CH671235A5 - - Google Patents

Description

DESCRIPTION

The invention relates to a non-aqueous liquid heavy-duty detergent, and in particular to phosphate-free or low-phosphate-containing non-aqueous liquid detergent compositions which contain a suspension of a polyhydroxyacrylic acid, a salt thereof or a polyacetal carboxylate as builders salt in nonionic surfactants, the compositions being stable against phase separation and gelation and easy to pour. The heavy duty detergent can be used to clean soiled textiles.

Liquid non-aqueous heavy-duty detergents are known, such as, for example, compositions which contain a liquid nonionic surfactant in which particles of a builder are dispersed according to US Pat. Nos. 4,316,812, 3,630,929 and 4,264,466 and GB Patents 1,205,711, 1 270 040 and 1 600 981.

US Pat. No. 4,450,089 discloses a particulate detergent containing an inorganic peroxygen bleach and a polyhydroxyacrylate as a stabilizer for the bleach, and US Pat. No. 4,450,249 discloses a particulate bleaching composition containing an organic peroxyacid. Bleach and a stabilizing polyhydroxyacrylate known.

The use of polyhydroxycarboxylic acid is known as a substitute for phosphate and polyphosphate builders according to US Pat. No. 3,825,498 for particulate or liquid dishwashing detergents and according to US Pat. Nos. 3,706,672 and 5,922,230 for detergents.

The detergency of synthetic nonionic surfactants in detergents can be increased by adding builders. Sodium tripolyphosphate is one of the preferred builders. However, the use of sodium poly-1 ° phosphate in dry, powdery detergents has several disadvantages, such as the tendency of the polyphosphates to hydrolyze to pyrophosphates and orthophosphates, which are less valuable builders. In addition, the polyphosphate content of detergents is responsible for the undesirably high phosphate content in water. An increased phosphate content in the water leads to a greater algae growth with the result that the biological balance of the water is adversely changed.

20 Due to state regulations, a reduction in the polyphosphate content in detergents was recently ordered and in some cases detergents are said to contain no polyphosphate builders at all.

Liquid detergents are often considered to be more practical than dry, powdery or particulate products when used and are therefore preferred by consumers. They can be easily measured, dissolve quickly in the wash water and can easily be applied in concentrated solutions or dispersions to soiled areas of clothes to be washed and do not dust and generally require less storage space. In addition, components can be used in the liquid detergents that cannot withstand drying processes without destruction, and 35 which are often used in the production of particulate detergents. Despite numerous advantages of liquid detergents over one-piece or particulate solid products, they also have some disadvantages that must be overcome to produce acceptable commercial products. Some of these products separate on storage, others show separations on cooling and are not easily redispersed. In some cases, the viscosity of the product changes, which is either too thick to pour or so thin that it appears watery. Some clear products become cloudy, while others gel on standing.

In addition to the problem of settling or phase separation, the non-aqueous liquid textile detergents based on liquid nonionic surfactants have the disadvantage that the nonionic surfactants gel when added to cold water. This is particularly a problem with the usual European household washing machines if the user puts the detergent composition into a dispensing unit, for example into the dispensing container 55 of the washing machine. When the washing machine is in operation, the detergent in the dispensing compartment is exposed to a stream of cold water in order to rinse it into the total wash liquor. Particularly during the winter months, when the detergent composition and the water fed into the dispensing chamber are particularly cold, the viscosity of the detergent increases considerably and forms a gel. As a result, the detergent is not completely rinsed out of the dispenser compartment during operation of the washing machine and after repeated washing processes, deposits are formed which can only be removed by rinsing the dispenser compartment with hot water.

Gelling can also become a problem when washing with cold water, as is often the case for v

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certain synthetic textiles and sensitive textiles lymerisation i.e. the value of n is generally recommended or recommended for textiles that fit in warm or hot water due to the limit of compatibility with regard to running. Solubility of the polymer in water.

The tendency that concentrated detergents during the polyacetal

gelling during storage is made more difficult when these washing carboxylates are also known. The preparation of these agents is stored in unheated storage rooms or during builder salts in US Pat. Nos. 4,315,092 and 4,144,226 and in winter in unheated transport vehicles their use as builder salt for detergents can be found in portieri. U.S. Patent 4,146,495.

Partial solutions for the gelling problem in aqueous and in the polyacetal carboxylates are water soluble and depoly-

essential composites containing no builders quickly in neutral or non-alkaline medications have been proposed, for example, by; they form low molecular components that are biolose the liquid nonionic surfactant with certain that are visually degradable. The polyacetal carboxylates and viscosity-regulating solvents are therefore used in formulations which are diluted in addition agents, such as according to US Pat. No. 3,953,380, with a pH to 7, e.g. ren alkanols such as ethyl alcohol or according to US-PS 15 from 8 to 10 such as 9 to 10. Although the polyacetal

4,368,147 with alkali formates and adipates or with hexacarboxylates when used in alkaline medium are effective glycol, polyethylene glycol and by modification and me builders salts, they are when the optimization of the nonionic structure is released. As an example of wash liquor in the drain or other sewage systems new - the modification of the nonionic structure with specially tralized and depolymerized into small fragments, the good success was achieved by acidifying the hydroxyl-20 which are easily biodegradable. The polyacetal carboxylate end groups of the nonionic molecule. The advantage of are good builder salts in particular because the introduction of a carboxylic acid at the end of the non-ionic ne high sequestering capacity for calcium and magnesi surfactant also results in gel prevention when diluted to have ions in wash water.

a lowering of the pour point and the formation of anio- The polyacetalcarboxyla- used according to the invention

niche surfactants when neutralized in the wash liquor 25 te have the following general formula:

becomes. The optimization of the nonionic structure has essentially been based on the chain length of the hydrophobic / lipophilic group and the number and formation of the alkylene oxide units, e.g. Directed ethylene oxide units in the hydrophilic residue. For example, it has been found that a C13-30 fatty alcohol ethoxylated with 8 moles of ethylene oxide shows little tendency to gel. where M is an alkali or ammonium cation, n is a value of

Nevertheless, both in terms of stability and which is at least 4, and R] and R2 are selected such that they prevent geliking improvements in phosphate-individually stable residues that polymerize against depo-free non-aqueous liquid textile treatment agents Stabilize alkaline solution and also wishes. with the other components of the nonionic liquid

The invention is compatible due to the features in the independent detergent according to the invention. A han claim marked. A highly concentrated, commercially available polyacetal carboxylate builder salt is sold under phosphate-containing and in particular no polyphosphate according to the name “Builder U” as the sodium salt of non-aqueous liquid heavy-duty washing machine containing 40 tons of monsan builders.

Detergents or textile detergents can be prepared. In order to improve the viscosity properties of the composition to which polyhydroxyacrylic acid or a salt thereof is considered, a nonionic surfactant with a terminal builders or a polyacetal carboxylate as a buildersalt acid group is added. To continue the viscosity egg-dispersed in a liquid nonionic surfactant. properties of the composition and to improve the

Polyhydroxyacrylic acid or its salts are known per se to improve the properties of the composition. Their preparation and use for stabilization is added to the composition a viscosity-improving peroxygen and peracid bleaching agent in detergents and a gel-preventing agent, namely alkylene glycol is described in US Pat. Nos. 4,450,089 and 4,455,249. colmonoalkyl ethers, and anti-settling agents-The low molecular weight polyhydroxyacrylic acids and dense, such as aluminum stearate and phosphoric acid esters. With their salts are easily biodegradable; They are a good embodiment according to the invention, can bleach stabilizers and also act as a non-ionic surfactant to prevent incrustation. The polyhydroxyacrylates are terminated with acid, an alkylene glycol monoalkyl ether especially good builder salts because they contain a high and an anti-settling agent. Have sequestering capacity for calcium and magnesium ions in disinfectant or bleaching agents and activators of the wash liquor. 55 for these can improve the bleaching power and the

The polyhydroxyacrylates consist of monomeric cleaning properties added to the composition by the following general formula.

In one embodiment according to the invention, the builder components of the composition are ground to a particle size of less than 100 μm and preferably less than 10 μm in order to improve the stability of the suspension of the builder components in the liquid nonionic surfactant.

Furthermore, other constituents can also be added to the detergents in which R (and R2 are the same or different and water compositions are added, such as agents for fabrication or an alkyl radical having 1 to 3 carbon atoms to prevent incrustation, foam depressants, optical inducements, while M is hydrogen or an alkali, alkaline earth, enzymes, perfume and dyes.

or can be an ammonium cation. The extent of the Po- In the household washing machine used today-

CHO -

I.

COOM

J n

R, OH

-4c-ç -

R "COOM

Normally, washing temperatures of up to 95 ° C are used and about 20 liters of water are used during washing and rinsing. Normally 175 g of a powdery detergent are used per wash.

When using highly concentrated liquid detergents, only 80 g or 67 ml of the liquid detergent are required for a full load of dirty laundry.

Accordingly, according to the invention, in one respect, a liquid heavy-duty detergent containing no or essentially no phosphate builders is provided, which is built up from a suspension of an alkali salt of a polyhydroxyacrylic acid or a polyacetal carboxylic acid as builders in liquid nonionic surfactant.

According to a further aspect of the invention, such a coarse textile detergent is proposed which is stable during storage and does not settle and does not gel during storage and use. The liquid compositions according to the invention are easy to pour, easy to measure and easy to put into the washing machine.

According to a further aspect, a method is proposed for dispensing a phosphate-free or low-phosphate, liquid nonionic detergent in and / or with cold water without gelation occurring. In particular, a method is provided for filling a container with a non-aqueous liquid textile detergent composition, the detergent being at least predominantly composed of a liquid nonionic surfactant containing no polyphosphate builder, and for disposing this composition from a container into the dispensing aqueous wash liquor, the dispensing being effected by directing a stream of unheated water onto the composition so that the composition is carried into the wash liquor by the water jet.

The advantages of the detergents according to the invention are based on the fact that, owing to the absence of polyphosphate builders, they do not give rise to problems with phosphate pollution in water. The polyphosphate-free or low polyphosphate content, preferably concentrated, non-aqueous nonionic textile detergents according to the invention have the further advantage that they are stable, do not settle when stored and do not gel during storage. The liquid compositions are easy to pour, easy to measure and easy to put into the washing machine.

It is an object of the present invention to provide a low-density, low-polyphosphate and in particular a polyphosphate-free liquid heavy-duty detergent based on a non-aqueous nonionic surfactant which does not pose any problems with regard to environmental pollution. To achieve this object, a detergent composition of this type is proposed which contains polyhydroxyacrylate builders or their salts or polyacetal carboxylates suspended in a nonionic surfactant.

A further object of the present invention is to propose a liquid textile treatment agent which is free of polyphosphate or contains small amounts of polyphosphate, which is a suspension of a polyhydroxyacrylate builder or a polyacetal carboxylate builder salt in a non-aqueous liquid and is stable, easy to pour and cold when stored , warm or hot water is dispersible.

Another object of the invention is to propose the formulation of a non-aqueous liquid textile detergent based on nonionic surfactants which contains no or only a little polyphosphate builders, which is pourable at all temperatures and which can be poured several times

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Dispenser compartments of conventional washing machines can be dispensed without blockages or accumulations in the dispenser even during the colder season.

Another object of the invention is to propose polyphosphate-free or low polyphosphate, non-gelling, stable suspensions of a heavy-duty detergent with a non-aqueous liquid nonionic surfactant which contains an effective amount of a polyhydroxyacrylate as a builder or a polyacetal carboxylate builder salt .

Another object of the invention is to provide a non-gelling, stable suspension of a builder-containing, non-aqueous, liquid, nonionic heavy-duty detergent which contains an amount of phosphoric acid alkanol ester and / or aluminum fatty acid salt sufficient to increase the stability of the composition , ie prevent settling of the builder particles, etc., and preferably with a decrease or at least without an increase in the plastic viscosity of the composition.

These and other objects of the present invention are generally achieved by preparing a low polyphosphate or a polyphosphate-free detergent and builder composition by adding an effective amount of an alkali salt of a polyhydroxyacrylic acid or an alkali salt of a polyacetal carb to the non-aqueous liquid nonionic surfactant -oxylates and inorganic or organic textile treatment additives such as, for example, viscosity improvers or agents for preventing gel formation or agents for preventing settling, agents for preventing the formation of incrustations, bleaching agents, bleach activators, foam depressants, optical brighteners, enzymes, agents for preventing redeposition, Perfumes and dyes added.

Nonionic surfactants

One of the numerous compounds known per se can be used as nonionic surfactants in the detergents according to the invention. As is known, nonionic surfactants are characterized by having an organic hydrophobic group and an organic hydrophilic group, and are generally obtained by condensing an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide, which is intrinsically hydrophilic. Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino residue can be condensed with a hydrogen on nitrogen with ethylene oxide or with the polyhydrogenation product thereof such as polyethylene glycol to form a nonionic surfactant. The length of the hydrophilic chain or polyoxyethylene chain can be easily adjusted to achieve the desired balance between hydrophobic and hydrophilic groups. Suitable nonionic Jensides are e.g. U.S. Patent Nos. 4,316,812 and 3,630,929.

The nonionic surfactants are usually poly-low alkoxylated lipophiles, in which the desired hydrophilic / lipophilic balance is obtained by adding a hydrophilic poly-lower alkoxy group to a lipo-philè group. A preferred class of nonionic surfactants are poly-lower alkoxylated higher alkanols in which the alkanol has 9 to 18 carbon atoms and the number of moles of lower alkylene oxides with 2 or 3 carbon atoms ranges from 3 to 12. Products in which the higher alcohol is a fatty alcohol having 9 to 11 or 12 to 15 carbon atoms and which contains 5 to 8 or 5 to 9 lower alkoxy groups per mole are preferred. Preferably the lower alkoxy group is an ethoxy, but can

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may also be mixed with propoxy in some cases, the latter, if present, often being less than 50%.

Examples of these compounds are those in which the alkanol has 12 to 15 carbon atoms and contains 7 ethylene oxide groups per mole, such as “Neodol 25-7” and “Neodol 23-6.5” (Shell Chemical Company, Inc.).

The former is a condensation product of a mixture of higher fatty alcohols with an average of 12 to 15 carbon atoms and with about 7 moles of ethylene oxide, while the latter is a corresponding mixture, the carbon atom content of the higher fatty alcohol being 12 to 13 and the number of ethylene oxide groups on average around 6.5 . The higher alcohols are primary alcohols.

Other examples of such surfactants are "Tergitol 15-S-7" and "Tergitol 15-S-9" (Union Carbide Corp.), both of which are linear secondary alcohol ethoxylates. The first-mentioned product is a mixed ethoxylation product of linear secondary alkanol containing 11 to 15 carbon atoms with 7 moles of ethylene oxide while the latter is a similar product but with 9 moles of ethylene oxide.

A higher molecular weight nonionic surfactant such as “Neodol 45-11”, which is a similar ethylene oxide condensation product of a higher fatty alcohol, which has 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is approximately 11, can also be used as the nonionic surfactant in the compositions according to the invention .

Other suitable nonionic surfactants are sold under the name "Plurafac"; these are reaction products of higher linear alcohols and a mixture of ethylene and propylene oxides which contain a mixed chain of ethylene oxide and propylene oxide which ends with a hydroxyl radical. Examples are product A, namely a C13-CI5 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, product B, namely a C13-C15 fatty alcohol, which is condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide and product C, a Q3-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide.

Other nonionic surfactants are sold under the name “Dobanol” (Shell Chemical Company, Inc.), such as “Dobanol 91-5”, which is an ethoxylated C9-Ci p fatty alcohol with an average of 5 moles of ethylene oxide, and “Dobanol 25- 7 », which is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In the preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxy groups will usually be 40 to 100% of the number of carbon atoms in the higher alcohol, and preferably 40 to 60%, to achieve the best balance between hydrophilic and lipophilic groups; and the nonionic surfactant preferably contains at least 50% of such preferred poly lower alkoxy higher alkanol. Alkanols with a higher molecular weight and numerous other, normally solid, nonionic surfactants can contribute to the gelation of the liquid detergents and are therefore preferably not used or only in small amounts in the compositions according to the invention, although small proportions of these can be used due to their cleaning properties. Regarding the preferred and less preferred nonionic surfactants, the alkyl groups therein are generally linear, although branching may be allowed, such as on a carbon adjacent to or two carbon atoms away from the straight chain terminal carbon and away from the ethoxy chain if such a branched alkyl group is not more than 3 carbon atoms long. The proportion of carbon atoms in such branched compounds is normally low and hardly exceeds 20% of the total carbon atom content of the alkyl radical. Similarly, although linear alkyls that are terminally attached to the ethylene oxide chains are most preferred and provide the best combination of cleaning action, biodegradability and non-gelling properties, medial or secondary compounds to the ethylene oxide can appear in the chain. They are usually only present in a small amount and generally less than 20%, but can be larger, as with the «tergitols» mentioned. If propylene oxide is present in the lower alkylene oxide chain, it is usually present in amounts below 20% and preferably below 10%.

If larger proportions of non-terminally alkoxylated alkanols or poly-lower alk-oxylated alkanols containing propylene oxide and less balanced nonionic surfactants with regard to the hydrophilic / lipophilic character than mentioned above are used and if other nonionic surfactants can be used instead of the preferred nonionic surfactants mentioned the product obtained does not show the good cleaning effects, stability, viscosity and non-gelling properties as the preferred compositions have, however the use of the compounds according to the invention which control viscosity and gel formation can improve the properties of detergents which are based on such nonionic surfactants . In some cases, for example when poly-lower alkoxylated higher alkanol of higher molecular weight is mostly used because of its cleaning effect, the proportion is adjusted or limited accordingly on the basis of routine examinations in order to achieve the desired cleaning effect and still obtain a product which does not gel and has the desired viscosity. Furthermore, it was found that it is rarely necessary to use high molecular weight nonionic surfactants because of their cleaning effects, since the preferred nonionic surfactants described are excellent cleaning agents and additionally bring about the desired viscosity in liquid detergents without gelling at low temperatures.

Another suitable group of nonionic surfactants are the "Surfactant T" (British Petroleum), which are obtained by dieth-oxylation of secondary C13 fatty alcohols with a narrow ethylene oxide distribution. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 has an average of 7 moles of ethylene oxide; Suffactant T9 has an average of 9 moles of ethylene oxide and Surfactant T12 has an average of 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.

In the compositions according to the invention, the preferred nonionic surfactants include the C13-C15 secondary fatty alcohols with a relatively narrow content of ethylene oxide in the range from 7 to 9 mol and the C9-Cn fatty alcohols which are ethoxylated with about 5 to 6 mols of ethylene oxide .

Mixtures of two or more of these liquid nonionic surfactants can be used and, in some cases, also provide advantages.

Nonionic surfactants with terminal acid groups

The viscosity and gel properties of the liquid detergent compositions are improved by adding an effective amount of a liquid nonionic surfactant with a terminal acid group.

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These compounds consist of nonionic surfactants which have been modified so that a free hydroxyl group is converted into a radical which has a free carboxyl group, such as an ester or partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride. These nonionic surfactants with modified free carboxyl group, which can be generally referred to as polyether carboxylic acids, lower the temperature at which the liquid nonionic products form a gel with water. io

The addition of the nonionic surfactants with a terminal acid group to the liquid nonionic surfactants supports the dispensability of the composition, i.e. pourability, and reduces the temperature at which the liquid nonionic surfactants gel in water 15 without reducing their stability in terms of settling. The acid-terminal nonionic surfactants react in the wash water with the alkalinity of the dispersed builder salt phase of the detergent composition and result in an effective anionic surfactant. 2 (>

Typical examples are the half esters of "Plurafac RA30" with succinic anhydride, the esters or half esters of "Dobanol 25-7" with 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 also be used, such as maleic acid, maleic anhydride, citric acid and the like.

The acid-terminal nonionic surfactants can be prepared in the following way: 30

Acid-free product A: 400 g of the nonionic surfactant product A, which is a C13-C15 alkanol which has been alkoxylated with 6 ethylene oxide and 3 propylene oxide units per alkanol unit, is mixed with 32 g of succinic anhydride and 7 hours at 100 ° C heated. The mixture is then cooled and filtered to remove unreacted succinic material. Infrared analysis showed that about half of the nonionic surfactant had been converted into the acid half ester. 40

Acid-terminated «Dobanol 25-7»: 522 g «Dobanol 25-7», namely a nonionic surfactant, which is the ethoxylation product of a C12-C] 5-alkanol with about 7 ethylene oxide units per molecule of alkanol, were mixed with 100 g of succinic anhydride and 0.1 g of pyridine mixed, 45 the latter acting as an esterification catalyst, and heated to 260 ° C. for 2 hours, then cooled and filtered in order to remove unreacted succinic acid material. Infrared analysis indicated that essentially all of the free hydroxyl residues of the surfactant had been converted.

Acid-terminated «Dobanol 91-5»: 1000 g «Dobanol 91-5», which is a non-ionic surfactant and was obtained by ethoxylating a C9-Cn-alkanol with about 5 ethylene oxide units per molecule of alkanol, with 555 succinic anhydride and 0.1 g of pyridine catalyst mixed and heated to 260 ° C for 2 hours, then cooled and filtered to remove the unreacted succinic acid material. Infrared analysis showed that essentially all free hydroxyl residues of the surfactant had been converted 60.

Other esterification catalysts such as alkali alkoxides, e.g. Sodium methoxide can be used instead of or in a mixture with pyridine.

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The acidic polyether compound, i.e. the acid-terminated nonionic surfactant is preferably added in solution in the nonionic surfactant.

Builders salts

The liquid, non-aqueous, nonionic surfactants which are used in the compositions according to the invention contain, dispersed and suspended, fine particles of organic and inorganic builder salts.

According to the invention, a mixture of organic polyhydroxyacrylic acid, its salts or polyacetalcarb-oxyacid acid builder salts is an essential part of the composition.

Organic builders

Polymeric hydroxyacrylic acid builders

Preferred organic builder salts are alkali metal salts of polyhydroxyacrylic acid and preferably sodium and potassium salts. A particularly preferred builder is poly-hydroxyacrylic acid and its sodium salt.

The polyhydroxyacrylic acid and its salts contain monomeric units of the following formula fJ

OH

Ç-Ç •

R2 COOM

in which R] and R2 are identical or different and can be hydrogen or an alkyl radical having 1 to 3 carbon atoms, such as a methyl, ethyl or propyl radical. Preferred substituents for R 1 and R 2 are hydrogen in both cases. M can be hydrogen, an alkali metal such as sodium or potassium or an alkaline earth metal such as calcium, magnesium or barium. The preferred substituent for M is sodium. The terminal groups of the polymer are not essential and can be H, OH, CH3 or a hydrocarbon chain.

The extent of the polymerization i.e. the value of n is generally limited by the compatibility with regard to the solubility of the polymer in water.

The value of n can be 10 to 10,000, preferably 10 to 1000 and in particular 20 to 200. The polyhydroxyacrylic acid or its salts can have a molecular weight from 1000 to 106 and preferably from 1000 to 105 and in particular from 2000 to 20,000. For example, reference is made on U.S. Patents 3,920,570 and 4,107,411 which disclose processes for making these polymers.

Polyacetal carboxylic acid builder salts

Other preferred organic builder salts are alkali salts of polyacetal carboxylic acids, preferably the sodium and potassium salts.

Generally, the polyacetal carboxylate builder salts used in the present invention have the following general formula

* 1-4

CHO-

I.

COOM

-R "

n in which M is selected from the group consisting of an alkali metal, ammonium, alkyl radicals with 1 to 4 carbon atoms, tetraalkylammonium radicals and alkanolamine radicals with 1 to 4 carbon atoms in the alkyl radical. Alkali metals are preferred, such as preferably sodium or potassium, n has at least a value of 4, and R 1 and R 2 are individually any chemically stable group. R] and R2 can be the same or different.

The end groups R) and R2 can be from a wide range

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Compounds are selected as long as they stabilize the polyacetal carboxylate polymer against rapid depolymerization in alkaline solution. The Rr and R2 end groups are also selected such that they are compatible with the components of the non-aqueous, liquid, nonionic composition according to the invention and in particular with the nonionic surfactant and the agents for preventing gel formation and settling.

The number of repeating groups i.e. the value of n is essential, since the effectiveness of the polyacetal carb oxylate salt as a builder is influenced by the chain length of the polymer. When n is 4, the polymer is effective as a sequestering agent, chelating agent, and builder. The value of n can be up to 400. However, there is no advantage in choosing n greater than about 200. If the value of n exceeds about 100, no significant improvement in the sequestering, chelating and builder properties is noticed.

Accordingly, the polyacetal carboxylate can contain between 10 and 400 units, i.e. an n can correspond to a value of 10 to 400, preferably 50 to 200 and in particular 50 to 100 of the repeating units.

If n has a value of 50 to 200, a very good sequestering effect for calcium and magnesium ions and very good builder properties are achieved.

Suitable, chemically stable end groups are, for example, stable substituents which are also derived from otherwise stable compounds, such as from alkanes, such as methane,

Ethane, propane and butane, from alkenes such as ethylene, propylene and butylene, from branched chain hydrocarbons which can be both saturated and unsaturated, such as 2-methylbutane and 2-methylbutene, from alcohols such as methanol, ethanol, 2-propanol , Cyclohexanol, of polyhydric alcohols such as 1,2-ethanediol and 1,4-benzene-diol, of ethers such as methoxyethane methyl ether, ethyl ether, ethoxypropane and cyclic ethers such as ethylene oxide, epichlorohydrin and tetramethylene oxide, of aldehydes and ketones such as ethanal, acetone , Propanal and methyl ethyl ketones and of carboxylates containing compounds such as alkali salts of carboxylic acids, esters of carboxylic acids and anhydrides. Particularly suitable end groups are alkyl radicals and cyclic alkyl radicals which contain oxygen, such as oxyalkyl radicals such as methoxy, ethoxy, carboxylic acids, and aldehydes, ethers and other oxygen-containing alkyl radicals.

The polyacetal carboxylates can contain polymer fragments; consequently, the polymer can be a linear homopolymer or a copolymer; it can also be branched. Any number of chain extending products can be copolymerized with the polyacetal carboxylates. It is only necessary that the chain-extending component provide at least two reactive sites and not cause depolymerization of the polyacetal carboxylate in an alkaline solution, and that they are compatible with the nonionic surfactant and the gelling and settling agents. Suitable chain-extending compounds are polyhydric alcohols, ethylene oxide, propylene oxide and epihalohydrin-epoxysuccinates, aldehydes such as formaldehyde and acetaldehyde. It is particularly expedient if the chain-extending component contains carboxyl radicals as a substituent. Aliphatic chain-extending compounds with 1 to 4 hydrocarbon atoms such as ethylene oxide or propylene oxide are particularly preferred.

When acetal carboxylate esters are copolymerized with a chain extending component, the amount of acetal carboxylate should be at least about 50% by weight based on the total weight of the polymer to ensure that the polymer effectively sequesteres calcium and magnesium ions and retains builder properties. Preferably the amount of acetal carboxylate is 50 to 80 e.g. at about 80% by weight based on the total weight of the polymer or even higher.

In a preferred embodiment according to the invention, the substituent R | selected from the group consisting of —0CHo

10th

-oc2H5,

/ CH2-C? 2

- OCH \

15 0

CH "

\

CH,

/ 2nd

HOCCHgCHgO ^ H3Ç or or

RC-

I.

H5C2 °

COOM

I.

- CR

I.

COOM

20th

25th

or mixtures of these, while R2 is selected from one of the following radicals:

-CH3, -C2Hs, - (CH2CH20) mH, or

H, C

3I

RC-

I.

H5C2 °

-CH

CH0-CH0 / \

CH "

\ /

0 — CH2

and mixtures thereof, wherein R is hydrogen or an alkyl radical having 1 to 8 carbon atoms and M has the meaning mentioned above.

Compounds in which R] are either preferred

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OCH0CH0 I 2 3 -CH I

CH "

or

COOM -C —CH,

I 3

COOM

or mixtures of these, while R2

40

0CH9CH-

I 2 3

-CH I

CH «

50

and M is sodium and n is 50 to 200.

Other 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 approximately equal molar amounts of methacrylic acid and maleic anhydride, which is completely neutralized to form the sodium salt. This builder is commercially available under the name "Sokalan CP5" and even in small quantities prevents incrustations.

Since the compositions according to the invention are generally highly concentrated and consequently can be used in relatively small doses, it is desirable to supplement the builders with an additional builders, such as with an alkali salt of a lower polycarboxylic acid which has a large calcium and magnesium binding capacity to inhibit incrustation that would otherwise be caused by the formation of insoluble calcium and magnesium salts. Suitable alkali metal salts of polycarboxylic acids are those of citric acid and tartaric acid, such as, for example, monosodium citrate (anhydrous), trisodium citrate, monosodium and disodium tartrate and disodium tartrate.

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Together with the polyhydroxyacrylic acid alkali salts as builders, the alkali salts of polyacetal-carboxylic acid can be used as builders salts (for example “Builder U”. Examples of organic alkaline sequestering builders salts which are compatible with the heptonate, carboxymethyloxy succinate and alginate builders salts or can be used in a mixture with other organic or inorganic builders are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, such as, for example, sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetate (NTA) and triethanolammonium-N- (2-hydroxyethyl) nitrilodiacetate, mixed salts of these aminopolycarboxylates are also suitable.

Other suitable organic builders are carboxymethyl succinates, tartranates and glycolates.

Inorganic builders salts

The detergents according to the invention can also contain inorganic water-soluble or water-insoluble builder salts. Suitable inorganic alkaline builder salts are, for example, alkali carbonates, borates, bicarbonates and silicates; ammonium salts and substituted ammonium salts thereof can also be used. Typical examples of these salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate and potassium bicarbonate.

The alkali silicates are suitable builders salts, which also control the pH value and make the compositions prevent corrosion in relation to the washing machine parts. Sodium silicates with a Na20 / Si02 ratio of 1.6 / 1 to 1 / 3.2 and in particular 1/2 to 1 / 2.8 are preferred. The potassium silicates can also be used in the same proportions.

Although the detergent compositions are preferably phosphate-free or polyphosphate-free or essentially polyphosphate-free, small amounts of conventional polyphosphate builders can be added, provided there are no legal restrictions. Typical examples of such builders are sodium tripolyphosphate (TPP), sodium or potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate.

Sodium tripolyphosphate (TPP) is preferred. In the compositions in which polyphosphates are added, it is added in amounts of 0 to 30, such as 0 to 20 and 5 to 15% by weight.

Other typical suitable builders include also those as described in U.S. Patents 4,316,812, 4,264,466 and 3,630,929. The inorganic alkaline builder salts can be used with the nonionic surfactants or in mixtures with other organic or inorganic builder salts.

Water-insoluble crystalline and amorphous aluminosilicate zeolites can be used as the inorganic builder salts. The zeolites have the general formula

(M20) x (Al203) y (Si02) zwH20

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

A wide variety of crystalline zeolites, i.e. thus aluminosilicates are used, as are described, inter alia, in British Pat. No. 1,504,168, US Pat. No. 4,409,136 and CA Patents 1,072,835 and 1,087,477. An example of a suitable amorphous zeolite is described in BE-PS 835 351.

Other additives such as clays, in particular water-insoluble types, are suitable additives in the compositions according to the invention. Bentonite is particularly suitable. This material is primarily a montmorillonite, which is a hydrated aluminum silicate, in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which the various amounts of hydrogen, sodium, potassium, calcium etc. can be loosely combined. The bentonites in their cleaned form, i.e. products that are free of gravel and sand, are suitable for detergents and contain at least 50% montmorillonite and have a cation exchange capacity of at least 50 to 75 meq / 100 g bentonite. Preferred bentonites are the Wyoming or Western U.S. Bentonites, also sold as Thixo-Jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites can soften textiles as described in GB-PS 401 413 and 461 221.

Viscosity control and gel prevention agent.

The addition of an effective amount of low molecular weight amphiphilic compounds to the detergent compositions which control the viscosity and prevent gel formation with the nonionic surfactants essentially improves the storage properties of the composition. The chemical structure of the amphiphilic compounds can be regarded as analogous to the liquid ethoxylated and / or propoxylated fatty alcohol nonionic surfactants, but they have a relatively short hydrocarbon chain with lengths of C2 to C8 and a low content of ethylene oxide of about 2 to 6 ethylene oxide groups each Molecule.

Suitable amphiphilic compounds have the following general formula

R0 (CH2CH20) nH

in which R is a C2 to C8 alkyl radical and n is a number from 1 to 6 on average.

In particular, the compounds are low, ie C2 to C3 alkylene glycol mono C2 to C5 alkyl ethers and in particular mono-, di- or tri C2 to C3 alkylene glycol mono C] to C5 alkyl ethers. Typical examples of suitable amphiphilic compounds include Ethylene glycol monoethyl ether, C2H5-0-CH2CH20H, diethylene glycol monobutyl ether, C4H9-0- (CH2CH20) 2H, tetraethylene glycol monobutyl ether, C4H7-0- (CH2CH20) 4H and dipropylene glycol mono-methyl ether, CH3-0- (CH2CH0) 2.

I.

CH3

Diethyl glycol monobutyl ether is particularly preferred.

By incorporating the low molecular weight lower AI -kylenglykolmonoalkylether in the compositions of the invention, their viscosity is reduced so that they are easier to pour; settling stability and dispersibility when added to warm or cold water are also improved.

The compositions according to the invention have better viscosity and stability properties and remain stable and pourable at temperatures down to 5 ° C. and lower.

Stabilizing agent

In one embodiment of the present invention

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the physical stability of the suspension of builders and all other suspended additives such as bleach in the liquid carrier is improved by the presence of a stabilizing agent which is an alkanol ester of phosphoric acid or an aluminum salt of a higher fatty acid.

Improvements in the stability of the composition can be achieved in some formulations by adding a small amount of an acidic organic phosphorus compound that has an acidic -POH group, such as a partial ester of a phosphoric acid with an alkanol. These can increase the stability of the suspension of builders in a non-aqueous liquid nonionic surfactant.

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

A typical example is a partial ester of phosphoric acid with a C16 to C18 alkanol (Empiphos 5632 from Marchon), which consists of about 35% monoesters and 65% diesters.

The incorporation of very small amounts of these acidic, organic phosphorus compounds makes the suspension remarkably more stable against settling when standing, although it remains pourable, although in view of the low concentration of stabilizing agent e.g. below about 1% the plastic viscosity generally decreases.

Further improvements in stability and to prevent settling can be achieved by adding small but effective amounts of an aluminum salt of a higher fatty acid.

Higher aliphatic fatty acids having 8 to 22 and preferably 10 to 20 and in particular 12 to 18 carbon atoms are preferred. The aliphatic residue can be saturated or unsaturated, straight or branched. In the case of nonionic surfactants, mixtures of fatty acids can also be used, namely those derived from natural products such as tallow fatty acid, coconut fatty acid etc.

Examples of fatty acids with which the aluminum salt stabilizer can be formed include Decanoic acid, do-decanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid and mixtures of these acids. The aluminum salts of these acids are commercially available products and are preferably used as tri-acids such as aluminum stearate as aluminum tristearate Al (CI7H35COO) 3. The monoacid salts such as Aluminum monostearate, Al (OH) 2 (C17H35 COO) and diacid salts such as aluminum distearate, Al (OH) (C17H35COO) 2 and mixtures of two or three of the mono-, di- and tri-acid salts of aluminum can also be used. The trisau real aluminum salt preferably forms at least 30, preferably 50 and in particular at least 80% of the total amount of the aluminum salt of the fatty acid.

The above-mentioned aluminum salts are commercially available and can be easily, e.g. by saponification of a fatty acid e.g. of animal fat, stearic acid, etc. and then treating the side obtained with alum, alumina, etc.

Without being bound by theory, it is believed that the aluminum salt prevents the suspended particles from settling by increasing the wettability of the solid surfaces by the nonionic surfactant. This increase in wettability consequently allows the suspended particles to remain more easily in the suspension.

Only very small amounts of this stabilizing aluminum salt are required to achieve significant improvements in physical stability.

In addition to the effect of the aluminum salt as a stabilizing agent, it has further advantages over other stabilizing agents, since it is nonionic and is compatible with the nonionic surfactants and does not interfere with the cleaning action of the detergent composition. It shows a certain foam suppressing effect and it can increase the effectiveness of fabric softening agents and thus contributes to a longer rest period for the suspensions

Bleach

For the sake of simplicity, the bleaches can be divided into chlorine bleach and oxygen bleach. Chlorine bleaches are generally sodium hypochlorite (NaOCl), potassium dichloroisocyanurate with 59% available chlorine and trichloroisocyanuric acid with 95% available chlorine. Oxygen bleaching agents are preferred and are per-compounds that release oxygen peroxide in solutions, such as sodium and potassium perborates, per-carbonates and perphosphates and potassium monopersulfate. Perborates and especially sodium perborate monohydrate are particularly preferred.

The peroxygen compound is preferably used together with an activator. Suitable activators which reduce the operating temperature of the peroxy bleaching agent are disclosed, for example, in US Pat. No. 4,264,466 or in US Pat. No. 4,430,244 (column 1). Polyacylated compounds are preferred activators such as tetraacetylethylene diamine (TAED) and pentaacetyl glucose.

Other suitable activators are, for example, acetyl salicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TA-GU) and its derivatives. Other suitable activators are described, for example, in U.S. Patents 4,111,826, 4,422,950 and 3,661,789.

The bleach activator reacts with the peroxy compound and forms a peroxy acid, which has a bleaching effect in the wash liquor. A sequestering agent with a high complexing effect is preferably used in order to prevent any undesirable reactions between the peroxyacid and hydrogen peroxide in the wash liquor in the presence of metal ions.

Suitable sequestering agents for this purpose are the sodium salt of ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepenetamethylenephosphonic acid (DTPMP), which is sold under the name "Dequest 2066", and ethylenediaminetetra-methylenephosphonic acid (EDITEMPA). The sequestering agents can be used alone or in mixtures.

To prevent loss of peroxide bleach e.g. of sodium perborate due to enzyme-induced decomposition e.g. To prevent them by catalase enzymes, the compositions may additionally contain an enzyme inhibitor, i.e. a compound capable of preventing enzyme-induced decomposition of the peroxide bleach. Suitable inhibitors are disclosed in U.S. Patent 3,606,990.

A particularly suitable inhibitor are hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred non-aqueous compositions according to the invention, suitable amounts of hydroxylamine salt inhibitors can be used in an amount of only about 0.01 to

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0.4% by weight should be present. In general, the suitable amounts of enzyme inhibitors are present in an amount of up to 15%, for example 0.1 to 10% by weight, based on the composition.

Other detergent additives

In addition to the builders, various other detergent additives can also be present in order to impart further functional or aesthetic properties to the detergent. The compositions may contain minor proportions of compounds which suspend or prevent dirt, such as polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A preferred agent for preventing redeposition is sodium carboxymethyl cellulose with a 2: 1 ratio of CM / MC, which is sold under the name “Relatin DM 4050”.

Optical brighteners for cotton, polyamide and polyester textiles can be used. Suitable optical brighteners are stilbenes, triazoles and benzidine sulfone compositions, in particular sulfonated substituted tri-azinyl stilbene, sulfonated naphthotriazole stilbene, benzidine sulfone, etc., with stilbene and triazole preparations being preferred. In particular, the stilbene brightener N4, which is a dimorpholinodianilinostilbenesulfonate, is preferred.

Furthermore, enzymes, preferably proteolytic enzymes such as subtilisin, bromelin, papain, trypsin and pepsin, but also amylase enzymes, lipase enzymes and mixtures thereof can be used. Preferred enzymes are protease slurries, Esperase slurries and amylase. A preferred enzyme is «Esperase SL8», which is a protease.

Foam pressers e.g. Silicon compounds such as "Silicane L 7604" are used in small but effective amounts.

Bactericides, such as, for example, tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments which are dispersible in water, preservatives, UV absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color-fast bleaches, Perfume and dyes and bluing agents such as ultramarine blue can be used.

The compositions can also contain inorganic insoluble thickeners or dispersants with a very large surface area, such as finely divided silicon dioxide with an extremely small particle size of 5 to 100 μm in diameter, such as e.g. Contain "Aerosil" or other voluminous inorganic carriers as disclosed in US Pat. No. 3,630,929 in proportions of 0.1 to 10 and for example 1 to 5%. However, the compositions which produce peroxy acids in the wash liquor, that is to say compositions which contain peroxy compounds and an activator suitable therefor, should preferably not contain any such compounds and other silicates. It has been found that, for example, silicon dioxide and silicates cause undesired decomposition of the peroxyacid.

In one embodiment according to the invention, the stability of the builder salts in the composition during storage and the dispersibility of the composition in water were improved by reducing the particle size of the solid builders to less than 100 μm and preferably less than 40 μm and in particular less than 10 μm crushed. The solid builders are generally supplied in particle sizes of 100, 200 or 400 μm. The nonionic liquid surfactant phase can be mixed with the solid builders before or after crushing them.

In a preferred embodiment according to the invention, the mixture of liquid nonionic surfactant and solid constituents is treated in a grinder by reducing the particle size of the solid constituents to below 10 μm, for example to an average particle size of 2 to 10 μm or even lower, such as for example 1 pm. Preferably less than 10% and in particular less than 5% of all suspended particles have a particle size above 10 μm. Compositions whose dispersed particles have such a small particle size show improved stability against separation or settling during storage The acid-terminal nonionic surfactants support the dispersibility of these dispersions without a corresponding reduction in the dispersion stability compared to settling.

When comminuting, the proportion of solid components should preferably be large enough, i.e. at least about 40% such as about 50% so that the solid particles are in contact with one another and are not substantially shielded from one another by the liquid nonionic surfactant.

After grinding, any remaining liquid nonionic surfactant can be added to the ground formulation. Grinders such as ball mills or similar grinders give good results here. You can use a laboratory mill with abrasion elements made of steatite balls with a diameter of 8 mm. When working on a larger scale, continuously operated grinders are used, in which the grinding balls have a diameter of 1 to 1.5 mm and work in a very small space between a stator and a rotor, which is operated at a relatively high speed. When using such a grinder e.g. In a "CoBall mill", the mixture of nonionic surfactant and solids is preferably first passed through a grinder which does not produce such a fine comminution, such as a colloid mill, to bring the particle size to less than 100 (eg about 40 (im) before grinding to an average particle size below about 10 µm in a continuous ball mill.

In a preferred liquid heavy-duty detergent composition for textiles according to the invention, the proportions based on the total weight of the composition of the individual components are in the following ranges:

Liquid nonionic surfactant in a range from about 20 to 60, such as 25 to 50% by weight.

Acid-terminated nonionic surfactant is preferably added in an amount ranging from about 2 to 30, such as 2 to 20 or 10 to 25% by weight.

Polyhydroxyacrylic acid or its salt or polyacetal carboxylate builder salts in the range from 5 to 50, such as 10 to 30% by weight

Polyphosphate builders in a range from 0 to 30, such as 0 to 20 and 5 to 15% by weight.

Copolymers of polyacrylate and polymaleic acid hydride alkali salts as an incrustation preventing agent in the range of about 0 to 10, such as 2 to 8% by weight.

Alkylene glycol monoalkyl ether as an antigelling agent is preferably added to the composition in amounts ranging from about 0 to 20, e.g. from 5 to 30, such as 5 to 15 or 20% by weight.

Phosphoric acid alkanol esters as stabilizing agents in a range from 0 to 2.0 or 0.1 to 2.0 such as 0.10 to 0.5 or 1% by weight.

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Aluminum salt of a fatty acid as a stabilizing agent in the range of about 0 to 3.0 e.g. 0.5 to 2.0 such as 0.1 to 1.0% by weight.

At least one of the stabilizing agents, namely phosphoric acid ester or aluminum salt, should preferably be present in the composition according to the invention.

Bleaches in a range from about 0 to 35, e.g. 5 to 40, such as 5 or 30% by weight.

Bleach activators in a range from about 0 to 25, e.g. 2 to 25, such as 5 to 20% by weight.

Sequestering agents for the bleaching agents in the range from about 0 to 3.0 and preferably 0.5 to 2.0% by weight.

Redeposition preventing agents in the range of about 0 to 3.0, preferably 0.5 to 2.0% by weight.

Optical brightener in the range from about 0 to 2.0, preferably 0.1 to 1.5% by weight.

Enzymes in the range of about 0 to 3.0, preferably 0.5 to 2.0% by weight can be present.

Perfumes in the range of about 0 to 2.0, preferably 0.1 to 1.0% by weight) can be present.

Furthermore, the various additives mentioned can optionally also be added in order to achieve the desired function of these additives.

Mixtures of acid-terminated nonionic surfactants and alkylene glycol alkyl ethers can be used as antigelling agents, and in some cases advantages are achieved by using these mixtures alone or by adding a stabilizing agent and a sedimentation preventing agent to the mixture.

When choosing the additives, it must be taken into account that they are compatible with the main components of the detergent composition.

The concentrated non-aqueous, nonionic, liquid detergent compositions according to the invention can be easily dispensed into the water of the washing machine. In the washing machines currently customary, 175 g of powdery detergent are normally required for a full charge, while according to the invention only about 67 ml or 80 g of the concentrated liquid nonionic detergent composition are required.

In a preferred embodiment according to the invention, the following formulations can be used:

Formulations with an alkali polyhydroxyacrylate as a builder

Component weight%

Nonionic surfactant 30-55

Acid-terminated surfactant 1-10

Alkylene glycol monoalkyl ether 3-15

Polyhydroxyacrylate 7-22

Alkanol phosphoric acid esters 0.1-0.9

Alkaline perborate bleach 10-22

Bleach Activator (TAED) 4-15

Optical brightener 0.1-0.6

Enzymes 0.5-1.5

Perfume 0.1-0.8

Alkali salt of polyacetal carboxylic acid as a builder

Nonionic surfactant 30-55

Acid-terminated surfactant 2-18 alkali salt of a polyacetal carboxylic acid as

Builders 5-22

Polyphosphate builder salt 0-20

Alkanol phosphoric acid esters 0.1-0.9

Alkaline perborate bleach 7-22

Bleach Activator (TAED) 4-12

Optical brightener (Stilbene brightener N4) 0.1-0.8 Enzyme (Protease-Esperase SL8) 0.5-1.5

Perfume 0.1-0.8

The invention is explained in more detail below by the following examples.

example 1

A concentrated non-aqueous liquid nonionic detergent composition was made from the following ingredients:

Ingredients% by weight

Ethoxylated secondary C13 fatty alcohol with 20 on average 9 moles of ethylene oxide (surfactant T9)

Ethoxylated secondary C13 fatty alcohol with 20 on average 7 moles of ethylene oxide (surfactant T7)

Acid-terminated reaction product with 4.0 succinic anhydride (Dobanol 91-5)

Diethyl glycol monobutyl ether 10

a-Poly-hydroxyacrylate as sodium salt 17.0

Alkanol phosphoric acid ester 0.3

Sodium perborate monohydrate as bleach 17.0

Tetraacetylethylenediamine (TAED) as a bleach activator

Stilbene whitener 0.4

Esperase slurry 1.0

Perfume 0.3

100.0

Example 2

A concentrated non-aqueous liquid ■ nonionic detergent was made from the following ingredients.

Ingredients% by weight

Nonionic surfactant consisting of equal 40.0 parts of a C13 to C15 fatty alcohol which is partly condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide and partly with 5 moles of propylene oxide and 10 moles of ethylene oxide

Acid-terminated «Dobanol 91-5», which is reacted with 14.0 succinic anhydride Sodium salt of polyacetal carboxylic acid (Buil- 17.0 der U)

Alkanol phosphoric acid ester 0.3

Sodium perborate monohydrate as bleaching agent 17.0 tetraacetylethylenediamine (TAED) as bleaching agent 10.0 activator

Optical brightener (Stilben N4) 0.4

Esperase slurry 1.0

Perfume 0.3

The compositions according to Examples 1 and 2 are or can be ground for about 1 hour in order to bring the particle size of the suspended builder salts down to less than 10 μm. The detergent compositions are stable and do not gel when stored and have a high washing performance.

The compositions can be made to a small particle size without grinding the builder salts and suspended solid particles, but the best results are obtained by grinding the composition to reduce the particle size of the suspended solid particles.

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The builders salts, as supplied, can be used; the builder salts and the suspended solid particles can also be completely or partially milled before being mixed with the nonionic surfactant. The grinding can partly be carried out before the mixing and is then continued after the mixing; the entire comminution can also be carried out after mixing with the liquid surfactant.

The compositions according to the invention, which contain the alkali salt of polyhydroxyacrylic acid as a builder, can be processed with conventional thickeners such as bentonite and «Aerosil» if you want a creamy or pasty mass; they can also be used as an abrasive cleaning agent.

C.

Claims (14)

671235 2nd PATENT CLAIMS 1. Non-aqueous liquid heavy-duty detergent characterized by a content of at least one liquid nonionic surfactant, a polyhydroxyacrylic acid optionally substituted in the β-position by 1 or 2 Cr to C3-alkyl radicals or a salt thereof as a builder or an organic polyacetal carboxylate builder salt, - At least one compound selected from the group consisting of a nonionic surfactant with a terminal acid group as an agent preventing gel formation and an alkylene glycol monoalkyl ether and - a stopping device. 2. Detergent according to claim 1, characterized in that it contains 5 to 50% by weight of a polyhydroxyacrylic acid or a salt thereof as a builder or a polyacetal carboxylate as a builder salt. 3. Detergent according to claim 1, characterized in that the polyhydroxy acrylic acid monomeric units of the following formula fr C - A OH l C - COOM fr c ■ I. Ro OH I ■ C COOM contains n in which R] and R2 are identical or different and denote hydrogen, methyl, ethyl or propyl and M is sodium or potassium and the value of n is selected so that the polymer is water-soluble. 6. Detergent according to claim 1, characterized in that it is free of phosphate builders and a nonionic surfactant in an amount of about 30 -55 wt.% An acid group-terminated surfactant in an amount of about 1 -10 wt.% Alkylene glycol monoalkyl ether in an amount of about 3 -15% by weight the sodium salt of a polyhydroxyacrylic acid as builder in an amount of about 7 -22% by weight a C16 to C18 alkanol ester of phosphoric acid in an amount of about Contains sodium perborate monohydrate as a bleaching agent in an amount of about tetraacetylethylene diamine as a bleach activator in an amount of about. 0.1-0.9% by weight 10 -22% by weight 4 -15% by weight 10th 7. Detergent according to claim 6, characterized in that the polyhydroxyacrylate has a molecular weight of 2000 to 20,000. 8. Detergent according to claim 1, characterized in that the polyacetal carboxylate has the general formula R1 "" for 110 = 1 R2 IÇOOHJ 20th n contains, in which Rj and R2 are identical or different and are a hydrogen and / or a Q to C3 alkyl radical, while M is hydrogen or an alkali, alkaline earth or ammonium cation. 4. Detergent according to claim 1, characterized in that it at least one liquid, nonionic surfactant in an amount of 25 to 50% by weight, an acid group-terminated nonionic surfactant in an amount of 2 to 20% by weight, an alkylene glycol monoalkyl ether in an amount of about 5 to 20% by weight, a polyhydroxyacrylate builder in an amount of about 10 to 30% by weight and - Contains an alkanol phosphoric acid ester in an amount of about 0.1 to 1.0 wt.%. 5. Detergent according to claim 4, characterized in that the polyhydroxyacrylic acid builder has monomeric units of the formula in which M is selected from the group consisting of an alkali metal, ammonium, Q to Q alkyl radicals, tetraalkylammonium radicals and alkanolammonium radicals having 1 to 4 carbon atoms in the alkyl radical, and n has a value of 25 of at least 4, and R, and R2 are selected such that they are individually stable radicals which stabilize the polymer against depolymerization in alkaline solution and are compatible with the constituents of the nonionic detergent. 9. Detergent according to claim 1, characterized in that it is free of polyphosphates or has a low polyphosphate content and at least one liquid, nonionic surfactant in an amount of about 25 to 50% by weight, an acid group-terminated nonionic surfactant in an amount of about 10 to 25% by weight, a polyacetal carboxylate builder in an amount of about 10 to 30% by weight, contains an alkanol phosphoric acid ester in an amount of et-40 wa 0.1 to 1.0 wt.%. 10. Detergent according to claim 9, characterized in that the polyacetal carboxylate has the following general formula 30th 35 45 CHO " I. COOM L_ -in «2 50 in which M is an alkali metal, and n has a value from 50 to 200, and R 1 and R 2 are selected so that they are individually stable radicals which stabilize the polymer against depolymerization in alkaline solution and which comprise the Be-55 of the nonionic detergent are compatible. 11. Detergent according to claim 1, characterized in that it 60 a nonionic surfactant in an amount of about an acid group terminal surfactant in an amount of about a sodium salt of a polyacetalcar-65 acid in an amount of about a C] 6 to C! 8 alkanol ester of phosphoric acid in an amount of about 30 -45% by weight 2 -18% by weight -22% by weight 0.1-0.9% by weight 3rd 671 235 Sodium perborate monohydrate as Bleach in an amount of about 7-22% by weight Tetraacetylethylenediamine (TAED) as Bleach activator in an amount of about 4-12% by weight contains. 12. Detergent according to claim 1, characterized in that the polyacetal carboxylate has the following formula I. COOM n in which M is sodium or potassium and n is from 50 to 200 and Rj is a stabilizing end group, in particular COOM OCH, CH " I 2 J -CH I CH, -C -CH, I 2 COOM or a mixture of these and R2 OCH0CH, I 2 3 -CH I CH, and the polyacetal carboxylate segments make up 50 to 80% by weight of the total polyacetal carboxylate. 13. Detergent according to claim 12, characterized in that the polyacetal carboxylate is the sodium salt. 14. Detergent according to claim 1, characterized in that it is an alkali perborate monohydrate as a bleaching agent in an amount of about 5 to 30 wt.%, Contains tetraacetylethylenediamine as a bleach activator in an amount of about 5 to 20% by weight and optionally one or more detergent additives selected from the group consisting of optical brighteners, enzymes and perfume.