriamine pentamethylenephosphonate, 1-hydroxyethane diphosphonate, ethylenediamine N,N'-diacetic acid or mixtures thereof. 11. A mixture according to any one of the preceding claims wherein said mixture further comprises at least one optional ingredient selected from the group consisting of builders, surfactants other than ethoxylated nonionic surfactants and zwitterionic betaine surfactants, stabilizers, bleaching activators, soil suspending agents, polyamine soil suspending polymers, polymeric soil release agents, radical scavengers, catalysts, dye transfer agents, solvents, optical brighteners, perfumes, dyes, pigments and mixtures thereof. 12. A process for cleaning substances comprising the steps of diluting a liquid composition according to any preceding claim in an aqueous bath, in its unmixed form, leaving said substances in contact with said aqueous bath consisting of said liquid mixture, and then rinse, or wash and then rinse said substance. 13. A process according to claim 12 where the substances are allowed to soak up in said aqueous bath comprising said liquid mixture for a period which can vary from 1 minute to 48 hours, preferably from 1 to 24 hours. 14. A process according to claim 12 where said aqueous bath is formed by dissolving or dispersing a conventional detergent in water. 15. One process for pre-treating fabrics comprising the steps of applying a liquid composition according to any one of claims 1 to 11, in its unmixed form, to said fabric, preferably only the soiled portions thereof, prior to rinsing said substance, or washing and then rinsing said substance. 16. A process for cleaning a hard surface with a composition according to any one of claims 1 to 11, wherein said process comprises the steps of applying said composition to said hard surface and optionally rinsing said hard surface. 17. The use of a mixture comprising a salt-free zwitterionic betaine surfactant and a peroxygen bleaching agent for washing/bleaching fabrics whereby the color fastness and/or safety of the fabric is improved.