GB2046295A - A slurry detergent - Google Patents

Abstract

A slurry detergent comprises the following components: Components Wt. % water 25.0 to 80.0 a water dispersible cross-linked interpolymer of a monomeric polymerizable alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acid, and a polyether of a polyol having 1 to 4 mono-saccharide units or a reduced derivative thereof in which a carbonyl group is converted to an alcohol group, and pentaerythritol, the hydroxyl groups of said polyol being etherified such that the polyol has at least two allyl or methallyl ether groups per molecule 0.1 to 3.0 sodium or potassium hydroxide dry basis 2.5 to 25.0 a non-ionic surfactant 0 to 12.0 a polyphosphate 0 to 30.0 a polyacrylate or polymethacrylate salt, dry basis 0.2 to 4.0 an anionic surfactant 0 to 10.0 an optical brightener 0 to 2.0 a crystalline sodium aluminosilicate zeolite 0 to 30.0 sodium carboxymethylcellulose 0 to 2.0 with the proviso that at least one of a non-ionic or anionic surfactant is present.

Description

SPECIFICATION Slurried detergent The present invention relates to a highly concentrated heavy duty built laundry washing product in a form amenable to mechanical metering ((i.e., in slurry form), containing Na or K hydroxide, detergent, sodium polyacrylate, a modified polyacrylic acid salt and water and, optionally, a water-insoluble aluminosilicate ion exchange material, or a polyphosphate such as sodium tripolyphosphate or mixtures thereof, optical brightener, colouring agent, sodium carboxymethyl cellulose and perfume).

Both granular and liquid laundry products have a number of inherent deficiencies. Granular products are subject to caking in their package or in the dispenser from which they are fed into the laundry machine. They contain bulk aids or fillers which serve no direct purpose in laundering fabric.

On the other hand, conventional liquid laundry washing products are limited in the amount of active ingredients which can be dissolved in water and still provide a stable system.

We have discovered, according to the present invention, that incorporating the best properties of the liquid laundry detergent and the granular laundry detergent into a single new laundry product is best achieved by using a novel blend in a slurry form. The slurry form eliminates the caking and the dusting of powdered laundry detergents and provides a positive means of mechanically dispensing into the laundry machine. It also provides improved performance over liquid products, which are limited in concentration by the mutual compatibility of its ingredients.

The use of a slurry allows the use of materials normally incompatible and/or insoluble since in a slurry, no true solution need be formed. Rather, a semi-fluid, essentially homogeneous mass is the only prerequisite for a satisfactory product.

The new compositions of this invention are particularly useful in areas where the water supply contains high calcium and magnesium hardness. The composition has good physical stability; at 1 20 F. for two weeks it generally shows only very slight separation. It can easily be metered using a peristaltic dispensing pump.

Table 1 identifies the components and quantities of the slurry composition of the present invention and also includes preferred quantities. It will be understood that at least one of a nonionic or an anionic surfactant must be present. Of course, other ingredients such as perfume can be present if desired.

Table 1 Preferred Preferred Preferred Narrow Broad Components Formulation Range. Wt. % Range, Wt. % Water 45.4 Wt. % 45.0 - 73.0 25.0 - 80.0 Modified polyacrylic acid thickening agent (defined below) 0.5 " 0.3 - 1.3 0.1 - 3.0 Sodium or potassium hydroxide Dry Basis 12.5 " 5.5 - 19.5 2.5 - 25.0 e.g. liquid caustic soda 50% active 25.0 " 11.0 - 39.0 5.0 - 50.0 Colouring agent e.g. brilliant alizarine 14 or 15 g/.

milling blue BL 1000 lbs.

Non-ionic surfactant 5.0 Wt. % 2.0 - 8.0 0 - 12.0 Polyphosphate 16.0 " 0 - 20.0 0 - 30.0 Sodium polyacrylate, Dry Basis 1.2 " 0.2 - 2.0 0.2 4.0 e.g. as a 20% solution in water 6.0 " 1.0 - 10.0 1.0 - 20.0 Anionic surfactant 2.0 " 0 - 4.0 0 - 10.0 Optical brightener 0.1 " 0.05 - 1.0 0 - 2.0 Crystalline sodium aluminosilicate zeolite --- 0 - 18.0 0 - 30.0 Sodium carboxymethylcellulose --- 0.5 - 1.5 0 - 2.0 The modified polyacryiic acid thickening agent used in the slurry of the present invention is a dispersible cross-linked interpolymer of a monomeric polymerizable alpha-beta monoolefinically unsaturated lower (i.e. of 1 to 6 carbon atoms) aliphatic carboxylic acid, especially acrylic acid, and a polyether of a polyol which contains 1 to 4 monosaccharide units, typically an oligo saccharide, or a reduced derivative thereof of said polyol in which the carbonyl group is converted to an alcohol group, and pentaerythritol, the hydroxyl groups of said polyol being etherified with allyl (or methallyl) groups, such that the polyol has at least two allyl ether groups per polyol molecule, generally used as a monomer mixture. A typical such polymer can be made by co-polymerizing about 98-99.5 parts, especially about 98.75 parts, by weight of acrylic acid with about 0.5-2.0 parts of polyallyl polyether of sucrose having about 2 or 4 to 8 allyl groups per molecule, especially about 1.25 parts of polyallyl polyether of sucrose having about 5.6 allyl groups per molecule. A typical preparation is given below.

Preparative Example Solution polymerization using the following reaction mixture can be used: Raw Material Parts by Weight Acrylic acid 98.75 Polyallyl sucrose 1.25 Azoisobutyronitriie 1.0 Benzene 880.0 The polymerization is carried out under autogenous pressure at 50"C until the reaction is complete, which may require 20 hours. The polymer formed is a fine friable powder. The powder, freed from solvent, is in the acid form, and is ready to use. Molecular weight is about 1,000,000. Preferably the product is neutralized with alkali, e.g., NaOH or KOH, to develop its thickening properties in formulations. Such alkali is provided in the formulations in Table 1.

The polyallyl sucrose can be made by the allylation of sucrose. Typically the sucrose is dissolved in concentrated aqueous sodium hydroxide solution, 1 1/2 equivalent weights of allyl chloride for every hydroxyl group in the sucrose molecule added and the mixture sealed in a reaction autoclave. The autoclave and its contents are heated to 80 to 83"C for about five hours until no further drop in pressure occurs. The autoclave is cooled and the contents diluted with water until all precipitated salts are dissolved. An organic layer separates out and is isolated and steam distilled. The crude product resulting from steam distillation is then washed with a large volume of water. The wet polyallyl sucrose is then dissolved in toluene, decolourized with "Darco" activated charcoal and dried with sodium sulphate.The toluene is finally removed by distillation under reduced pressure at 100"C. The residue remaining is a polyallyl polyether of sucrose. It has an average of 5.6 allyl groups and 1.97 hydroxyl groups per molecule. The yield is about 91%.

The polymers formed from the reaction of polyallyl sucrose and acrylic acid are described in U.S. Patent No. 2 798 053, Example 5 being a typical example of their preparation. Similar procedures for making the same or similar acrylic-allyl sucrose copolymers are given in U.S.

Patent No. 4 130 401. Carbopol 941, a modified polyacrylic acid available commercially from B.F. Goodrich, Akron, Ohio, is considered similar to that prepared in the Preparative Example and is especially suitable. Other commercially available resins which can be used include Carbopol 934 and Carbopol 940.

This Preparative Example gives a polyacrylic acid modified by slight cross-linking with polyallyl sucrose. The molecular weight is about 500,000 to 10,000,000 typically about 1,000,000.

As indicated above, the modified polyacrylic acid thickening agent used in this invention is derived from a polyether of a polyol having 1 to 4 monosaccharide units. In addition to the oligosaccarides themselves, their reduction products such as the alcohols, keto-alcohols and aldo-alcohols and their oxidation products which retain the original saccharide chain such as the sugar acids, the keto-acids, and the aldo-acids can be used. Illustrative saccharides of this class are the monosaccharides such as glucose, galactose, fructose, sorbose, and rhamnose, disaccharides such as sucrose, arabinose, maltose and lactose, and trisaccharides such as raffinose.

Of these the disaccharide, sucrose, is much preferred because of its ready availability and its ability to produce polyethers of great reactivity with carboxylic monomers.

The non-ionic surfactant is preferably an oxyethylenated linear long-chain, e.g. C,2-C,5, alcohol, for example obtained using 3-12 moles of ethylene oxide, especially 7 moles of ethylene oxide per mole of alcohol, but other non ionic detergents or mixtures thereof can be used.

The polymethacrylate salt is generally sodium polyacrylate which typically has a molecular weight from 50,000 to 200,000, especially about 90,000. It is available as PSK-20 from Dearborn Div., Chemed Corp. (Molecular weights herein given are weight average unless otherwise stated). The sodium polyacrylate is preferably incorporated/added in liquid form in solution, e.g., in water. A 20% solution in water is preferred. Other monovalent polyacrylic and polymethacrylic acid salts are also suitable.

The anionic surfactant is preferably an alkyl aryl sulphonic acid or salt thereof. These are well known surfactant detergents and are available commercially as compounds of the formula alkyl

where the alkyl group is C8-C,8 and R is Na, K, or H. The preferred product is linear dodecylbenzene sulphonic acid but other anionic detergents or mixtures thereof are also suitably incorporated.

The optical brightener or whitener is suitably 4,4'-di(2-sulphostyryl biphenyl), disodium salt, available commercially as Tinapol CBS from Ciba-Geigy. Numerous other suitable optical brighteners are commercially available, and the type is not critical, except that it should be chemically stable in the composition. A typical optical brightener for laundry use is made by diazotization of 4-aminostilbene-2-sulphonic acid, followed by coupling with e.g., a naphthylamine derivative, and oxidation to the triazole compound.

The zeolite, a crytalline sodium aluminosilicate, generally has the formula Na,2[(AI02),2 (SiO,),,l . XH2O; it is available commercially as zeolite 4A from various sources, e.g., as Sylosiv 100 from W.R. Grace 8 Co. with X = 0-2, typically 1 or 2. When it is put in water, it rapidly hydrates until X = about 20-30. Hence, operationally, X = 0-30.

As for the polyphosphate, there are several well-known polyphosphates useful as builders in laundry operations, e.g., the alkali metal pyrophosphates, sodium hexametaphosphate and sodium tripolyphosphate which is preferred, especially in powdered form. These are also known as complexing or condensed phosphates.

The following Example further illustrates the present invention.

Example A slurried detergent was prepared as follows. The ingredients as given in Column 1 of Table 1, using liquid sodium hydroxide, and the most preferred ingredients given above, were added in order to a kettle equipped with a jacket capable of heating and cooling and a mixer capable of running at a minimum of 1 50 rpm. Sufficient ingredients were used to make a 1000 pound mix. The water was added first, at 50"-80"F. Next the modified polyacrylic acid was added, using a funnel disperser. This component was added slowly to avoid lumping. It was mixed into the water with high agitation until dissolved. The liquid caustic soda was added next and mixed for ten minutes. The alizarine blue dye was predissolved in three quarts of hot tap water and added to the batch.The ethoxylated alcohol detergent (non-ionic surfactant) was added slowly and mixed for ten minutes with maximum agitation. At this point water is run through the kettle jacket to provide cooling to 120 or less. The sodium tripolyphosphate was added slowly through a four-to-the-inch screen with the mixer going at the highest speed. A good rate of addition is five minutes per 100 pounds with a five-minute pause between each 100 pounds added. If the powder floats or otherwise does not mix or wet, allow more time between additions. The rate of addition of the sodium tripolyphosphate is very important for good mixing.

After all of the sodium tripolyphosphate is added, mix one hour. The temperature is maintained at 120"F or less after the addition of the sodium tripolyphosphate. At the end of that time pull a sample for inspection. The sample should flow like a lotion with no curding. If curding occurs, mix an additional hour and recheck. Continue mixing until smooth. Next add the sodium polyacrylate and mix for fifteen minutes. Next add the dodecyl benzene sulphonic acid, which is typically used in an amount up to 0.35 wt.%., and mix for fifteen minutes. The anionic surfactant is typically used in an amount from 0.5 to 4 wt.%. Next add the sulphostyryl derivative and mix for one hour. This completes preparation of the composition.

In compositions that include sodium aluminosilicate, which is typically used in an amount up to 25 wt.%, and/or sodium carboxymethylcellulose, these ingredients should be stirred into the vessel in similar fashion, with a view to eliminating lumps and sediment.

This slurried laundry product, in effect, uses a water softener system suspended in a base thickened with a modified polyacrylic acid salt and a polyacrylic acid salt. The modified polyacrylic acid salt and the polyacrylic acid salt act as suspending aids to keep the water softener (zeolite, sodium tripolyphosphate or other water softener) suspended uniformly for prolonged periods of storage.

Claims (13)

1. A slurry detergent which comprises the following components: Components Wt. % water 25.0 to 80.0 a water dispersible cross-linked interpolymer of a monomeric polymerizable alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acid, and a polyether of a polyol having 1 to 4 mono-saccharide units or a reduced derivative thereof in which a carbonyl group is converted to an alcohol group, and pentaerythritol, the hydroxyl groups of said polyol being etherified such that the polyol has at least two allyl or methallyl ether groups per molecule 0.1 to 3.0 sodium or potassium hydroxide dry basis 2.5 to 25.0 a non-ionic surfactant 0 to 12.0 a polyphosphate 0 to 30.0 a polyacrylate or polymethacrylate salt, dry basis 0.2 to 4.0 an anionic surfactant 0 to 10.0 an optical brightener 0 to 2.0 a crystalline sodium aluminosilicate zeolite and 0 to 30.0 Sodium carboxymethylcellulose 0 to 2.0, with the proviso that at least one of a non-ionic or anionic surfactant is present.

2. A slurry detergent according to Claim 1, in which the interpolymer is derived from acrylic acid and a polyallyl polyether of sucrose.

3. A slurry detergent according to Claim 2, in which the interpolymer is the reaction product of 98 to 99.5 parts by weight of acrylic acid and 0.5 to 2 parts by weight of a polyallyl polyether of sucrose having 4 to 8 allyl groups per molecule.

4. A slurry detergent according to any one of the preceding Claims, in which the non-ionic surfactant is a polyethoxylated alcohol.

5. A slurry detergent according to Claim 4, in which the non-ionic surfactant is derived from a G2 to G5 straight-chain saturated alcohol and 3 to 10 moles of ethylene oxide per mole of alcohol.

6. A slurry detergent according to Claim 5, in which 7 moles of ethylene oxide are used per mole of alcohol.

7. A slurry detergent according to any one of the preceding Claims, in which the polyphosphate is sodium tripolyphosphate.

8. A slurry detergent according to any one of the preceding Claims, in which the anionic surfactant is an allyl aryl sulphonic acid.

9. A slurry detergent according to Claim 8, in which the anionic surfactant is linear dodecylbenzene sulphonic acid.

1 0. A slurry detergent according to any one of the preceding Claims, in which the optical brightener is 4,4'-di(2-sulphostyryl-biphenyl) disodium salt.

11. A slurry detergent according to any one of the preceding Claims which comprises the following components: Components Wt. % water 45.0 to 73.0 The interpolymer 0.3 to 1.3 Caustic soda, dry basis 5.5 to 19.5 Non-ionic detergent 2.0 to 8.0 Polyphosphate O to 20.0 Polyacrylate, dry basis 0.2 to 2.0 Anionic surfactant 0 to 4.0 Optical brightener 0.05 to 1.0 Sodium aluminosilicate 0 to 18.0 Sodium carboxymethylcellulose 0.5 to 1.5

1 2. A slurry detergent according to Claim 11 which comprises the following components: Components Wt. % Water about 45.4 The interpolymer about .5 Caustic soda about 1 2.5 Non-ionic detergent about 5.0 Polyphosphate about 16.0 Polyacrylate about 1.2 Anionic surfactant about 2.0 Optical brightener about 0.1 Brilliant alizarine milling blue BL 15 g./1000 Ibs.

of formula

1 3. A slurry detergent according to Claim 1 substantially as described in the Example.