CH674358A5 - - Google Patents

Description

DESCRIPTION

The invention relates to non-aqueous liquid textile treatment agents. In particular, the invention relates to non-aqueous liquid laundry cleaning compositions which contain a suspension of builder salt in nonionic surfactants which are resistant to phase separation and gelling and are easy to pour. These compositions can be used to clean soiled fabrics. Above all, the invention relates to detergents with highly biodegradable nonionic surfactants.

Liquid non-aqueous heavy-duty detergents for cleaning laundry are well known. For example, compositions of this type may contain a liquid nonionic surfactant in which particles of a builder are dispersed, e.g. in U.S. Patents 4,316,812, 3,630,929 and 4,264,466, and in UK Patents 1,205,711,1 270,040 and 1,600,981.

Applicant's relevant applications are: US-SN SN 687 815, 597 793, 597 948, 767 570 and 762 163. These applications are concerned with liquid non-aqueous nonionic detergent compositions. The detergency of the synthetic nonionic surfactants in laundry detergents can be increased by adding builders.

Liquid detergents are often more pleasant to use than dry, powdered or particulate products, which is why they have become much more popular with consumers

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to have. They are easy to measure, dissolve quickly in water, can easily be applied in concentrated solutions or dispersions to soiled parts on collars to be washed and do not dust, and in general they take up less storage space. In addition, materials can be incorporated into the liquid detergent formulations which could not survive dry processes without decomposition, but which are often desirable in the manufacture of particulate detergent products. Although they have numerous advantages over unitary or particulate solid products, liquid detergents also often have certain disadvantages that must be overcome if you want to make detergents that are accepted commercially. These products have a low degree of biodegradability, separate or settle when stored, have a high pour point temperature and foam excessively when used, while others separate when cooled and are no longer easily redispersed. In some cases the product viscosity changes and the product either becomes too thick to cast or so thin that it appears watery. Some clear products become cloudy, others gel when standing.

The commonly produced and commercially available nonionic detergent surfactants generally contain only polyethoxy groups, although some of the commonly used nonionic surfactants have both polyethoxy and polypropoxy groups. However, the propoxy groups are usually only present in smaller amounts. The ethoxy and propoxy groups are generally statistically distributed in the ethoxypropoxy chain linked to the fatty alcohol, the ethoxy group generally being linked to the alkyl group of the fatty alcohol.

The biodegradability of the commonly used nonionic surfactants largely varies depending on the presence of the propoxy group and the position or localization thereof and the localization and distribution of the propoxy and ethoxy group components of the chain in the polyalkoxy chain.

It has now been found, for example, that a low surfactant of the formula

R- (OC2H4) y (OC3H6) xOH,

that is, one in which the polyethoxy group is linked to the alkyl group of the fatty alcohol and the polypropoxy group is linked to the hydroxy group, is only at most (only a out) 20% or less biodegradable.

On the other hand, it has surprisingly been found that a nonionic surfactant of the formula

R- (OC3H6) x (OC2H4) yOH,

that is, when the polypropoxy group is linked to the alkyl group of the fatty alcohol and the polyethoxy group is linked to the hydroxy group, the biodegradability of the surfactant is at least 60% and usually at least 80%. Some special nonionic surfactants of the invention have shown 90 to 100% biodegradability.

The biodegradability of the nonionic surfactants of the invention is tested using the OECD test method.

In addition to the problems of poor biodegradability, settling or phase separation, the non-aqueous liquid laundry detergents based on nonionic surfactants have the disadvantage that the nonionic surfactants tend to gel if they are added to cold water. This is a particularly serious problem in the usual application in European household washing machines, in which the consumer puts the detergent into a dispenser compartment (e.g. a distributor drawer) of the machine. When the machine is operating, the detergent in the compartment is exposed to a stream of cold water to be rinsed into the main wash solution. Especially during the winter months, when the detergent added to the distributor and the water are particularly cold, the viscosity of the detergent increases noticeably and a gel forms. The consequence of this is that some of the detergent is not completely rinsed out of the distribution compartment when the machine is in operation and a detergent deposit builds up with repeated wash cycles, which may make it necessary to rinse it with hot water. 15 The gelling phenomenon can also be a problem whenever you want to wash with cold water, which is recommended for certain synthetic and sensitive fabrics or for those that can shrink in warm or hot water.

20 The tendency of the concentrated detergent compositions to gel during storage is reinforced by storing them in unheated storage rooms or shipping them in unheated transport rooms in the winter months.

25 partial solutions to the gel problem in aqueous, essentially builder-free compositions have already been proposed, for example by diluting the liquid nonionic surfactant with certain viscosity-controlling and gelling-preventing solvents, for example with lower alkanols, such as ethyl alcohol (US Pat. No. 3,953,380), Alkali formates and adipates (US Pat. No. 4,368,147), hexylene glycol, polyethylene glycol etc. as well as by modification and optimization of the nonionic structure. Acidification of the part of the nonionic molecule bearing the terminal hydroxyl group is mentioned as a particularly successful example of the modification of the nonionic surfactants. The benefits of introducing a carboxylic acid at the end of the nonionic surfactant include preventing gelation upon dilution, lowering the pour point of the nonionic surfactant, and forming an anionic surfactant upon neutralization in the wash medium. The optimization of the non-ionic structure has focused on the chain length of the hydrophobic-lipophilic part as well as on the connection (makeup) of the alkylene oxide (e.g. ethylene oxide) units of the hydro-45 phile part. For example, it was found

that a Ci3 fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to gel.

Nevertheless, there is a need for improvements in biodegradability, stability, and gelling prevention in the non-aqueous liquid fabric treating agents.

According to the invention, a concentrated, highly biodegradable, non-aqueous liquid detergent composition is thus provided by using a propoxylated fatty alcohol ethoxylate as the main surfactant, in which the propylene oxide groups are adjacent to the alkyl group and the ethylene oxide groups are adjacent to the hydroxy group.

Surprisingly, it was found that when the 60 propylene oxide groups are adjacent to the alkyl group R and the ethylene oxide groups are at the end of the molecule next to the OH group, the nonionic surfactant is highly biodegradable, i.e. that more than 80% are biodegradable. On the other hand, it has been found that when the 65 ethylene oxide groups are adjacent to the alkyl group R and the propylene oxide groups at the end of the molecule are next to the OH group, the nonionic surfactant has a low degree of biodegradability, i.e. less than 20%

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is biodegradable. The invention is characterized by the features in the independent claims.

The highly biodegradable nonionic surfactants of the invention, namely the propoxylated ethoxylated fatty alcohols, have the general formula

R- (OC3H6) x (OC2H4) yOH,

wherein R represents a Cg to C26 alkyl, preferably C9 to C] g alkyl, x + y = 20 to 100%, preferably 40 to 80% of the number of carbon atoms in the alkyl, x at least 1, preferably is at least 2 and y is at least 1, preferably at least 2.

The nonionic propoxylate ethoxylate fatty alcohol surfactants of the invention are at least 60%, preferably at least 80% biodegradable. The nonionic propoxylated ethoxylated fatty alcohol surfactants of the invention can be used as the only detergent surfactants or in mixtures with commonly available nonionic surfactants. It is preferred that the nonionic propoxylated ethoxylated fatty alcohol surfactant makes up at least 50%, particularly preferably at least 70%, of the nonionic surfactants used in the detergent composition.

To improve the viscosity properties of the composition, a nonionic surfactant with a terminal acid group can be added. To further improve the viscosity properties and the storage properties of the composition, viscosity-improving and gelling-preventing compounds such as alkylene glycol monoalkyl ether and sedimentation-preventing compounds such as phosphoric acid ester and aluminum stearate can be added. According to a preferred embodiment of the invention, the detergent composition contains a nonionic surfactant with a terminal acid group and / or an alkylene glycol monoalkyl ether, and a sediment-preventing substance.

Sterilizing or bleaching substances and activators therefor can be added to improve the bleaching and cleaning properties of the composition.

According to one embodiment of the invention, the builder constituents of the composition are ground to a particle size below 100 micrometers, preferably below 10 micrometers, in order to improve the stability of the suspension of the builder constituents in the liquid surfactant or detergent.

In addition, other constituents can be added to the composition, such as incrustation-preventing substances, foam-preventing substances, optical brighteners, enzymes, re-precipitation-preventing substances, perfume and dyes.

The household washing machines currently manufactured generally operate at washing temperatures up to 100 ° C. Up to 70 liters of water are used during the wash and rinse cycles.

Normally about 175 g powder detergent is used per wash.

According to the invention, a liquid heavy-duty detergent for textiles is made available which contains a highly biodegradable nonionic surfactant which consists of a propoxylated ethoxylated fatty alkyl alcohol in which the propylene oxide groups with the alkyl, the ethylene oxide groups at one end with the terminal propylene oxide group and at the other End connected to the hydroxy group.

According to one aspect of the invention, therefore, a liquid heavy-duty or heavy-duty detergent for laundry is created which has a suspension of a builder salt in the liquid nonionic surfactant.

In another aspect, the invention provides a heavy duty liquid detergent composition in which the nonionic surfactant is highly biodegradable, the composition being stable, not settling on storage, and not gelling on storage and consumption. 10 The liquid compositions of the invention are easy to pour, easy to measure and easy to put in the washing machine.

In another aspect, the invention provides a method of dispensing a highly biodegradable liquid nonionic laundry detergent composition into cold and / or cold water without gel formation. In particular, a method is provided for filling a container with a liquid, non-aqueous laundry detergent, the detergent, 20 at least predominantly, consisting of a highly biodegradable liquid nonionic surfactant of the invention, and for distributing the composition from the container into an aqueous washing medium, the distribution being done by directing a stream of unheated water onto the composition such that it is carried into the wash bath by the water stream.

The heavy duty liquid laundry detergents of the invention advantageously have a significantly improved biodegradability, since they form a major component of the compositions, a propoxylated ethoxylated fatty alcohol. contain hol in which the propylene oxide groups are connected to the alkyl and the ethylene oxide groups to the hydroxy group.

The compositions of the invention have the advantages of being low in pouring temperature, non-gelling upon contact with water, non-foaming and having good cleaning power.

The nonionic propoxylated ethoxylated fatty alcohol surfactants of the invention have a high degree of biodegradability, i.e. they are more than 80% biodegradable, foam little when used, have a low pour point, e.g. of -20 ° C, and do not gel on contact with water at 5 ° C. The nonionic surfactants of the invention also have good cleaning power. 45 The concentrated, non-aqueous, liquid nonionic surfactant-containing detergent compositions of the invention have the further advantages that they are stable, do not settle when stored and do not gel. The liquid compositions are easy to pour, 50 easy to measure and easy to put into the washing machine.

It is an object of the invention to provide a highly biodegradable nonionic propoxylated ethoxylated fatty alcohol surfactant in which the propylene oxide 55 groups are attached to the alkyl group and the ethylene oxide group is attached to the hydroxy group.

It is another object of the invention to provide liquid fabric treating agents which are suspensions of builder salt in the propoxylated ethoxylated fatty alcohol surfactant which are stable, readily pourable and dispersible in cold, warm or hot water when stored.

Another object of the invention is to propose buil-containing non-aqueous liquid heavy-duty textile detergents containing 65 nonionic surfactants which contain the nonionic propoxylated ethoxylated fatty alcohol surfactants as the main nonionic surfactant, are pourable at all temperatures and are repeated by the distributor

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It is easy to dispense European washing machines without them becoming dirty or clogged, not even during the winter months.

Another object of the invention is to provide low-foaming, non-gelling, stable, non-aqueous, builder-containing liquid heavy duty nonionic detergent compositions containing as the main surfactant the propoxylated ethoxylated fatty alcohol surfactants of the invention.

Another object of the invention is to provide non-gelling, stable suspensions of builder-containing, non-aqueous, liquid nonionic surfactant heavy duty detergent compositions containing a sufficient amount of phosphoric acid alkanol ester and / or aluminum fatty acid salt as a sedimentation preventing agent to increase the stability of the composition, e.g. to prevent settling of the builder particles, etc., preferably reducing, at least not increasing, the plastic viscosity of the composition.

These and other objects arising from the description of preferred forms of formation are achieved by preparing a detergent composition by adding an effective amount of builder salt and inorganic or organic additives for textile treatment to the non-aqueous liquid nonionic surfactant of the invention, such as, for example, viscosity-improving and gel-preventing substances, sediment-preventing substances, Crust-preventing substances, bleaching agents, bleach activators, foam-preventing substances, optical brighteners, enzymes, substances that prevent reprecipitation, perfume and dyes.

The highly biodegradable nonionic surfactants of the invention, the propoxylated ethoxylated fatty alkyl alcohols, have the general formula

R- (OC3H6) x (OC2H4) yOH

wherein R represents C8 to C26 alkyl, preferably C9 to C! 8 alkyl and particularly preferably C9 to C! r and Q2 to Q5 alkyl. The value of the integers x + y is equal to 20 to 100, preferably 40 to 80 and particularly preferably 45 to 60% of the number of carbon atoms of the R-alkyl. The value of x is at least 1, preferably at least 2 and particularly preferably x is 3 or more. The value of y is at least 1.

The nonionic propoxylated ethoxylated fatty alcohol surfactants of the invention are at least 60%, preferably at least 80% and particularly preferably at least 90% biodegradable.

The biodegradable nonionic surfactants of the invention are prepared by (1) condensing an aliphatic fatty alcohol with propylene oxide or polypropylene glycol and (2) then further reacting the first condensation product obtained with ethylene oxide or polyethylene glycol.

The fatty alkyl alcohol reacts with the propylene oxide or polypropylene glycol to link a linear low molecular weight propylene oxide polymer chain, e.g. x is 2 to 15, preferably 2 to 8 and particularly preferably 3 to 6. The propylene oxide chain is usually attached to the alkyl group at a primary or secondary carbon atom of the fatty alcohol. The condensation product of fatty alcohol and propylene oxide is then reacted with ethylene oxide or polyethylene glycol to add the desired number of ethylene oxide groups. The ethylene oxide groups normally combine with the terminal propylene oxide group and are formed to form an ethylene oxide polymer.

low molecular weight chain, e.g. y 2 to 15, preferably 2 to 8 and particularly preferably 3 to 6 is fused on, at the end of which is the hydroxyl group.

By performing separate condensation reactions with propylene oxide and ethylene oxide, a linear low molecular weight propylene oxide polymer binds to a primary or secondary carbon atom of the fatty alcohol and a linear low molecular weight ethylene oxide polymer binds to the terminal propylene oxide molecule. The end of the ethylene oxide polymer chain carries a hydroxy group.

The highly biodegradable nonionic surfactants of the invention are ethoxylated polypropoxylate lipophiles in which the hydrophilic-lipophilic balance is established by adding the hydrophilic polypropoxypolyethoxy groups to the lipophilic aliphatic residue.

A preferred class of nonionic surfactants are the C9 to Qg fatty alkyl alcohols containing 4 to 16 propylene oxide and ethylene oxide groups, i.e. x + y = 4 to 20 16. Other classes of nonionic surfactants are the fatty C9 to Cu alkyl alcohols, in which x + y = 5 to 10, and the fatty C12 to C15 alkyl alcohols, in which x + y = 5 to 15.

The higher molecular weight Ci9 to C26 fatty alcohol propylene oxide-ethylene oxide condensation products show a high degree of biodegradability, but have a tendency to form gels more easily in the detergent concentrate and in some cases can be solid at room temperature. Although the C] 9 to C26 surfactants contribute to the gelation of the liquid detergent, they can be added to the detergent composition if necessary in small amounts, especially when weakly gel-forming concentrates are not required.

In the preferred higher alkanols polyalkoxylated with lower alkoxy (poly (lower) alkoxylated higher alkanols), the number of lower alkoxy groups, i. the sum of x + y, 20 to 100% of the number of carbon atoms in the higher alkanol, preferably 40 to 80% and particularly preferably 45 to 40 60% of the same. The nonionic surfactant component of the composition preferably contains at least 50%, more preferably at least 70%, of the highly biodegradable nonionic surfactant of the invention.

Suitable highly biodegradable propoxylated ethoxylated fatty alkyl alcohols of the invention include the following:

R- (OC3H6) x (OC2H4) yOH

50

R

X

y

1.

Cj2-to C15

3rd

5

2nd

C12-to C] 5

5

4th

3rd

C9 to C]]

3rd

5

4th

C9 to C]]

2nd

4th

55 5.

C9 to C18

3rd

6

6.

C9 to C18

2nd

4th

In both the preferred C9 to C! 8 and the less preferred C19 to C26 nonionic surfactants, the alkyl groups present therein are generally linear, although a small amount of branching is tolerable, for example on a carbon atom that terminates Carbon is adjacent to the straight chain or two carbon atoms are then removed and "away" from the 65 propoxy chain, provided that such a branched alkyl is no longer than 3 carbon atoms long. Usually the proportion of carbon atoms in such a branched configuration is low, e.g. less than 20% of the ge

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entire carbon atom content of the alkyl. Similarly, although linear alkyls that are terminally attached to the propoxy chains are highly preferred and are believed to have the best combination of detergency, biodegradability, and non-gelling behavior, medium or secondary binding of the alkoxy- , ie Propoxy chains to which alkyl occurs. Such branched alkyl is normally only present in a small amount of these alkyls and makes e.g. generally less than 20%, preferably less than 10% thereof.

The propoxylated ethoxylated fatty alcohol surfactants of the invention can be used as the sole nonionic surfactant or in mixtures with nonionic surfactants commonly available on the market for detergents. The nonionic propoxylated ethoxylated fatty alcohol surfactants of the invention can make up 40 to 100%, preferably 50 to 100 and particularly preferably 70 to 100% of the nonionic surfactant component of the detergent composition.

Numerous such compounds are well known as common nonionic synthetic organic surfactants that can be used with the highly biodegradable propoxylated ethoxylated fatty alcohol surfactants of the invention. Typical suitable nonionic surfactants are described in U.S. Patents 4,316,812 and 3,630,929.

Usually the nonionic surfactants are poly (low) alkoxylated lipophiles, the desired hydrophilic-lipophilic balance being obtained by adding a hydrophilic poly (low) alkoxy group to a lipophilic part. A preferred class of applied nonionic surfactants are higher alkanols polyalkoxylated with lower alkoxy, wherein the alkanol comprises 9 to 18 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) is 3 to 12. Of these materials, preferred are those in which the higher alkanol is a higher fatty alcohol having 9 to 11 or 12 to 15 carbon atoms and has 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably the lower alkoxy is ethoxy, but may in some cases be desirably mixed with propoxy.

Exemplary of such examples are those with 12 to 15 carbon atoms in the alkanol and with about 7 ethylene oxide groups per mole, such as Neodol 25-7 and Neodol 23-6.5 from Shell Chemical Company Inc .. The former is a condensation product of a mixture of higher fatty alcohols of an average of about 12 to 15 carbon atoms with about 7 moles of ethylene oxide, the latter being a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present on average is about 6.5. The higher alcohols are primary alkanols.

Other examples of such surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates from Union Carbide Corp. The former is a mixed ethoxylation product of a linear secondary alkanol having 11 to 15 carbon atoms. 7 moles of ethylene oxide, the latter a similar product, but with 9 moles of ethylene oxide.

Also useful in the composition according to the invention as a nonionic surfactant component are nonionic surfactants with a higher molecular weight than Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, in which the higher fatty alcohol has 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is about 11. These products are also manufactured by Shell Chemical Company.

15

Other useful nonionic surfactants are represented by the well known Plurafacs. The Plurafacs are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides containing a mixed chain of ethylene oxide and propylene oxide, with a hydroxyl group being the terminal group. Examples of this are product A (a C13 to Ci5 fatty alcohol, condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), product B (a C13 to C15 fatty alcohol, condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), Product C (a C! 3 to C] 5 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide), Plurafac B26, and Product D (a mixture of equal parts of Product C and Product B).

Another group of liquid nonionic surfactants is available from Shell Chemical Company under the name Dobanol: Dobanol 91-5 is an oxylated (with an average of 5 moles of ethylene oxide) C9 to Cir fatty alcohol, Dobanol 25-7 is an ethoxylated (with an average of 7 moles of ethylene oxide 20 each Moles of fatty alcohol) C12 to C15 fatty alcohol.

If larger amounts of the non-terminally alkoxylated alkanols, propylene oxide-containing poly (lower) alkoxylated alkanols and less hydrophilic-lipophilic balanced nonionic surfactants than indicated above and other 25 nonionic surfactants are used instead of those mentioned as preferred here, the product obtained may be less good Washing power, stability, viscosity and non-gelling behavior are shown as the preferred compositions, but the use of the viscosity and gel regulating compounds of the invention can also improve the properties of detergents based on such nonionic surfactants. In some cases, for example, when using a higher molecular weight poly (lower) alkoxylated higher alkanol, which is often the case because of its detergency, the amount thereof is regulated or limited after routine experimentation to achieve the desired detergency and yet obtain a non-gelling product of desired viscosity.

It has also been found that it is hardly necessary to use the non-40 ionic surfactants with a higher molecular weight because of their washing properties, since the preferred nonionic surfactants described here are excellent detergents and moreover enable the desired viscosity in the liquid detergent without gelation at low temperatures 45 .

Another useful group of nonionic surfactants are the nonionic surfactants available as Surfactant T from British Petroleum. The nonionic surfactant T surfactants are obtained by ethoxylation of secondary C] 3 fatty alcohols 50 with a narrow ethylene oxide distribution. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 on average 7 moles of ethylene oxide Surfactant T9 on average 9 moles of ethylene oxide and Surfactant T12 on average 12 moles of ethylene oxide per mole of secondary 55 C13 fatty alcohol.

Preferred common nonionic surfactants in the compositions of the invention include the secondary Cj3 to C15 fatty alcohols with relatively narrow ethylene oxide - held in the range 7 to 9 moles, and the C9 to Cn ethoxylated with about 60 5 to 6 moles of ethylene oxide Fatty alcohols.

Mixtures of two or more of the conventional liquid nonionic surfactants with the highly biodegradable propoxylated ethoxylated fatty alcohol surfactants of the invention can be used, which is advantageous in some cases.

By incorporating an effective amount of a liquid nonionic surfactant with a terminal acid group,

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The viscosity and gel properties of liquid detergents can be improved. The nonionic surfactants with a terminal acid group are modified nonionic surfactants in which a free hydroxyl group has been converted to a radical with a free carboxyl group, for example an ester or partial ester of a nonionic surfactant with a carboxylic acid or an anhydride.

As indicated in US-SN 597 948, the knowledge of which is assumed here, the nonionic surfactants modified to form a free carboxyl group, which can be roughly characterized as polyether carboxylic acids, bring about a lowering of the temperature at which the liquid nonionic surfactant forms a gel with water.

The addition of the nonionic surfactants with a terminal acid group to the liquid nonionic surfactant supports the dispensability or distributability of the composition, i.e. the pourability, and lowers the temperature at which the liquid nonionic surfactants form a gel in water without reducing their stability against settling. The non-ionic surfactant with a terminal acid group reacts in the washing machine water with the alkaline part (alkalinity) of the dispersed builder salt phase of the detergent composition and acts effectively as an anionic surfactant.

Specific examples include the half esters of product A with succinic anhydride, the ester or half esters of Dobanol 25-7 succinic anhydride, and the esters or half esters of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, e.g. Maleic acid, maleic anhydride, citric acid and the like.

The nonionic surfactants with a terminal acid group can be prepared as follows:

Product A with terminal acid group: 400 g of the non-ionic surfactant Product A, a CI3 to C | 5 alkanol alkoxylated with 6 units of ethylene oxide and 3 units of propylene oxide per alkanol unit, are mixed with 32 g of succinic anhydride and heated at 100 ° C for 7 hours. The mixture is cooled and filtered to remove unreacted succinic material. The result of the infrared analysis shows that about half of the nonionic surfactant is converted into the acid half ester of the same.

Dobanol 25-7 with terminal acid group: 522 g Dobanol 25-7, an ethoxylation product of a Ci2 to Ci5-A1-kanol with about 7 ethylene oxide units per mole of alkanol, are mixed with 100 g of succinic anhydride and 0.1 g of pyridine (as an esterification catalyst) and heated to 260 ° C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis shows that essentially all free hydroxyl groups of the surfactant are converted.

Dobanol 91-5 with terminal acid group: 1000 g nonionic surfactant, namely the ethoxylation product of a C9 to Cn alkanol with about 5 ethylene oxide units per molecule of alkanol (Dobanol 91-5) are mixed with 265 g succinic anhydride and 0.1 g pyridine as a catalyst and heated to 260 ° C for 2 hours, cooled and filtered to remove unreacted succinic acid material. Infrared analysis shows that essentially all free hydroxyls of the surfactant have been converted.

Instead of or in a mixture with the pyridine, other esterification catalysts such as alkali alkoxide (e.g. sodium methoxide) can be used.

The acidic polyether compound, i.e. the nonionic surfactant with a terminal acid group is preferably added in solution in the nonionic surfactant.

In the compositions of the invention, the liquid non-aqueous nonionic surfactant used contains dispersed and suspended fine particles of organic and / or inorganic builder salts.

5 Preferred organic builder salts include alkali metal salts of polyacetal carboxylic acid (US SN 767 570), alkali metal salts of lower polycarboxylic acids (US SN 762 165), alkali metal salts of nitrilotriacetic acid, (NTA), (US SN 762 164) and alkali metal hydroxyhydroxyacrylic acid polymers (US SN 10 767 535) .

In certain detergent compositions, the above organic builder salts can be used as the main builder salt and without the addition of an inorganic builder salt such as polyphosphate builder or with only a small amount of a polyphosphate builder salt, but it can also be polyphosphate as the main builder.

Other applicable organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali salts. Such builder salts can in particular consist of a copolymer which is the reaction product of equal amounts of methacrylic acid and maleic anhydride and is completely neutralized to form the sodium salt. The builder is commercially available as Sokalan CP5. If used, this builder is also used in small amounts to prevent incrustation, i.e. as an anti-incrustation agent.

Since the compositions of the invention are generally highly concentrated and can therefore be used in relatively low concentrations, it is desirable to supplement the builder with an auxiliary builder, for example with alkali (low) polycarboxylic acid, which has a large calcium and magnesium binding capacity Avoid incrustation that might otherwise occur due to the presence of insoluble calcium and magnesium salts 35. Suitable alkali polycarboxylic acids are the alkali salts of citric acid and tartaric acid, e.g. Monosodium citrate (anhydrous), trisodium citrate, glutaric acid salt, gluconic acid salt and diacid salt with a longer chain.

Examples of organic alkaline sequestering builder 40 salts which can be used or used in a mixture with other organic and inorganic builders are alkali, ammonium or substituted ammonium aminopolycarboxylates, e.g. Sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilo-45 acetate (NTA) and triethanolammonium N- (2-hydroxy-ethyl) nitrilodiacetate. Mixed salts of these aminocarb oxylates are also suitable.

Other suitable organic type builders include oxymethyl succinates, tartronates and glycolates. The detergents of the invention can also contain inorganic water-soluble and / or water-insoluble builder salts. Suitable inorganic builder salts are alkali carbonate, borates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used 55.) Specific examples of these salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesqui carbonate and potassium bicarbonate.

The alkali silicates are useful builder salts that also control the pH and make the composition anticorrosive to parts 60 of the washing machine. Sodium silicates with Na20 / Si02 ratios of 1.6 / 1 to 1 / 3.2, particularly of about 1/2 to 1 / 2.8, are preferred. Potassium silicates with the same proportions can also be used. The preferred alkali silicate is sodium disilicate. 65 Although the detergent composition can be free of phosphate or polyphosphate or essentially free of polyphosphate, small amounts of the usual polyphosphate builders can be added, provided that the local

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Legislation allows their application. Specific examples of such builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium umtripolyphosphate and sodium hexametaphosphate. Sodium tripolyphosphate (TPP) is a preferred polyphosphate. In the formulations to which polyphosphate is added, it is added in an amount of 0 to 50, for example 0 to 30% and 5 to 15%. However, as mentioned above, the formulations are polyphosphate-free or essentially polyphosphate-free.

Other typical suitable builders are described, for example, in U.S. Patents 4,316,812, 4,264,466 and 3,630,929. The inorganic alkali builder salts can be used with the nonionic surfactant or in a mixture with other organic or inorganic builder salts.

The water-insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites generally have the formula

(M20) x (Al203) y (Si02) z-wH20,

where x is 1, y is 0.8 to 1.2, preferably 1, z is 1.5 to 3.5 or more and preferably 2 to 3, w is 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is of type A or a similar structure, with type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per g or more, e.g. 400 meq / 1 g.

Various usable crystalline zeolites (i.e. aluminosilicates) are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, the knowledge of which is assumed here. An example of amorphous zeolites which can be used according to the invention can be found in Belgian PS 835 351, the knowledge of which is likewise assumed here.

Other materials such as clays, especially the water-insoluble types, can be useful additives in the detergents of the invention. Bentonite is particularly suitable. This material is mainly montmorillonite, a hydrated aluminum silicate in which about 1/6 of the aluminum atoms are replaced by magnesium atoms and which can be loosely combined with different amounts of hydrogen, sodium, potassium, calcium etc., in its more purified form (ie free of Gravel, sand etc.) in which it is suitable for detergents, the bentonite contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq / 100 g bentonite. Particularly preferred bentonites are the Wyoming or Western US bentonites, which have been sold by Georgia Kaolin Co. as Thixojels 1, 2, 3 and 4. These bentonites are known to soften textiles as described in GB-PS 401 413 and 461 221.

The shelf life of the detergents is significantly improved by incorporating an effective amount of low molecular weight amphiphilic compounds which are viscosity regulating and gel preventing agents for the nonionic surfactant. The chemical structure of the amphiphilic compounds can be regarded as analogous to the ethoxylated and / or propoxylated liquid fatty alcohol nonionic surfactants, but they have relatively short hydrocarbon chain lengths (C2 to C8) and a low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the following general formula

R0 (CH2CH20) nH,

in which R represents a C2 to Cg alkyl group and n is a number from about 1 to 6 on average.

The compounds are especially low (C2 to 5 C3) alkylene glycol mono low (C2 to C5) alkyl ethers.

Above all, the compounds are di- or tri-lower (C2 to C3) alkylene glycol mono (Cr to C5) alkyl ethers.

Specific examples of suitable amphiphilic compounds are ethylene glycol monoethyl ether (C2Hj-0-CH2CH20H), 10 diethylene glycol monobutyl ether (C4H9-0- (CH2CH20) 2H), tetraethylene glycol monobutyl ether (C4H7-O- (CH2CH20) 4H) and dipropylene glycol CH2CH2H2H2CH2H2CH2CH2H2CH2CH2CH2CH2H2CH2 (CH2CH2) CH2CH2H2CH2H2CH2H2CH2 (CH2CH20) CH2CH2H2H2CH2H2CH2 (CH2CH20) CH2CH2H2CH2H2CH2CH2 (CH2CH20) CH2CH2H2CH2H2CH2CH2H2 (CH2CH20) CH2CH2CH2H2CH2H2CH2H2H2H2CH2H2H2CH2H2CH2H2H2CH2H2CH2H2H2CH2H2H2H2 CH2CH2H2 Diethylene glycol monobutyl ether is particularly preferred.

15 The incorporation of lower molecular weight lower alkylene glycol monoalkyl ethers into the composition of the invention lowers their viscosity so that it becomes easier to pour, improves their stability against settling and their dispersibility when added to warm or cold water.

The compositions of the invention have improved viscosity and stability properties and remain stable and pourable at low temperatures such as about 5 ° C and below.

According to one embodiment of the invention, the physical stability of the suspension of the builder (s) and any other suspended additives such as bleaching agents etc. in the liquid carrier is improved by the presence of a stabilizing agent which is an alkanol ester of 30 phosphoric acid or an aluminum salt of a higher fatty acid.

In certain formulations, improvements in the stability of the composition can be achieved by incorporating a small effective amount of an acidic organic phosphorus compound with an acidic - POH group, for example a partial ester of phosphoric acid and an alkanol.

As indicated in US SN 597 948, the knowledge of which is assumed here, the acidic organic phosphorus compound with an acidic - POH group can increase the stability of the suspension of the builders in the nonaqueous liquid nonionic surfactant.

The acidic organic phosphorus compound may, for example, be a partial ester of phosphoric acid and an Al-45 alcohol, such as an alkanol with a lipophilic character, for example having more than 5 carbon atoms, e.g. Contains 8 to 20 carbon atoms.

A specific example is a partial ester of phosphoric acid with a CI6 to C18 alkanol (Empiphos 5632 from Mar-sochon); it is made with 35% monoester and 65% diester.

The incorporation of very small amounts of the acidic organic phosphorus compound makes the suspension significantly more stable against settling when standing, but it remains pourable, while, due to the low concentration of the stabilizer, for example below about 1%, its plastic viscosity generally decreases.

Further improvements in the stability and sedimentation-preventing properties of the composition can be achieved by adding a small amount of an aluminum salt of a higher fatty acid to the composition.

The aluminum salts used as stabilizing substances are the subject of US-SN 725 455, the knowledge of which is assumed here.

The preferred higher aliphatic fatty acids have about 8 to 22, especially about 10 to 20, and most preferably 12 to 18 carbon atoms. The aliphatic rest can

be saturated or unsaturated and straight-chain or branched. As in the case of non-ionic surfactants, mixtures of fatty acids such as those from natural sources can also be used, for example tallow fatty acid, coconut fatty acid etc.

Examples of the fatty acids with which the aluminum salt stabilizers can be formed are decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicoanic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally commercially available and are preferred used in the triacid form, e.g. Aluminum stearate as aluminum tristearate A1 (Ci7H35COO) 3. The mono acid salts, e.g. Aluminum monostearate A1 (OH) 2 (Ci7H35COO) and the diacid salts, e.g. Aluminum distearate Al (OH) (C17H35COO) 2 and mixtures of two or three of the mono-, di- and tri-acid aluminum salts can also be used. However, it is most preferred that the triacid aluminum salt make up at least 30, preferably 50, most preferably at least 80% of the total amount of the aluminum fatty acid salt.

The aluminum salts are commercially available as mentioned. They can be easily prepared, for example by saponifying a fatty acid, e.g. of animal fat, stearic acid etc., and then treating the soap obtained with aluminum, aluminum oxide etc.

Without wishing to be bound by any particular theory as to how the aluminum salt prevents the suspended particles from settling, it is believed that the aluminum salt increases the wettability of the solid surfaces by the nonionic surfactant. This increase in wettability therefore enables the suspended particles to remain in suspension more easily.

Only very small amounts of aluminum salt are required as a stabilizing agent in order to obtain the significant improvements in physical stability.

In addition to its effect as a physical stabilizer, the aluminum salt has the additional advantage over other physical stabilizers that it has a nonionic character and is compatible with the nonionic surfactant component and does not interfere with the overall cleaning power of the composition; it shows a certain foam-preventing effect; it can increase the effectiveness of fabric softeners and it gives the suspensions a longer relaxation time.

The bleaching agents can be appropriately divided into chlorine bleaching agents and oxygen bleaching agents. Typical representatives of the chlorine bleaching agents are sodium hypochlorite, (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by per-compounds that release hydrogen peroxide in solution. Preferred examples are sodium and potassium perborates, percarbonates and perphosphates and potassium monopersulfate. The perborates, especially sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in a mixture with an activator. Suitable activators which can lower the temperature of action of the peroxide bleaching agent are described, for example, in US Pat. No. 4,264,466 or in column I of US Pat. No. 4,430,244, the knowledge of which is assumed here. Polyacylated compounds are preferred activators; Of these, compounds such as tetraacetylethylene diamine (TAED) and pentaacetyl glucose are particularly preferred.

Other useful activators are, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and

9 674 358

Alkenyl succinic anhydride, tetraacetyl glycouril (TA-GU) and the derivatives thereof. Other applicable classes of activators are described, for example, in U.S. Patents 4,111,826, 4,422,950 and 3,661,789. 5 The bleach activator usually interacts with the peroxygen compound and forms a peracid bleach in the wash water. It is preferred to incorporate a sequestering substance with a large complex binding capacity in order to avoid any undesired reaction between

10 see this to prevent peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.

Suitable sequestering substances for this purpose are the sodium salts of nitrilotriacetic acid (NTA), ethyl 15-lendiamine tetraacetic acid (EDTA), diethylenetriaminepentaesacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), which is sold under the name Dequest 2066; and ethylenediaminetetraethylenephosphonic acid (EDITEMPA). These sequestering substances can be used alone or in a mixture.

To prevent loss of peroxy bleach, e.g. To avoid sodium perborate, by enzyme-induced decomposition, for example by catalase enzyme, the compositions can also contain an enzyme-inhibiting compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxy bleach. Suitable inhibitors are described in US Pat. No. 3,606,990, the knowledge of which is assumed.

Hydroxylamine sulfate and other water-soluble hydroxylamine salts are particularly interesting inhibitor compounds. In the preferred non-aqueous compositions of the invention, suitable amounts of the hydroxylamine salt inhibitors can only be about 0.01 to 0.4%. In general, however, suitable amounts of the 35 enzyme inhibitors are up to about 15, for example 0.1 to 10% by weight of the composition.

In addition to the builders, various other detergent additives or adjuvants can be present in the detergent product to give it additional desired properties of a functional or aesthetic nature. For example, small amounts of dirt-suspending or reprecipitating substances, e.g. Polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose can be built-45. A preferred re-precipitation preventing substance is sodium carboxymethyl cellulose with a CM / MC ratio of 2: 1, which is sold under the name Re-latin DM 4050.

Optical brighteners for cotton, polyamide and poly-50 ester substances can be used. Suitable optical brighteners are stilbene, triazole and benzidine sulfone compositions, in particular sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidine sulfone etc., with stilbene and triazole combinations being most preferred. Preferred brighteners are Stilben Brightener N4, a dimorpholinodianilinostilbenesulfonate, and the well-known Tinopal ATS-X.

Enzymes, preferably proteolytic enzymes such as subti-lisin, bromelin, papain, trypsin and pepsin, and enzymes 60 of the amylase type, lipase type and mixtures thereof can be used. Preferred enzymes are protease paste, esperase paste and amylase. A preferred enzyme is Esperse SL8, which is a protease. Anti-foaming substances, e.g. Silicone compounds such as Silica-65 ne L 7604 can also be added in small amounts.

Bactericides, e.g. Tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water-dispersing

674 358

10th

bar), protective substances, ultraviolet absorbers, yellowing-preventing substances such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color-preserving bleaching agents, perfume, and dyes and bluing agents such as ultramarine blue can be used.

The composition can also contain an inorganic insoluble thickening or dispersing agent with a very large surface area, such as finely divided silica with extremely fine particle size (e.g. with diameters from 5 to 100 millimicrometers, sold under the name Aero-sil) or the other high-volume inorganic carrier materials used in US Pat. No. 3,630,929 are described, in amounts of 0.1 to 10, for example 1 to 5%. However, it is preferred that compositions which form peroxyacids in the wash bath (e.g. compositions containing peroxygen compounds and an activator) are essentially free of such compounds and other silicates; it has been found that silicic acid and silicates promote the undesired decomposition of the peroxy acid.

According to one embodiment of the invention, the stability of the builder salts in the composition during storage and the dispersibility thereof are improved by grinding or reducing the particle size of the solid builders to less than 100 micrometers, preferably less than 40 micrometers and particularly preferably less than 10 micrometers. The solid particles, for example alkali polyphosphate, are generally supplied in particle sizes of about 100, 200 or 400 microns. The liquid nonionic surfactant phase can be mixed with the solid builders before or after grinding.

According to a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and the solid constituents is placed in an attritor, in which the particle size of the solid constituents is reduced to less than about 10 micrometers, for example to an average particle size of 2 to 10 micrometers or else below (e.g. 1 micron). Preferably less than about 10, particularly less than about 5% of all suspended particles have particle sizes over 10 microns. Compositions whose dispersed particles have such small particle sizes have better stability against separation or settling when stored. The addition of the nonionic surfactant with a terminal acid group contributes to the dispersibility of the dispersions without correspondingly reducing their stability against settling.

When grinding, it is preferred that the amount of the solid constituents is sufficiently large (e.g. at least about 40, for example about 50%), that the solid particles are in contact with one another and not substantially shielded from one another by the nonionic surfactant liquid. After the grinding step, all remaining liquid nonionic surfactant can be added to the ground formulation. Mills with grinding balls (ball mills) or similar mobile grinding elements have given very good results. So you can use a batch-type laboratory attritor with steatite grinding balls with a diameter of 8 mm. For work on a larger scale, a continuously working mill can be used, in which grinding balls (diameter 1 mm or 1.5 mm) work in a very narrow gap between a stator and a rotor, which is operated at a relatively high speed (e.g. a CoBall -Mill); when using such a mill, it is desirable to first pass the mixture of nonionic surfactant and solids through a mill that is not so finely ground (e.g. a colloid mill) to reduce the particle size to less than 100 microns (e.g. about 40 microns) before Reduce the stage at which the average particle diameter is less than about 10 microns in the continuous ball mill.

5 In the preferred heavy duty liquid detergents of the invention, typical proportions (percent based on the total weight of the composition, unless otherwise stated) of the ingredients are as follows:

Highly biodegradable liquid nonionic prop-io oxylated ethoxylated fatty alcohol surfactant in the range of about 10 to 60, for example 20 to 50 and 30 to 40%.

Acid-terminated nonionic surfactant which can be omitted but is preferably added to the composition in an amount ranging from about 0 to 30, 15 for example 5 to 25 and 5 to 15%.

Organic builder salt in the range of about 0 to 50, for example 10 to 40 and 25 to 35%.

Polyphosphate builder salt in the range of about 0 to 50, for example 0 to 30 and 5 to 15%.

20 copolymer of polyacrylate and polymaleic anhydride, alkali salt, as the crust preventing agent, in the range of about 0 to 10, for example 2 to 8 and 2 to 6%.

Alkylene glycol monoalkyl ether as a gel-preventing substance in an amount in the range of about 0 to 20, for example 5 to 15 and 8 to 12%.

Phosphoric acid alkanol ester as a stabilizing compound in the range of 0 to 2.0 or 0.1 to 1.0, e.g. 0.10 to 0.5%.

30 fatty acid aluminum salt as a stabilizing agent in the range of about 0 to 3.0, for example 0.1 to 2.0 and 0.5 to 1.5%.

It is preferred that at least one of the stabilizing compounds phosphoric acid ester or aluminum salt 35 is incorporated into the composition.

Bleaching agents in the range 0 to 35, for example 5 to 30 and 8 to 15%.

Bleach activator in the range of about 0 to 25, for example 3 to 20 and 4 to 8%.

40 bleach sequestering substance, in the range of about 0 to 3.0, preferably 0.5 to 2.0 and 0.5 to 1.5%.

Anti-reprecipitation substance in the range of about 0 to 3, for example 0.5 to 2.0 and 0.5 to 451.5%.

Optical brightener in the range of about 0 to 2.0, for example 0.1 to 1.5 and 0.3 to 1.0%.

Enzymes in the range of about 0 to 3.0, for example 0.5 to 2.0 and 0.5 to 1.5%.

so perfume in the range of about 0 to 2.0, for example 0.10 to 1.0 and 0.5 to 1.0%.

Dye in the range of about 0 to 1.0, for example 0.0025 to 0.050 and 0.25 to 0.0100%.

Various of the additives 55 mentioned above can be added as desired to achieve the desired effect of the added materials.

Mixtures of nonionic surfactant with a terminal acid group and alkylene glycol alkyl ether can be used as gel-preventing substances, in some cases the use of only such mixtures being advantageous, or a stabilizing and settling-preventing agent, e.g. Phosphoric acid alkanol esters are added. The additives are selected so that they are compatible with the main components of the detergent composition. In this application, as mentioned, all amounts and percentages are based on the total formulation or composition, unless otherwise stated.

11

674.358

The concentrated non-aqueous, nonionic liquid detergent composition of the invention is readily dispersed in the water in the washing machine. Household washing machines currently in use typically require 175 grams of powder detergent to wash a full drum. According to the invention, only about 77 ml or about 100 g of the concentrated liquid nonionic detergent composition are required.

Comparative tests

In order to compare the physical properties of the nonionic propoxylated ethoxylated fatty alcohol surfactants of the invention with those of the commonly available nonionic surfactants, the following comparison tests were carried out:

1. A nonionic surfactant of the formula R- (0C3H6) x (0-C2H4) yOH, in which R is C12- to CI5, x = 3 and y = 5, was compared with product D with regard to the biodegradability of the respective surfactants. Product D, as indicated above, is a mixture of equal parts of Product B (a C13 to C] 5 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide) and Product C (a C13 to C] 5 fatty alcohol with 5 moles of propylene oxide and 10 moles of ethylene oxide).

In the product B-surfactant, the propylene oxide molecules are not bound to the alkyl part of the surfactant structure. In the product C-surfactant, the propylene oxide molecules are not bound to the alkyl part of the surfactant structure.

The biodegradability comparison tests were performed using the OECD test method (as mentioned). The tests show that the surfactant of the invention is at least 90% biodegradable and that product D is less than 40% biodegradable. The biodegradability properties of the surfactant of the invention are thus superior to that of Product D.

2. The nonionic surfactants of the invention are low in foam when used. To demonstrate low foaming, the nonionic surfactant of the invention of Comparative Test 1 above was compared to the commonly used surfactant T 7/9. The surfactant T 7/9 used was obtained by ethoxylating a secondary CI3 fatty alcohol with an average of 7 to 9 ethylene oxide groups per mole of fatty alcohol. Standard foam tests were carried out.

The test results showed that the nonionic surfactant of the invention was low in foam compared to the commonly used nonionic surfactant, the surfactant T 7/9.

3. The nonionic surfactant of the invention used in Comparative Test 1 above was compared to Surfactant T 7/9 to determine the pour point behavior of each surfactant. The pour point temperature was increased in each case by slowly increasing the temperature by 2 ° C / min. certainly. The pour point temperature is the temperature at which the nonionic surfactant begins to flow.

The results of the comparative tests showed that the surfactant of the invention has a pour point temperature of -2 ° C, which is lower than that of Surfactant T 7/9, which has a casting temperature of 3 ° C.

4. To determine the gelling properties of the nonionic surfactant of Test 1 invention, it was compared to Product D and Surfactant T 7/9. The test was carried out by contacting the respective surfactants with water at 5 ° C. and measuring the relationship between viscosity and concentration.

The comparative tests show that the nonionic surfactant of the invention does not gel on contact with water at 5 ° C (although an increase in the viscosity of the surfactant was found), whereas product D and surfactant T 7/9 gel on contact with water at 5 ° C .

According to a preferred embodiment of the invention, a typical detergent formulation is as follows:

5

% By weight

Highly biodegradable non-ionic 30 to 40 propoxylated ethoxylated fatty alcohol surfactant with terminal acid group 5 to 15 sodium tripolyphosphate, builder salt 25 to 35 crust-preventing agent 0 to 10 (Sokalan CP-5)

Organic builder salt 0 to 30

15 alkylene glycol monoalkyl ethers 8 to 12

Alkanol phosphoric acid esters 0.1 to 0.5

(Empiphos 5632)

Anti-reprecipitation 0 to 3.0

Agent (Relatine DM 4050)

20 alkali perborate, bleaching agents 8 to 15

Bleach Activator (TAED) 4 to 8

Sequestering agent (Dequest 2066) 0 to 3.0

Optical brightener (ATS-X) 0.3 to 1.0

Enzymes 0.5 to 1.5

25 perfumes 0.5 to 1.0

The following example is intended to explain the invention.

example 1

A concentrated non-aqueous liquid detergent containing 30 nonionic surfactants was prepared from the following ingredients in the amounts indicated:

% By weight

35 Highly biodegradable nonionic 38.7 surfactant of formula R- (OC3H6) x (OC2H4) y

Nonionic surfactant (Dobanol 91-5) 5.0 with terminal acid group,

40 Reaction product of C9 to Cn fatty alcohol ethoxylate (5 EO on average) with succinic anhydride

Sodium tripolyphosphate 26.0

45 diethylene glycol monobutyl ether 6.0

Alkanol phosphoric acid ester 0.3

(Empephos 5632)

Anti-incrustation agent 4.0 (Sokalan CP-5)

50 sodium perborate monohydrate, 12.0

Bleach

Tetraacetylethylenediamine (TAED), 4.0 bleach activator

Sequestrant (Dequest 2066) 1.0

55 Optical brightener (Tinopal ATS-X) 0.5 anti-repellant 1.0 (Relatin DM 4050)

Protease (Esperase SL8) 1.0

Perfume 0.5

60 100.0

(1) R = C] 2 to C15, x = 3, y = 5.

The formulation was milled for about 1 hour to reduce the particle size of the suspended builder salts to less than 40 microns. The nonionic surfactant component of the formulation was 90% biodegradable. The formulated detergent composition was stable, ge

674 358

did not form during storage, had a high washing power and did not foam when used.

The formulations can be made into a small particle size without grinding the builder salts and the suspended particles, but the best results are obtained if the formulations are ground to reduce the particle size of the suspended solid particle.

The builder salts can be used as supplied, but the builder salts and suspended solid particles can also be ground or partially ground before being mixed with the nonionic surfactant. The grinding can be done partly before mixing and after mixing

12

complete the grinding, or carry out the whole grinding process after mixing with the liquid surfactant. Formulations containing suspended builders and solid particles less than 100 microns in size are preferred.

The highly biodegradable propoxylated ethoxylated fatty alcohol nonionic surfactants of the invention can be used to formulate polyphosphate builder salt, low polyphosphate builder salt, and no polyphosphate builder-10 salt detergent at all. They can also be used as the sole or main nonionic surfactant in aqueous builder-containing or non-builder-containing heavy duty detergent compositions.

C.

Claims (17)

674 358 1. Compounds of the formula R- (OC3H6) x (OC2H4) yOH, wherein R represents an aliphatic C8 to C26 group, the value of x + y is 20 to 100% of the number of carbon atoms of the R group, and wherein x is at least 1 and y is at least 1. 2. Compounds according to claim 1, characterized in that R is C9 to C18 alkyl and that x is at least 2 and y is at least 2. 2nd PATENT CLAIMS 3. Compounds according to claim 1, characterized in that R represents C9 to Cu alkyl and x is at least 3 and y is at least 3. 4. Compounds according to claim 1, characterized in that R is C12 to cis alkyl and x is at least 3 and y is at least 3. 5. Heavy duty detergent, characterized by the content of a highly biodegradable nonionic surfactant of the formula R (OC3H6) x (OC2H4) yOH, wherein R represents an aliphatic C8 to C26 group, x is 2 to 15 and y is 2 to 15, and the value of x + y is 20 to 100% of the number of C atoms in the R group. 6. Detergent according to claim 5, characterized in that it contains at least one member from the group of organic builder salt and inorganic builder salt. 7. Detergent according to claim 5, characterized in that there is at least one member from the group of - nonionic surfactant with a terminal acid group as a gelling-preventing agent, - Alkylene glycol monoalkyl ether and - Contains alkanol phosphoric acid ester as a stabilizing agent. 8. Detergent according to claim 5, characterized in that it contains one or more additives from the group consisting of bleach, bleach activator, optical brightener, enzymes and perfume. 9. Detergent according to claim 5, characterized in that R is C9- to Qg-alkyl, x is at least 2 and y is at least 2 and x + y = 4 to 16. 10. Detergent according to claim 5, characterized in that R is C9 to C] r alkyl, x is at least 2 and y is at least 2 and x + y = 5 to 10. 11. Detergent according to claim 5, characterized in that R is C] 2 "to C ^ alkyl, x is at least 2 and y is at least 2 and x + y = 5 to 15. 12. Detergent according to claim 5, characterized by the content of a nonionic surfactant of the formula R (OC3H6) x (OC2H4) yOH, in which R is C9- to Qg-alkyl, x is 2 to 8 and y is 2 to 8, in an amount of about 20 to 50%, a builder salt in an amount of about 10 to 40%, a surfactant with a terminal acid group in an amount of about 5 to 25%, an alkylene glycol monoalkyl ether in an amount of about 5 to 15%, and - an alkanol phosphoric acid ester in an amount of about 0.1 to 1.0%. 13. Detergent according to claim 12, characterized by a content of alkali borate bleach in an amount of about 5 to 30%, tetraacetylethylenediamine (TA- ED) bleach activator in an amount of about 3 to 20%, and optionally one or more additives from the group consisting of anti-scale agent, anti-re-precipitation agent, sequestering agent 5 for bleaching, optical brighteners, enzymes and perfume. 14. Detergent according to claim 12, characterized in that it is not aqueous, that the surfactant is liquid and that the builder salt contains sodium tripolyphosphate. 15 15. Detergent according to claim 5, characterized in that it is not aqueous, and that it - Highly biodegradable liquid nonionic surfactant of the formula 15 R- (OC3H6) x (OC2H4) yOH, where R is C9- to Qg-alkyl, x + y = 4 to 16, x at least 2 and y at least 2, in an amount of 20 to 50%, 20 - surfactant with terminal acid group in an amount of about 5 to 25%, Sodium tripolyphosphate as builder salt in an amount of about 10 to 40%, Alkylene glycol monoalkyl ether in an amount of about 5 25 to 15%, Alkanol esters of phosphoric acid in an amount of about 0.1 to 1%, Sodium perborate monohydrate as a bleaching agent in an amount of about 8 to 15%, and Contains 30 - tetraacetylethylenediamine (TAED) as a bleach activator in an amount of about 4 to 8%. 16. Detergent according to claim 15, characterized in that it is pourable at high and low temperatures, is stable during storage and when mixed 35 not gelled with cold water. 17. Detergent according to claim 5, characterized in that the nonionic surfactant is at least 80% biodegradable.