CH669604A5 - - Google Patents

Description

DESCRIPTION The invention relates to a liquid textile detergent and bleach, in particular for household laundry, which is constructed in particular on a non-aqueous basis, is easy to pour and does not gel when added to water.

Liquid textile detergents or heavy-duty detergents on a non-aqueous basis, in which builder particles are dispersed in a liquid nonionic surfactant, are known, for example, from US Pat. Nos. 4,316,812, 3,630,929, 4,264,466 and from GS-PS 1 205 711, 1 270 040 and 1,600,981.

Liquid textile detergents are easier to use than powdery or particulate products because they are easier to measure, dissolve quickly in the wash liquor and can be applied as a concentrated solution or dispersion to heavily soiled areas of the textiles to be washed and also do not dust and require less space. Furthermore, these liquid detergents can also contain additives which would otherwise decompose during drying steps and are mostly used in the production of particulate detergents. Despite these advantages over solid heavy-duty detergents, liquid detergents have some disadvantages common for household products, since separating layers form during storage or at lower temperatures and easy redispersion is not possible; in other cases the viscosity changes and the product either becomes too viscous or gives a thin watery consistency; clear liquid detergents can also become cloudy or gel when standing.

These disadvantages depend on the theological properties of the nonionic liquid surfactant systems with or without particulate constituents suspended in them, particularly in the case of non-aqueous liquid detergents containing builders, where the difficulties of gelling and settling of the suspended builders or other additives is of particular importance for the pourability, dispersibility and stability. The rheological behavior of these non-aqueous detergents corresponds to that of paints in which inorganic pigments are dispersed in a non-aqueous carrier liquid.

Stability problems arise both with paints and with liquid textile detergents with builders because the density of the pigments or builders is greater than that of the liquid phase and the particles settle according to Stoke's law. Such sedimentation can be countered by either influencing the viscosity of the carrier liquid or reducing the size of the solid particles.

For example, such suspensions can be stabilized by adding inorganic or organic thickeners or dispersants, such as by adding inorganic materials with a large surface area such as finely divided silica, clay or by adding organic thickeners such as cellulose ethers, polyacrylic compounds or polyacrylamides or polyelectrolytes. However, such an increase in the viscosity of the suspension is limited by the requirement that the liquid suspension must remain pourable even at a low temperature. In addition, these additives do not contribute to the cleaning effect of the detergent.

A reduction in the particle size is more advantageous and leads to an increase in the specific surface area of the solid particles, which proportionally improves the wetting of the individual particles by the non-aqueous carrier liquid, i.e. the liquid nonionic surfactant, while on the other hand reducing the average distance between the solid particles becomes, which leads to a corresponding increase in the mutual influence of the individual particles. Both effects increase the final gel strength and the yield stress of the suspension, while the plastic viscosity is noticeably reduced.

Non-aqueous, liquid detergents with builders such as polyphosphates and in particular sodium tripolyphosphate (TPP) in non-ionic surfactants behave rheologically according to the Casson equation, according to which the yield stress corresponds to the minimum load required to trigger plastic deformation or flow of the suspensions.

If you view a suspension as a loose network of solid particles and the applied forces are below the yield stress, the suspension behaves like an elastic gel and there is no plastic flow. However, when the yield stress is overcome, the network breaks down at some points and the corresponding sample shows a flow with a very high apparent viscosity. However, if the applied forces are much higher than the yield stress, the pigments are partially divided by the shear forces and the apparent viscosity decreases. If the shear forces become much greater than the yield stress, the solid particles are completely distributed by the shear forces, and an extremely low apparent viscosity is established, as if there was no influence on the individual particles at all.

It follows that the higher the yield stress of the suspension, the higher the apparent viscosity at a low shear rate and the better the physical stability of the product.

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Apart from the problems of settling or phase separation, non-aqueous liquid textile detergents based on liquid nonionic surfactants have the disadvantage that the nonionic surfactants tend to gel when added to cold water, which occurs particularly in European household washing machines in which the detergent is added via a cold device Water is rinsed into the wash liquor. This is particularly noticeable during winter when both the detergent and the rinse water for the dispensing container are cold and lead to an increase in the viscosity or gelation of the detergent. As a result, the detergent is not completely fed into the washing drum and deposits over time in the addition area and can only be removed with hot water.

Gelling presents additional difficulties when washing with cold water, as is recommended for items made of synthetic fibers or for delicate textiles that run in warm or hot water.

In order to reduce the gelling problems with aqueous and essentially scaffold-free detergents, attempts have been made in part to mix the liquid nonionic surfactants with solvents which influence the viscosity and substances which prevent gel formation, such as, for example, low alkanols such as ethyl alcohol according to US Pat. No. 3,953,380. or with alkali formats and adipates according to US Pat. No. 4,368,147 or with hexylene glycol or polyethylene glycol.

According to this literature, the use of up to at most 2.5% lower (Ci-Q) alkyl ether derivatives of lower (C2-C3) polyols, such as, for example, ethylene glycol, instead of ethanol in these aqueous detergents containing no builders is suggested, as is is also described analogously in US Pat. Nos. 4,111,855 and 4,201,686. However, there is no indication here that these compounds, which are commercially available, for example, under the name cello acid, are effective for viscosity control or for gel prevention in the case of non-aqueous, liquid, non-ionic surfactants, in particular not in the case of such liquid and non-aqueous, non-ionic surfactants , in which builder salts such as poly-phosphates are suspended, and in particular also for those detergents which require lower alkanols as viscosity regulators.

GB-PS 1,600,981 also mentions that, for non-aqueous detergents containing suspended builders, it may be advantageous to use mixtures of nonionics using certain dispersants for these compounds, such as finely divided silicic acid and / or polyether group-containing compounds with a molecular weight of at least 500 To use surfactants, one component of which is surface-active and the other of which is both surface-active and reduces the pour point of the mixture. The first component of this mixture is, for example, a Ci2-Cis fatty alcohol with 5 to 15 moles of ethylene and / or propylene oxide per mole, while the other component is, for example, a linear Cö-Cs or branched Cs-Cn fatty alcohol with 2 to 8 moles Ethylene and / or propylene oxide per mole. However, there is no indication here that these short-chain compounds influence the viscosity and influence the gelling of a non-aqueous heavy-duty detergent based on nonionic surfactants with builders suspended in them.

It is also known to improve the resistance of nonionic surfactants to gelling on contact with cold water in particular, for example by incorporating a carboxylic acid in the terminal remainder of the nonionic molecule and thus preventing gelation upon dilution, reducing the pour point and the formation of an anionic one Surfactants favor neutralization in the wash liquor. The gelling of nonionic compounds can also be improved by, for example, changing the chain length of the hydrophobic-lipophilic radicals and changing the number and proportion of alkylene oxides such as ethylene oxide in the hydrophilic radical. For example, a Cn fatty alcohol ethoxylated with 8 moles of ethylene oxide shows little tendency to gel.

Nevertheless, the aim is to improve the stability, the viscosity and the gel prevention of non-aqueous, liquid detergents.

Accordingly, the object of the invention is to provide a liquid textile detergent, which is preferably in non-aqueous form, which does not gel when combined or when cold water is added in particular, and which is also storage-stable, easy to pour and in cold, warm or hot water is easily dispersible. It can be used as a heavy-duty detergent with a high proportion of builders. The agent according to the invention is pourable at all temperatures and can be used in conventional European washing machines without impairing the dispensing devices, even under cold temperature conditions. The preferred heavy duty detergent has a low viscosity and contains tripolyphosphate builders dispersed in the non-aqueous, liquid, nonionic detergent, low molecular weight amphiphilic compounds being present in an amount sufficient to reduce the viscosity of the detergent in the absence of water and also together with cold water.

The liquid textile washing and bleaching agent according to the invention is characterized by a content of a liquid nonionic surfactant, a water-soluble, inorganic peroxide salt as bleaching agent and an effective amount of an inhibitor against the decomposition of the peroxide salts caused by enzymes.

A low molecular weight amphiphilic compound, in particular a mono-, di- or tri- (C2-C3) alkylene glycol mono- (Ci-C3) alkyl ether, can be added to the agent according to the invention in order to prevent gelation of the nonionic surfactant in the presence of cold water. This preferred agent can also contain a suspension of a builder salt in the liquid nonionic surfactant together with a (C2-C3) alkylene glycol colmono (Ci-C5) alkyl ether to reduce the viscosity in the absence of water and with the subsequent addition of cold water .

In particular, the invention proposes a non-aqueous liquid cleaning mixture which is pourable at temperatures below about 5 ° C. and does not gel in the presence of water below 20 ° C., this agent being essentially free of water and a liquid nonionic surfactant and a C2-C3 -Alkylene glycol mono (Ci-Cs) alkyl ether contains.

To wash, a container can be filled with the liquid detergent and added to the aqueous washing liquor, usually without adding heated water to the detergent so that it enters the washing liquor together with the water. Due to the preferred presence of a low molecular weight amphiphilic compound, namely a lower C2-C3-alkylene glycol mono (Ci-C5) alkyl ether, the agent can be easily transported into the washing drum, even if the detergent is at temperatures below room temperature. In addition, the mixture does not gel on contact with the water and is easy to disperse in the washing drum.

In addition to the liquid nonionic surfactant, the agent according to the invention contains a water-soluble peroxide salt as bleaching agent, e.g. Sodium perborate monohydrate. These persalt bleaches release hydrogen peroxide as an essential oxidizing agent. On the other hand, hydrogen peroxide is easily decomposed by catalase, an enzyme that is absent from the dirt that is usually present. This decomposition also occurs in the presence of bleach activators because the reaction rate between hydrogen peroxide and

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the activator is less than the decomposition of the hydrogen peroxide by catalase. The activity of catalase is very high even at room temperature, so that a considerable amount of active oxygen is lost before the catalase can be deactivated by increasing the temperature of the wash liquor.

To overcome these difficulties, an excess of perborate or other peroxide salt bleaching agents has hitherto been provided, for example in a 2 to 4 times the amount required for effective bleaching of the contaminants in the absence of the peroxide-decomposing enzymes, or in a second - up to 4 times the molar excess compared to the moles of bleach activator present.

It is also known to carry out bleaching with an aqueous peroxide salt bleach solution in the presence of a compound which prevents the decomposition of the bleaching agents caused by enzymes. According to US Pat. No. 3,606,990, numerous inhibitors such as, for example, hydroxylamine salts, hydrazines and phenylhdrazines and their salts, which can be substituted with phenols and polyphenols, are known as inhibitors and also numerous detergents which contain water-soluble inorganic peroxide bleaching agents and inhibitors. However, no liquid detergent mixture containing such inhibitors is suggested, nor is there any indication that these inhibitors are effective in mixtures which contain a bleach activator in addition to the peroxide salt bleach; in particular in column 7, lines 25-29 of this literature it is found that with hydroxylamine sulfate the effective amount of inhibitor compounds must be 0.5 to about 2% by weight, based on the total mixture.

It was found that in the case of the liquid detergents according to the invention containing water-soluble inorganic peroxide bleaching agents of the persalt type, the addition of an inhibitor counteracts the decomposition of the peroxide salts caused by enzymes. Preferably, only small amounts of less than 0.5% by weight and, for example, 0.01 to 0.45% by weight of the inhibitor are used. A preferred inhibitor is a hydroxylamine salt, e.g. Hydroxylamine sulfate. This salt is extremely stable in these compositions, and a preferred activation of the bleach system is not at all disturbed by conventional persalt bleach activators.

The liquid textile detergent and bleaching agent according to the invention preferably additionally contains an activator for the bleaching agent, which forms a peroxy acid with the bleaching agent in the aqueous washing liquor at a temperature of 40 ° C. or less.

The nonionic surfactants used for the textile detergents according to the invention are sufficiently known from "Surface Active Agents", Volume II by Schwartz, Perry and Berch (1958) and from "Detergents and Emulsiflers" by McCutcheon's (1969). Usually, these nonionic surfactants are poly-alkoxylated lipophilic compounds with lower alkyl residues, the desired balance between hydrophilic and lipophilic groups being achieved by adding a hydrophilic lower polyalkoxy group to the lipophilic residue. Preferred nonionic surfactants are polyalkoxylated higher alkanols with lower alkyl radicals, the alkanol containing 10 to 18 carbon atoms and the lower alkylene oxide with 2 to 3 carbon atoms containing a total of 3-12 carbon atoms. Higher alkanols of higher fatty alcohols having 10-11 or 12-15 C atoms which contain 5 to 8 or 5 to 9 lower alkoxy radicals per mole are preferably used. The lower alkoxy group is preferably an ethoxy radical, but can also be mixed with propoxy radicals, but these are generally present in a smaller proportion of less than 50%. Examples of such compounds are alkanols with 12-15 C atoms which contain about 7 ethylene oxide residues per mole (for example Neodol 25-7 the former is a condensation product of a mixture of higher fatty alcohol with an average of 12-15 C atoms and with 7 moles of ethylene alkoxide, while the latter a corresponding one

Mixture of a higher Ci2-Ci3 fatty alcohol with an average of 6.5 ethylene oxide residues. The higher alcohols are primary alkanols. Other surfactants include linear secondary alcohol ethoxylates (Tergitol 15-S-7 and Tergitol 15-S-9) from Union Carbide Corp., the former of which is a mixed ethoxylated product of a Cn to Cis linear secondary alkanol with 7 moles of ethylene oxide and the latter corresponding product with 9 moles of ethylene oxide.

Furthermore, high molecular weight nonionic surfactants such as Neodol 45-11 can be used, which are similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohols containing 14-15 C atoms and the number of ethylene oxide groups per mole being approximately 11. Other suitable nonionic surfactants are the commercially available Plurafac products, which are the reaction product of a higher linear alcohol with a mixture of ethylene and propylene oxides and have a mixed chain of ethylene oxide and propylene oxide and have a terminal hydroxyl group, such as one with 6 moles of ethylene oxide and 3 moles of propylene oxide condensed Ci3-Ci5 fatty alcohol (Plurafac RA30) or a Cu-Cis fatty alcohol (Plurafac RA40) condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide or a Ci3-Cis condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide Fatty alcohol (Plurafac D25).

In general, the mixed ethylene oxide / propylene oxide / fatty alcohol condensation products can be represented by the general formula R0 (C2H40) x (C3H (j0) yH, where R is a straight-chain and branched primary or secondary aliphatic hydrocarbon radical and preferably an alkyl or alkenyl with 6 to 20 and preferably 10 to 18 and in particular 14 to 18 carbon atoms, where x is a number from 2 to 12 and preferably 4 to 10 and y is a number from 2 to 7 and preferably from 3 to 6.

Other preferred nonionic surfactants are ethoxylated C9-Cn fatty alcohols with an average of 5 moles of ethylene oxide (Dobanol 91-5) or ethoxylated Ci2-Ci5 fatty alcohols with an average of 7 moles of ethylene oxide (Dobanol 25-7).

In order to obtain the best balance between hydrophilic and lipophilic groups in the preferred polyalkoxylated higher alkanols, the number of lower alkoxy radicals should generally make up 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60%, while the nonionic surfactant preferably contains at least 50% of such preferred lower polyalkoxyalkanols. Higher molecular weight alkanols and other normally solid nonionic surfactants can contribute to the gelation of the liquid detergents and are therefore preferably not used or only in a limited amount, although smaller proportions of these may be present due to their cleaning properties. In the more or less preferred nonionic surfactants, the alkyl radicals are generally linear, although branched radicals can also be tolerated, such as those with a carbon atom which is up to 2 carbon atoms away from the final carbon atom of the straight chain and also from the ethoxy chain is removed, provided that such branched alkyl radicals are no longer than 3 carbon atoms. In general, the proportion of branched carbon atoms is small and does not exceed 20% of the total alkyl carbon atoms. Linear alkyls which are terminal to the ethylene oxide chains are likewise preferred and are preferred with regard to the cleaning action, the biological decomposability and because of their non-gelling properties, although medial or secondary ethylene oxides can occur in the chain. This is usually only possible in smaller proportions of such alkyls, and generally less than 20%, but can also be higher. If propylene oxide is present in the alkylene oxide chain, it will usually be present in an amount below 20% and preferably below 10%.

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If e.g. Larger proportions of non-terminal alkoxylated alkanols, polyalkoxylated alkanols containing propylene oxide with low alkoxy radicals and less hydrophilic / lipophilic balanced nonionic surfactants than mentioned above are used and if other nonionic surfactants are used instead of the preferred nonionic surfactants mentioned, the detergent no longer has such a good cleaning power , Stability, viscosity and non-gelling properties, but the use of the compounds which control the viscosity and the gel formation can also improve the properties of detergents based on such nonionic surfactants. If, in some cases, a higher molecular weight polyalkoxylated higher alkanol with lower alkoxy residues is mostly used because of the cleaning power, its proportion is regulated or restricted according to appropriate test approaches in order to obtain the desired cleaning power with the desired viscosity and non-gelling properties. It is seldom necessary to use high molecular weight nonionic surfactants because of their cleaning action, since the preferred and mentioned nonionic surfactants are excellent cleaning agents and additionally ensure that the desired viscosity is maintained in the liquid detergent without gelling at low temperatures. Mixtures of two or more of these liquid nonionic surfactants can also be used and, if appropriate, further advantages can be achieved.

As mentioned, the structure of the liquid nonionic surfactants can be optimized with regard to the carbon chain length, the configuration with regard to linear or branched chains and with regard to the content and distribution of alkylene oxide units. These structural properties also influence the properties of the non-ionic products with regard to the pour point, cloud point, viscosity, tendency to gel and of course also with regard to the cleaning effect.

Most of the commercially available nonionic surfactants have a relatively large distribution of ethylene oxide (EO) and propylene oxide (PO) units and the lipophilic hydrocarbon chain length, the stated EO and PO contents and hydrocarbon chain lengths being total average values. The “polydispersibility” of the hydrophilic and lipophilic chains has a major influence on the properties of the product as well as the specific values of the average values. The relationship between polydispersibility and specific chain length with regard to product properties can be shown for a well-defined nonionic surfactant from the following values for a “surfactant T”. These surfactants from the “Surfactant T” series are obtained by ethoxylation of secondary Ci3 fatty alcohols with a narrow EO distribution and have the following physical properties:

EO content

Pour point in ° C

Cloud point (I% solution) in ° C

Surfactant T5

5

-2

25th

Surfactant T7

7

-2

38

Surfactant 19

9

6

58

Surfactant T12

12

20th

88

Surfactant TBa

8th

2nd

48

Surfactant TBb

8th

15

20th

The last two values of Surfactant TBa and T8b show the influence of the EO distribution. These two products were made from the following blends:

Surfactant T8a:

A mixture of T7 and T9 in a 1: 1 ratio

Surfactant T8b:

A mixture of T5 and T12 in the ratio of 4: 3.

From this table follows:

1. The product T8a corresponds very closely to the product T8, since it lies between the products T7 and T9 both in terms of pour point and cloud point.

2. The T8b product is highly polydisperse and would generally not be satisfactory due to its high pour point and low cloud point.

3. The properties of TBa are essentially additive and lie between those of T7 and T9, while the pour point for T8b is close to the product T12 with the long EO chain and the cloud point is close to that of the product T5 with the short EO- Chain lies.

The viscosities of "Surfactant T" were determined for some products at various concentrations at 25 ° C as follows, the apparent viscosity being determined in the case of a gel.

Concentration in%

Viscosities in mPa

s of

T5

17th

T7 / T9 (1: 1)

19th

112

100 36

63

61

149

80 65

104

112

165

60 750

78

188

239

32200

50 4000

123

233

634

89100

40 2050

96

149

211

187

30 630

58

38

27th

20 170

78

28

100

From these values it can be concluded that the product T7 is less sensitive to gel than the product T5 and that the product T9 is less sensitive to gel than T12. The mixtures of T7 and T9 (corresponding to T8) do not gel and have a viscosity that does not exceed 225 mPa-s. T5 and T12 do not form the same gel structure.

Without making any commitments, one can conclude from these results:

Regarding T5:

With only 5 EO units, the hydrodynamic volume of the EO chain is almost like that of the fat chain. The surfactant molecules can arrange themselves to form a lamellar structure.

Regarding T12:

With 12 EO units, the hydrodynamic volume of the EO chain is larger than that of the fat chain. When the molecules line up, a curved interface appears and rods are obtained. The overall structure is then hexagonal. With a longer EO chain or with a higher hydration, the bending at the interfaces can be such that spheres are actually obtained, and the arrangement of the smallest energy is a face-centered cubic lattice.

For T5 to T7 and T8:

the curvature between the surfaces increases and the energy of the lamellar structure increases. As the lamellar structure loses its stability, the melting temperature is reduced.

For T12 and T9 and T8:

the curvature of the intermediate surfaces decreases and the energy of the hexagonal structure increases, whereby the rods become larger and larger. If a loss of stability occurs, the melting temperature of the structure is reduced.

The product T8 appears to be at a critical point where the lamellar structure is destabilized, i.e. the hexagonal structure is not yet stable enough and no gel is obtained on dilution. In fact, a 50% solution of T8 ultimately gels after two days, but the formation of the overall structure is delayed for a sufficiently long time,

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so that easy water dispersibility is obtained.

The effects of molecular weight on the physical properties of the nonionic surfactants show that the product 18 in the form of a mixture of T7 and 19 in a ratio of 1: 1 shows a good compromise between the lipophilic chain Cn and the hydrophilic chain EO-8, although the The pour point and the maximum viscosity when diluted at 25 ° C are still high. A corresponding EO compromise for the lipophilic C-10 and C-8 chains was determined with the products of the Dobanol-91-x series (from Shell Chemical Co.), which are ethoxylated derivatives of Cs-Ci î fatty alcohols with an average C value of 10; and also on the products of the "Alfonic 610-y" series (the Conoco), which are ethoxylated derivatives of Cö-Cio fatty alcohols with an average of 8 C atoms, where x and y represent the EO weight in%. The physical properties are shown in the following table:

Nonionic EO flow turbidity T | maximum with surfactant value point dilution and in ° C in ° C 25 ° CinmPa-s

Alfonic 610-50R

3rd

-15

gel

(60%)

Alfonic 610-60

4.4

-4

41

36

(60%)

Dobanol 91-5

5

-3

33

gel

(70%)

Dobanol 91-5T

6

+ 2

55

126

(50%

Dobanol 91-8

8th

+ 6

81

gel

(50%)

The products Dobanol 91-5 and 91-8 are commercial products; Dobanol 91-5 topped (1) was manufactured on a laboratory scale. The free alcohol was removed from Dobanol 91-5. Since the portions with the lowest ethoxylation values were also removed, the average EO number is 6. Dobanol 91-5T gives the best results with a C10 lipophilic chain since it does not gel at 25 ° C. The 1% cloud point of 55 ° C is higher than that of the «Surfactant 1B» at 48 ° C. This is probably due to the lower molecular weight, since the entropy of the mixture is higher. «Alfonic 610-60» gives the best results from the series of C8 lipophilic chains.

A compilation of the best EO contents for each lipophilic chain length examined is shown in the following table, in which the C and EO values represent average values:

Nonionic C

EO-

Flow

Cloudy

T] maximum at

Surfactant

Value point exercise

Dilution and

in ° C

Point

25 ° CinmPa-s

in ° C

Surfactant TB 13

8th

+ 2

48

223 (50%)

Dobanol 91-5T 10

6

+2

55

126 (50%)

Alfonic 610-60 8

4.4

-4

41

36 (60%)

The following can be concluded from the values in the table: Flow point: As the molecular weight of the nonionic surfactants decreases, the flow point also decreases. The relatively high pour point of Dobanol 91-5T is probably due to the higher polydispersibility, which was also observed with the products T8a and TBb, namely that the chain polydispersibility increases the pour point.

Cloud point: Theoretically, the entropy of the mixture is higher with increasing number of molecules as the molecular weight decreases, so that the cloud point would increase with decreasing molecular weight. This applies from «Surfactant TB» to «Dobanol 91-5T», but is not confirmed with «Alfonic 610-60»; Here one can assume that the lipophilic hydrocarbon chain with its polydispersibility is responsible for the cloud point, which is theoretically too low. The relatively large proportion of C10 and EO reduces solubilizability.

Maximum viscosity when diluted at 25 ° C: None of the nonionic surfactants gel at 25 ° C when diluted with water. The maximum viscosity decreases sharply with the 5 molecular weight. As the molecular weight of the nonionic surfactants decreases, the hydrogen bonds become less effective. Unfortunately, non-ionic surfactants with too low a molecular weight are not suitable for laundry detergents because their micellar critical concentration (MCC) is too high and a real solution with only limited cleaning power would be obtained under normal washing conditions.

Based on these findings, the effects of low molecular weight amphiphilic compounds on the rheological properties of liquid detergents or cleaning agents based on nonionic surfactants were investigated. The result was that the pour point of the mixture can be prevented and a certain inhibition of gel formation can be achieved if short-chain hydrocarbons with, for example, 8 carbon atoms with short-chain ethylene oxide substituents, for example about 4 20 moles, as an amphiphilic additive such as «Alfonic 610-60» used, these additives not noticeably affect the overall cleaning behavior towards textiles and under normal conditions of use also give no overall satisfactory viscosity control.

Accordingly, the present invention is based, at least in part, on the finding that low molecular weight amphiphilic compounds, which in their chemical structure can be regarded as analogous to the ethoxylated and / or propoxylated fatty alcohols, but have short hydrocarbon chains with 1 to 5 30 carbon atoms and a low content Have alkylene oxides such as ethylene oxide and / or propylene oxide of about 1 to 4 EO / PO per molecule, are effective agents for controlling the viscosity and preventing gel formation in liquid nonionic detergents and cleaning agents.

The preferred amphiphilic compounds which control the viscosity and prevent gel formation in the products according to the invention have the following general formula: R,

40 R0 (CHCH20) nH

in which R is a Ci-Cs, preferably a C2-C5 and in particular a Cî-Ci radical and in particular a Ct-alkyl radical, while R is either CH3 or preferably H and n is a number from 45 1 to 4 and preferably is on average 2 to 4.

Preferred examples of suitable amphiphilic compounds are ethylene glycol monoethyl ether (C2H5-O-CH2CH2OH) and the diethylene glycol monobutyl ether C4Hs0- (CH2CH20) 2H, the latter being particularly preferred because of its unique action in order to control the viscosity.

Although the amphiphilic compound and in particular the diethylene glycol monobutyl ether are preferably used as the only viscosity control additive for preventing a gel in the detergents according to the invention, the rheological properties of the anhydrous liquid nonionic detergents can be improved by providing a small amount of a nonionic surfactant which has been modified to convert a free hydroxyl group to a free car-boxyl group, such as a partial ester of a non-ionic surfactant and a polycarboxylic acid and / or an acidic organic phosphorus compound with an acidic POH group such as a partial ester of phosphoric acid and an alkanol . From U.S. Patent Application 597,948 dated April 9, 1984, to which express reference is made, it follows that nonionic 65 surfactants with free modified carboxyl radicals are generally characterized as polyether carboxylic acids and reduce the temperature at which the liquid nonionic surfactants mix with water Form gel. The acidic polyether compound can

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furthermore reduce the yield stress of such dispersions and support their dispersibility without correspondingly reducing the stability towards settling. Suitable polyether carboxylic acid contain groups of the following formula, namely

* OCH2-CH2 * * ÇH-CH2 * -Y-ch3

in which R2 is hydrogen or methyl, Y is oxygen or sulfur and Z is an organic bridge, while p is a positive number from 3 to 50 and q is a number from 0 or a positive number up to 10. Examples of these compounds are half esters of "Plurafac RA30" with succinic anhydride, half esters of "Dobanol 25-7" and "Dobanol 91-5" with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic anhydride, citric acid and the like can also be used. Furthermore, other bridges can also be provided, such as ether, thioether or urethane bridges, which are formed in the usual way. For example, to incorporate an ether bridge, the nonionic surfactant can be treated with a strong base to convert the OH residue into an ONa group, followed by reaction with a halocarboxylic acid such as chloroacetic acid or chloropropionic acid or a corresponding bromine compound. The carboxylic acid obtained can then have the formula R-Y-ZCOOH, in which R denotes the remainder of the nonionic surfactant after removal of the terminal OH group. Y means oxygen or sulfur and Z means an organic bridge such as a hydrocarbon group of, for example, up to 10 carbon atoms, which is attached to the oxygen or sulfur atom directly or by means of an intermediate bond, namely an oxygen-containing bond, for example

C = 0 C = 0

NH

The polyether carboxylic acid can be made from a polyether that is a nonionic surfactant, for example by reacting a polyalkoxy compound such as polyethylene glycol or a monoester or monoether thereof that does not have the long alkyl chains of the nonionic surfactants. He can therefore use the general formula

R2 i I

R (OCH-CH2) n-

in which R2 is hydrogen or methyl, R1 is an alkylphenyl or alkyl or other chain terminating group and n has at least a value of 3, for example 5 to 25. If the alkyl radical R1 is a higher alkyl, R is the radical of a nonionic surfactant. As mentioned, R1 can be hydrogen or a lower alkyl such as methyl, ethyl, propyl or butyl or a lower acyl radical such as acetyl. If the acidic polyether compound is present in the detergents according to the invention, it is preferably added in solution in the nonionic surfactant.

Other suitable additional means for preventing gel formation are Cc-Cn-alkyl or alkenyldicarboxylic acid anhydrides such as, for example, qctenylsuccinic anhydride, octenyl maleic anhydride, dodecylsuccinic anhydride etc. These compounds can either be used together with the gelling-preventing polyether carboxylic acids or can be partially or completely replaced.

As is apparent from U.S. Patent Application No. 597,793 dated April 6, 1984, which is incorporated herein by reference,

Acidic organic phosphorus compounds with an acidic POH group can improve the stability of the builders suspension and in particular the polyphosphate builders in the non-aqueous liquid nonionic surfactants.

5 The acidic organic phosphorus compound can, for example, be a partial ester of a phosphoric acid and an alcohol, such as, for example, an alkanol with a lipophilic character which has, for example, more than 5 carbon atoms, for example 8 to 20 carbon atoms.

A typical example of this is the partial ester of phosphoric acid and a Cir.-Cis-alkanol, which consists of about 35% monoester and 65% diester.

The preferred addition of very small amounts of, for example, 0.05 to 0.3% by weight of these acidic organic phosphorus compounds makes the suspensions significantly more stable against settling on standing; however, they remain pourable, presumably due to an increase in the flow value of the suspension; however, the plastic viscosity decreases. It is believed that the use of the acidic phosphorus compounds leads to the formation of an energetic physical bond between the POH residue of the molecule and the surfaces of the inorganic polyphosphate builders, so that these surfaces assume an organic character and are more compatible with the nonionic surfactant. 25 The acidic organic phosphorus compounds must not only be the above-mentioned partial esters of phosphoric acids and aikanoles, but also partial esters of phosphoric acid or phosphorous acid with a monoalcohol or a polyhydric alcohol such as hexylene glycol, ethylene-30 glycol, di- or triethylene glycol or higher polyethylene glycol -len, polypropylene glycol, glycerin, sorbitol, mono- or diglyce-ride of fatty acids and the like, in which one, two or more alcoholic OH groups are esterified with the phosphoric acid. The alcohol can be a nonionic surfactant, such as an ethoxylated or ethoxylated / propoxylated higher alcohol or a corresponding higher alkylphenol compound or a higher alkylamide. The -POH residue need not be bound to the organic part of the molecule via an ester bond; instead, it can also be directly attached to the carbon atom, such as a phosphonic acid, such as a polystyrene, in which some of the aromatic rings carry phosphonic acid residues or phosphinic acid residues; or alkylphosphonic acid such as propyl or laurylphosphonic acid; A connection with the carbon via other intermediate bridges such as oxygen, sulfur or nitrogen atoms is also possible. The atomic ratio of carbon to phosphorus in the organic phosphorus compounds is at least in a range of approximately 3: 1, for example 5: 1, 10: 1, 20: 1, 30: 1 or 40: 1.

50 The detergents according to the invention may furthermore, and preferably contain, water-soluble builder salts, such as the salts described in US Pat. Nos. 4,316,812,4264,466 and 3,630,929. The water-soluble inorganic alkaline builder salts, which can be used either alone or with other builders, are in particular alkali carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates, whereby ammonium salts or substituted ammonium salts can also be used. Examples include sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, 60 potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sequicarbonate, sodium mono- and diorthophosphate and potassium hydrogen carbonate. Sodium tripolyphosphate (TPP) is particularly preferred.

Alkali silicates are also suitable builders salts, which also have a corrosion-preventing effect on the parts of the washing machine. In preferred sodium silicates, the Na20 / SiO2 ratio is in a range from 1.6 to 1 to 1 to 3.2 and in particular in a range from 1 and 2 to 1 to 2.8; it can too

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Potassium silicates with the same proportions can be used.

Other suitable builders are water-insoluble aluminum silicates, both crystalline and amorphous. Numerous crystalline zeolites, such as those described in British Pat. No. 1,504,168, in US Pat. No. 4,409,136 and in CA Patents 1,072,835 and 1,087,477, can also be used as builders. An example of amorphous zeolites are the compounds of the general formula described in BE-PS 835 351

(M20) x- (Al203) y- (Si02) z-w H2Q

in which x has a value of 1, y a value of 0.8 to 1.2 and preferably 1 and z a value of 1.5 to 3.5 or higher and preferably 2 to 3 and w a value of 0 to 9 and are preferably 2.5 to 6 and M is preferably sodium. Typical zeolites are zeolites 4A with a calcium ion exchange capacity of about 200 or more meq / g; these values can also be higher, for example 400 mÂq / g. Furthermore, other additives, such as clays, in particular water-insoluble types, can be used as additives in the detergents according to the invention, bentonite being particularly suitable. Preferred is a bentonite, which is primarily a montmorillo-nit, which is a hydrated aluminum silicate, in which 1/6 of the aluminum atoms can be replaced by magnesium and which contains loose amounts of fluctuating amounts of hydrogen, sodium, potassium and calcium. The purified bentonites, i.e. Those that are free of sand and gravel contain at least 50% montmorillonite and have a cation exchange capacity of at least 50 to 75 meq / g bentonite. Particularly preferred bentonites are Wyoming or Western US bentonite, which are marketed by Georgia Kaolin Co. under the name Thixo-jels 1,2, 3 and 4. These bentonites have a softening effect on textiles, as described in GB-PS 401 413 and 461 221.

Furthermore, organic alkaline sequestering builder salts can be used alone or with other organic or inorganic builders such as the alkali, ammonium or substituted ammonium salts of aminopolycarboxylic acids, such as the sodium or potassium salt of ethylenediaminetetraacetic acid (EDTA), of nitrilotriacetic acid (NTA) and in particular triethanolammonium-N- (2-hydroxyethyl) nitri-iodiacetate and mixtures of these salts.

Other suitable organic builders are carboxymethyl succinates, tartronates and glycolates and in particular poly-acetal carboxylates as described in US Pat. Nos. 4,144,226,4,315,092 and 4,146,495. Analogous builders can also be used, as are described in US Pat. Nos. 4,141,676,4 169,934, 4,201,858.4,204,852, 4,224,420, 4,225,685.4,226,960, 4,233,422.4,233,423. 4 302 564 and 4 303 777 or in EU-A 0015024, 0021491 and 0063399.

Since the detergents according to the invention are generally highly concentrated and are therefore only used in relatively low doses, it is desirable to supplement the phosphate builders such as sodium tripolyphosphate with an additional builder, such as, for example, with a polymeric carboxylic acid with a high calcium binding capacity, in order to avoid incrustations which can otherwise occur due to the formation of insoluble calcium phosphates. Such additional builders are generally known.

Furthermore, the detergents according to the invention can be added with other customary additives to achieve further desired functional or aesthetic properties. For example, smaller amounts of dirt suspending agents or agents which are intended to prevent redeposition of dirt, such as polyvinyl alcohol, fatty acid amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, and optical brighteners such as, for example, cotton brighteners or amine and polyester brighteners such as stilbene, triazole and benzidine sulfone compounds, and in particular sulfonated compounds substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, with the style level and triazole combinations being preferred.

Ultramarine blue can be used as a bluing agent. Enzymes, preferably proteolytic enzymes such as subtilisin, bromelin, papain, trypsin, pepsin, and also amylase types and lipase types, alone or in mixtures, are suitable as additives. Other additives are bactericides such as tetrachlorosalicylic anilide, hexachlorophene, fungicides, dyes, water-dispersible pigments, preservatives, UV absorbers, agents for preventing yellowing such as sodium carboxymethyl cellulose or complexes of Ci2-C22-alkyl alcohols with Ci2-Ci8-alkyl sulfates Modifiers for the pH value and buffer substances, color-safe bleach, perfume, foam presser and agents for preventing the formation of deposits such as silicone compounds.

As already mentioned above, the agent according to the invention contains a water-soluble inorganic peroxide salt as a bleaching agent. The bleaching agents are per-compounds which release hydrogen peroxide in solutions, namely compounds which contain hydrogen peroxide or an inorganic perhydrate which releases hydrogen peroxide from the crystal lattice when dissolved. Examples of such compounds are sodium and potassium perborates, percarbonates and perphosphates and potassium monopersulfate. Perborates and in particular sodium perborate monohydrate are preferred.

Hydrogen peroxide and per compounds that release hydrogen peroxide in solutions are good oxidizing agents for removing a wide variety of stains from textiles, in particular wine, tea, coffee, cocoa and fruit stains.

Hydrogen peroxide or its releasing compounds bleach the textiles quickly and effectively at relatively high temperatures of around 80 to 100 ° C. However, these compounds tend to decompose and release oxygen at low temperatures. The release of oxygen is no longer available for the oxidation of the stained textiles and unnecessarily consumes a considerable amount of the compounds which supply hydrogen peroxide. In addition, numerous stains in textiles accelerate the decomposition of hydrogen peroxide to gaseous oxygen during washing at ordinary temperatures.

In general, when washing textiles, be it in a washing machine, by hand or in washing kettles or tubs, the bleaching or detergent mixture, for example containing perborate, is dissolved in cold or lukewarm water, whereupon the solution thus formed is added to the soiled textiles, from which some stains have already been removed by soaking or prewashing, after which the wash liquor is heated or often brought to a boil.

However, it has been found that, by a phenomenon similar to that mentioned above, all or a part of the perborate was decomposed during the heating and especially when the temperature was raised, before the actual and effective washing temperature was reached.

It is believed that this rapid decomposition of hydrogen peroxide, perborate or other hydrogen peroxide-producing compounds takes place with formation of gaseous oxygen at low temperatures due to the extremely powerful catalytic activity of certain enzymes, which are always in the stains of the textiles to be washed and in particular in soiled ones Laundry such as linen are present, these enzymes originating from excretions or of bacterial origin. Particularly active enzymes are hydroperoxydases and in particular catalase, which is known as an extremely effective catalyst for the decomposition of hydrogen peroxide into gaseous oxygen. These enzymes, which are also called "redox enzymes"

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are generally shown to have an increased tendency to initiate the decomposition of peroxide bleaching agents, the decomposition products being ineffective bleaching agents.

In order to take advantage of detergents effective at low temperatures and of washing operations at a lower temperature, as are customary for sensitive textiles, the peroxy compound is preferably used together with an activator for these. Suitable activators which reduce the operating temperature of the peroxide bleach to about 40 ° C. or less are described, for example, in US Pat. Nos. 4,264,466 and 4,430,244, to which express reference is made. Preferred activators are polyacylated compounds such as tetraacetylethylene diamine (TAED) and pentaacetylene glucose. Other suitable activators are, for example, acetylsalicylic acid and its salts, ethylidene benzoate acetate (EBA) and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacelyl glycouril (TAGU) and derivatives thereof. Other activators are described, for example, in U.S. Patent Nos. 4,111,826,4,422,950 and 3,661,789.

The bleach activator usually reacts with the peroxy compound and forms a bleaching peroxy acid in the wash liquor. A sequestering agent with a high level of complexity is preferably used in order to inhibit an undesired reaction between the peroxyacid and the hydrogen peroxide in the wash liquor in the presence of metal ions. Preferred sequestering agents are able to form complexes with Cu2 + ions, so that the stability constant (pK) of the complexation is equal to or greater than 6 at 25 ° C. in water with an ion concentration of 0.1 mol / 1, pK usually is defined as the negative logarithm of K and K is the equilibrium constant. For example, the pK values for complexing copper ions with NTA and EDTA under the specified conditions are 12.7 and 18.8, respectively. Suitable sequestering agents include nor diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and ethylenediaminetetramethylenephosphonic acid (EDITEMPA).

However, even in the presence of bleach activators and even at low temperatures to almost room temperatures, decomposition of the persalt takes place in the presence of the soiled textiles, since the reaction rate between the bleaching agent and the activator is lower than the rate of decomposition of hydrogen peroxide by catalase.

In order to prevent loss of bleaching agent due to the decomposition caused by enzymes, the detergents according to the invention also contain an effective amount of a compound which is able to inhibit this decomposition caused by enzymes. Suitable inhibitors of this type are described in US Pat. No. 3,606,990, to which express reference is hereby made.

Particularly suitable inhibitors are hydroxylamine sulfate and other water-soluble hydroxylamine salts including, for example, the hydrochloride or hydrobromide. It has been found that hydroxylamine salt and in particular the sulfate inhibit the adverse influence of catalase when they are present even in such small amounts, for example below 0.5% by weight, such as 0.01 to 0.4 and preferably 0.04 to 0, 2% by weight, in particular in amounts of 0.1% by weight, based on the total detergent, are present.

In addition, the hydroxylamine inhibitors in the detergent composition are extremely stable; they show a loss of less than 20% after two months of aging at 43 ° C. The hydroxylamine salts can be solubilized very quickly in water and can therefore react with the catalase before the perborate or other peroxide bleaching agent is dissolved. Another advantage of the hydroxylamine salts is that they are quickly destroyed in the wash liquor and consequently no nitrosamine derivatives can be found.

If the bleach system is activated by a bleach activator such as e.g. TAED is activated, the activator works better, and consequently suitable proportions of persalt bleach and bleach activator can be maintained in areas that are much closer to the stoichiometric equivalent weight or proportions in which there is only a small molar excess of bleach.

The detergents according to the invention can additionally contain inorganic insoluble thickeners or dispersants with a large surface area, such as finely divided silica with an extremely small particle size of, for example, 5 to 100 [in as "Aerosil" or other highly voluminous inorganic carriers, as described in US Pat. No. 3,630,929 are disclosed; these additives are present in amounts of 0.1 to 10 and for example 1 to 5% by weight. However, the detergents according to the invention which form peroxyacids in the wash liquor should preferably

that is, detergents containing peroxy compounds and an activator contain essentially no such compounds and other silicates, since silicic acid and silicates trigger an undesired decomposition of the peroxy acid.

In a preferred embodiment of the detergent according to the invention, the mixture of liquid nonionic surfactant and solid constituents is comminuted in a rolling mill, the particle size of the solid constituents being reduced to less than 10 μm, for example to an average particle size of 2 to 10 (in or lower of, for example, 1 Jim Detergents whose dispersive particles have such a small coffi size show improved stability against separation or settling on storage.

When comminuting, the proportion of solid components should preferably be as high, e.g. at least 40 or about 50% by weight that the solid particles are in contact with one another and are not shielded from one another by the liquid nonionic surfactant. Ball mills or crushing plants with corresponding movable grinding elements are suitable for this. For example, a grinder to be fed in batches with balls of 8 mm diameter made of steatite can be used. In the case of continuous comminution, appropriate friction mechanisms can be used, in which grinding balls with a diameter of 1 to 1.5 mm are effective in a very narrow gap between a stator and a high-speed rotor. When using such grinders, it is expedient to first add a mixture of nonionic surfactant and the solids to a comminution device which does not produce such fineness during grinding, e.g. a colloid mill to reduce the particle size to less than 100 µm and, for example, to about 40 µm before further grinding to an average particle size below about 10 µm in a continuous ball mill.

In a preferred liquid heavy-duty detergent according to the invention, the individual constituents, based on the total composition, are as follows:

The suspended builders are used in a range from about 10 to 60, for example 20 to 50% by weight, and for example in a range from 25 to 40% by weight.

The liquid phase containing the nonionic surfactant and the dissolved amphiphilic, viscosity controlling and gelation preventing compound can be used in an amount of about 30 to 70% by weight, for example in an amount of 40 to 60% by weight will.

This phase can also contain minor proportions of diluent such as a glycol, e.g. Contain polyethylene glycol (PEG 400) or hexylene glycol up to 10 wt .-% and preferably up to 5 wt .-%, for example in amounts of 0.5 to 2 wt .-%. The weight ratio of nonionic surfactant to amphiphilic compound is preferably in a range

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from about 100: 1 to 1: 1 and in particular from about 50: 1 to 2: 1 and especially at 25: 1 to 3: 1.

The gel formation-preventing polyether carboxylic acid compound can be present in an amount such that it provides 0.5 to 10 and, for example, 1 to 6 or 2 to 5 parts of COOH (molecular weight 45) per 100 parts of the mixture of the acid compound and the nonionic surfactant . In general, the amount of the polyether carboxylic acid compound is in a range of 0.01 to 1 part per part of the nonionic surfactant and, for example, 0.05 to 0.6 part and, for example, 0.2 to 0.5 part.

The acidic organic phosphorus compound to prevent settling is usually used in an amount up to 5% by weight, for example in a range from 0.01 to 5% by weight such as from 0.05 to 2% by weight and used, for example, from 0.1 to 1% by weight.

With regard to the other additives that may be used, the enzymes can be used in amounts of 0 to 2 and in particular 0.7 to 1.3% by weight, the corrosion inhibitors in amounts of approximately 0 to 40 and preferably 5 to 30% by weight Foam depressants and foam suppressants in amounts of 0 to 15 and preferably 0 to 5% by weight, for example 0.1 to 3% by weight, the thickeners and dispersants in amounts of 0 to 15, for example 0.1 to 10 and preferably 1 to 5% by weight, the dirt suspending agents or anti-redeposition agents and anti-yellowing agents in amounts of 0 to 10 and preferably 0.5 to 5% by weight, colorants, perfumes, optical brighteners and blue agents in a total amount of 0 to about 2 and preferably 0 to about 1% by weight, agents for modifying the pH and buffer substances in amounts of 0 to 5 and preferably 0 to 2% by weight, bleaching agents in amounts of 0 to about 40, and preferably 0 to about 25 G. % by weight, for example with 2 to 20% by weight, inhibitors for suppressing decomposition of the bleaching agent caused by enzymes in amounts of up to 0.5 and preferably from 0.01 to 0.4 or 0.5% by weight and in particular with 0.04 to 0.2% by weight, bleach stabilizers and bleach activators in amounts of 0 to about 15 and preferably 0 to 10% by weight, for example 0.1 to 8% by weight, sequestering agents with high Complexing power in amounts up to 5 and preferably from 0.25 to 3 wt .-% such as 0.5 to 2 wt .-% can be used.

In order to show the effect of the viscosity-controlling and gel-preventing substances, various detergents were made with the product "Surfactant T8" (C13, E08) described above, namely a mixture of products T7 and T9 in a ratio of 1: 1 from non-aqueous liquid non-ionic Surfactant used. Detergents with an amphiphilic compound content of 5,10,15 or 20% were tested at 5.10 15.20 and 25 ° C at various degrees of dilution with water, i.e. 100, 83.67, 50 and 33% total non-ionic « Surfactant T8 »plus additive concentrations, ie after dilution in water. The additives tested were «Alfonic 610-60» (C-8; EO-4,4), ethylene glycol monoethyl ether (C-2; EO-1) and diethylene glycol monobutyl ether (C-4; EO-2).

With «Alfonic 610-60», an addition of 5% is sufficient to prevent gelation at 25 ° C. However, when the viscosity was plotted against the concentration of nonionic product, there was a sharp viscosity maximum at a concentration of about 67%, and a shoulder area with 55 to 35% nonionic component was also observed. At 5 ° C it was necessary to add 15% additive to prevent gel formation. The viscosity drops to a minimum at a concentration of nonionic constituent of about 83%, namely in all areas of additive addition at 5 ° C., while at higher temperatures in the non-diluted compositions, i.e. viscosity minima were observed for 100% non-ionic constituents. At any temperature and at any concentration of additive tested, with the exception of

20% additive at 25 ° C showed a relatively sharp peak in viscosity at concentrations between 75 to 50% of non-ionic component, i.e. at 25 to 50% dilution.

s With an ethylene glycol monoethyl ether, 5% additive was sufficient to prevent gel formation even at 5 ° C. However, sharp peaks and / or viscosity maxima were again observed at any temperature and any additive concentration, although the effects were not as clear as with «Alfonic io 610-60»; for some applications, the maximum viscosities are particularly suitable for commercially available products at higher additive concentrations and / or higher temperatures.

On the other hand, no sharp viscosity peaks were observed with diethylene glycol monobutyl ether at all temperatures up to 5 ° C. in a range of 20% additive. Even at low additive concentrations, the viscosity peaks and the viscosity values for substantially all dilutions or concentrations of nonionic components were lower than for the C-8; EO-4,4 or C-2; EO-1 additive.

20 The following table is typical of the results obtained with different additive concentrations, dilutions and temperatures, but refers to 20% additive at a temperature of 5 ° C.

Compositions

Viscosity at 5 ° C

Pour point

in Pa-s

in ° C

without

50%

water

water

Surfactant T8 alone

1,140

1,240

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0.086

0.401

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0.195

0.218

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0.690

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35

The additives A, B and C mentioned in the table are ethylene glycol monoethyl ether and diethylene glycol monobutyl ether and «Alfonic 610-60» with C-8; EO-4.4.

example 1

A non-aqueous liquid heavy-duty detergent based on nonionic surfactants with the following composition was produced:

Component weight%

11 669 604

The detergent according to Example 1 is a stable, free-flowing, non-gelling and builder-containing liquid mixture based on a nonionic surfactant, the polyphosphate builder being stably suspended in the liquid phase of the nonionic surfactant 5.

Surfactant T7

17.0

Surfactant T8

17.0

Dobanol 91 S acid 1

5.0

Diethylene glycol monobutyl ether

10.0

Dequest 20662

1.0

Sodium tripolyphosphate

29.0925

Calcium sequestrant3

4.0

Sodium perborate monohydrate

9.0

Tetraacetylethylenediamine

4.5

Emphiphos 56324

0.3

Optical brightener of the stilbene type

0.5

Proteolytic enzyme Esperase

1.0

Means for preventing dirt build-up5

1.0

Perfume 787 («Duet 787»)

0.6

dye

0.0075

Example 2

io It was analogous to the example! made a non-aqueous liquid detergent containing an enzyme inhibitor.

1 A C9-Cn fatty alcohol ethoxylated with 5 mol EO, half of which was esterified with succinic anhydride.

2 sodium salt, the diethylenetriaminepentamethylenephosphoric acid.

3 A copolymer of approximately equal moles of methacrylic acid and maleic anhydride in completely neutralized form as sodium salts.

4 partial esters of phosphoric acid with a cic-cis alkanol and a content of Vi monoester and% diester.

5 Mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

component

30th

Wt% y

Plurafac RA 30 37.5

Diethylene glycol monobutyl ether 10.0

Octenyl succinic anhydride 2.0

Tripolyphosphate 28.4

Calcium sequestrant (Sokolan) 4.0

Dequest2066 1.0

Sodium perborate monohydrate 9.0

Tetraacetylethylenetetraacethylethylenediamine 4.5

Hydroxylamine sulfate 0.1

Emphiphos 5632 0.3

Optical brightener 0.2

Esperase 1.0

Perfume 0.6

Relatin DM 4050 1.0

T1O2 0.4

This detergent had the same advantageous properties as that according to Example 1 and moreover showed an even better bleaching effect.

Claims (9)

669 604 2nd PATENT CLAIMS 1. Liquid textile washing and bleaching agent, characterized by a content of a liquid nonionic surfactant, a water-soluble inorganic peroxide salt as bleaching agent and an effective amount of an inhibitor against the decomposition of the peroxide salts caused by enzymes. 2. Textile washing and bleaching agent according to claim 1, characterized in that the peroxide salts are perborate, percarbonate, persphosphate and / or persulfate and the inhibitor is a hydroxylamine salt. 3. Textile washing and bleaching agent according to claim 2, characterized in that the hydroxylamine salt is a hydroxylamine sulfate, hydrochloride and / or hydrobromide. 4. Textile washing and bleaching agent according to claim 1, characterized in that it contains an activator for the bleaching agent, which forms a peroxy acid with these in the aqueous washing liquor at a temperature of 40 ° C or less. 5. Textile washing and bleaching agent according to claim 4, characterized in that the bleach activator of N, N, N ', N'-tetraacethylethylenediamine. 6. Textile washing and bleaching agent according to claim 1, characterized in that it is essentially anhydrous. 7. Textile washing and bleaching agent according to claim 1, in particular for use at temperatures of 40 ° C or lower, characterized in that it is a liquid nonionic surfactant, a mono- or poly (Cz-C3) alkylene glycol iono (Ci-Cs) alkyl- ether, a water-soluble inorganic peroxide salt as a bleaching agent, a bleach activator for lowering the temperature at which the bleaching agent releases a peroxyacid in aqueous solution, and, based on the total composition, 0.01 to 0.4% by weight of hydroxylamine salt as an inhibitor for the contains decomposition of the bleaching agent caused by enzymes contained in the soiled textiles. 8. Textile washing and bleaching agent according to claim 7, characterized in that the bleaching agent sodium perborate monohydrate, the activator N, N, N ', N'-tetraacetylethylene diamine and the hydroxylamine salt is a hydroxylamine sulfate or hydroxylamine hydrochloride in an amount of 0.02 to Is 0.2% by weight. 9. Liquid textile washing and bleaching agent according to claim 7, characterized in that it also contains a builder salt in the liquid nonionic surfactant.