GB2168073A - Antistatic built synthetic organic detergent composition - Google Patents

Abstract

An antistatic particulate built synthetic organic detergent composition comprises a synthetic organic detergent or a mixture of such, a polyacetal carboxylate builder or a mixture of polyacetal carboxylate and zeolite builders, and N-higher alkyl isostearamide antistatic agent.

Description

SPECIFICATION Antistatic built synthetic organic detergent composition The present invention relates to detergent compositions. More particularly, it relates to detergent compositions comprising an anionic synthetic organic detergent or a mixture of such detergents, polyacetal carboxylate builder for such detergent(s) and a particular antistatic agent, N-higher alkylisostearamide. Also within the present invention are processes for making such compositions and for washing fibrous materials that have been soiled and or stained, to remove such soil and/or stain and to prevent static "clinging" of the materials.

The need for removing soils and stains from fibrous materials is age-old and many compositions have been described for accomplishing that result. Whereas once soap was extensively used for this purpose, today almost all home laundry detergent compositions are based on one or more of the synthetic organic detergents. Of such detergents the anionic and nonionic detergents are the most effective and the anionic detergents are the most used. Ampholytic, amphoteric, zwitterionic and cationic detergents have also been employed, but with less success. Cationic compounds can act as antistatic agents (antistats) to decrease static cling of washed items of synthetic organic polymeric plastics, e.g. nylons, polyesters, acrylics, and blends of such materials with cotton, with each other and with other polymeric fibres.N-alkylisostearamides have been suggested as antistats for anionic detergent compositions in U.S. Patent Application S.N. 404,794, filed 3rd August, 1982, because, unlike the cationic compounds, which have been used for this purpose in the past, they do not significantly adversely affect the detersive powers of such anionic detergent compositions.

recently, polyacetal carboxylate builders have been employed in detergent compositions in replacement of polyphosphate builders because they do not contain phosphorus and accordingly have not been thought to promote eutrophication of inland waters. Another advantage of such builders is their ready degradability in normally acidic waste waters. Zeolites and other builders, both water soluble and water insoluble and both organic and inorganic, have been used for years to improve the cleaning powers of synthetic organic detergents. Non-phosphate built detergent compositions have been made, in which polyphosphate builders are not present, and such detergent compositions are non-eutrophying.

Although the main components of the present detergent compositions have been employed in other detergent preparations the present products are novel, unobvious and useful, and possess unpredictably good soil and stain removing properties. Particularly important is the greatly improved capacity of the present compositions, especially non-phosphate compositions, to remove a variety of common and hard to remove stains and soils from textile materials and to impart antistatic properties to such materials during conventional machine washing, which antistatic properties prevent the washed materials from clinging together after automatic laundry drying.

In accordance with the present invention an antistatic build detergent composition, preferably in particulate form, comprises a detersive proportion of a synthetic organic detergent, preferably an anionic detergent, or a mixture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) our a building proportion of a mixture of such polyacetal carboxylate builder and zeolite builder, and an antistatic proportion of an antistatic amide, such as N-cocoisostearamide (CISA).

Preferred such compositions comprise about 5 to 30% of sodium linear higher alkylbenzene sulphonate wherein the higher alkyl group is of 12 to 14 carbon atoms, about 5 to 40% of sodium polyacetal carboxylate builder of a calculated weight average molecular weight in the range of 3,500 to 10,000, or a mixture of such builder and Zeolite A builder, about 2 to 20% of CISA, about 2 to 20% of moisture, and the balance, if any, of filler(s) and/or other builder(s) and/or other adjuvant(s). Also within the present invention are processes for making such compositions and for removing soils and stains from fibrous materials by washing such materials in wash water which contains such a detergent composition or the components thereof.

The anionic synthetic organic detergent of the present invention will normally be sulphonated and/or sulphonated lipophilic material(s) having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to 18 and a more preferably 12 to 16. While various water soluble salt-forming cations may be used to form the desired soluble sulphated and sulphonated detergents, including ammonium and lower alkanolamine (such as triethanolamine), and magnesium, usually an alkali metal, such as sodium or potassium, is employed, and very preferably such cation will be sodium. Among the various anionic detergents that are useful in the practice of this invention the linear higher alkylbenzenesulphonates with 10 to 18 carbon atoms making up the alkyl chain preferably 12 to 16 and more preferably about 12 to 14, are considered most suitable.Also, useful, among others, are the monoglyceride sulphates, higher fatty alcohol sulphates, sulphated polyethoxylated higher alkanols, wherein such alkanols may be synthetic or natural, containing from 3 to 20 or 30 ethoxy groups per mole, paraffin sulphonates and olefin sulphonates, in all of which compounds the alkyl group present is of 10 to 18 carbon atoms. Some such alkyl groups may be slightly branched but will still be of a carbon chain length within the described range.

Although the linear higher alkylbenzene sulphonates, as the sodium salts, are the preferred anionic detergents utilized in the practice of the present invention, mixtures of such detergents with other linear high alkylbenzene sulphonates containing different cations may be employed, as may be mixtures of such detergents with others, such as the fatty alcohol sulphates and sulphated pllyethoxylated higher alkanols. In some instances only minor proportions of the linear alkylbenzene sulphonates will be present or the anionic synthetic organic detergent may be a mixture of other anionic detergents of the types described. Also, other anionic detergents may be employed, such as those which are well known in the art, which are described in various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example, that which was issued in 1969.

While the present invention is primarily of anionic detergent compositions, which have antistatic properties, the desirable results mentioned herein are also obtainable with compositions containing other types of synthetic organic detergents with the anionic detergents, such as nonionic and amphoteric detergents, and in some instances cationic materials, such as the di-higher alkyl, di-lower alkyl ammonium halides, di-tallowyl di-methyl ammonium chloride, other quaternary ammonium halides, and other cationic materials may be present, primarily for fabric softening effects (although it is often preferred to utilize bentonite or other fabric softening clayforthis purpose instead, sometimes with additional cationic softener).The mentioned nonionic, amphoteric and cationic materials are normally present in only minor proportions, if present at all, and usually only half as much thereof will be present, at the most, as of the synthetic anionic organic detergent. Preferred nonionic detergents are the ethylene oxide condensation products of higher fatty alcohols, such as condensation products of higher fatty alcohols of 12 to 18 carbon atoms with from 3 to 20 moles of ethylene oxide, preferably condensation products of higher fatty alcohols of 12 to 15 carbon atoms with 5 to 15 moles of ethylene oxide.

The polyacetal carboxylate may be considered to be that described in U.S. Patent 4,144,226 and may be made by the method mentioned therein. A typical such product will be of the formula

wherein M represents an alkali metal, ammonium, or alkyl group of 1 to 4 carbon atoms, a tetralkylammonium group or an alkanolamine group, which are of 1 to 4 carbon atoms in the alkyls thereof, n averages at least 4, and R1 and R2 represent any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. Preferably the polyacetal carboxylate will be one wherein M is an alkali metal, e.g. sodium, n is from 20 to 200, R1 is

or a mixture thereof, R2 is

and n averages from 20 to 100, more preferably 30 to 80.The calculated weight average molecular weights of the polymers will normally be within the range of 2,000 to 20,000, preferably 3,500 to 10,000 and more preferably 5,000 to 9,000, e.g. about 8,000.

Although the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal carboxylates or related organic builder salts described in various Monsanto patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the Monsanto patents referred to, especially U.S. 4,144,226, may be utilized, providing that they have the desired stabilizing properties, which allow the mentioned builders to be depolymerized in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.

The zeolite component will usually be of the formula (Na20) (AI203)y (SiO2)z w H20 wherein xis 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or about 2, and w is from 0 to 9, preferably 2.5 to 6. Such zeolites are cation exchanging and have an exchange capacity for calcium ion in the range of about 200 to 400 or more milligram equivalents of calcium carbonate hardness per gram. They will very often be hydrated to the extent of 5 to 30%, preferably 10 to 25% moisture, e.g.

about 20% thereof. Zeolite A is preferred (X and Y are also useful) and for such zeolite type 4A is most preferred. Particle sizes of the zeolite(s) will usually be 100 to 400 mesh (or sieve number) U.S. Sieves (which have openings 149 to 37 microns across), preferably 140 or 200 to 325 mesh (which have openings 105, and 74 and 44 microns across respectively), but their ultimate sizes will be submicron. The various zeolites are described at length in the text Zeolite Molecular sieves, by Donald W. Breck, published in 1974 by John Wiley & Sons especially at pages 747-749 thereof.

In the compositions of the present invention other builders than the polyacetal carboxylate (and zeolite) may also be present although such are not necessary. Usually it will be desired to avoid the presence of phosphorus in the detergent composition so the polyphosphates which have been the builders of choice in the detergent art for many years (especially pentasodium tripolyphosphate), will preferably be omitted from the present formulations. Still, in some instances they may be present, if held to relatively small proportions, e.g. up to 5 or 10%.Among builders other than polyphosphates such as sodium tripolyphosphate and tetrasodium pyrophosphate and other than the previously mentioned polyacetal carboxylates and zeolites, those which may be desirably incorporated in the present compositions, to supplement the building action of the polyacetal carboxylate, include sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, NTA, sodium citrate, sodium gluconate, borax, other borates, and other builders known in the detergent art. Fillers may be present, such as sodium sulphate and sodium chloride, to add bulk to the product when that is considered to be desirable, and they also serve other purposes.Of the builders it is considered that the zeolites are especially effective with the polyacetal carboxylates in these compositions, as has been previously indicated, and of the fillers that preferred will usually be sodium sulphate.

The antistatic agent of choice in the practice of the present invention is N cocoisosteramide. Such antistatic agent is an amide which is chemically derivable from isostearic acid and cocoamine by the condensation reaction shown below:

Isostearic acid,

is a saturated fatty acid of the formula C17H35COOH, which is a complex mixture of isomers, primarily of the methyl-branched series, that are mutually soluble and virtually inseparable. While such acid normally has uses similar to those of stearic or oleic acids, it is considered that it is far superior to such materials in manufacturing effective antistatic agents, which are suitable for incorporation in the synthetic organic anionic detergent compositions of the present invention. Cocoamine is an aliphatic amine in which the aliphatic group is derived from coconut oil.Other primary aliphatic amines, preferably higher alkylamines of 7 to 18 carbon atoms in the alkyl, such as R'NH2, wherein R' is such a higher alkyl group, may also be used, but cocoamine produces an isostearamide of the best properties for incorporation in detergent compositions.

While CISA is the most highly preferred antistatic agent (such may be referred to as antistats) it is within the broader aspects of the present invention to employ other N-aliphatic isostearamides, such as those derived from primary aliphatic amines containing 7-18 carbon atoms, the aliphatic parts of which may or may not be hydrogenated, provided that the amides made have sufficient antistatic effect in the described use. Some examples thereof are the N-alkylisostearamides derived from N-tallowamine, N-decylamine and N-octylamine. However, it is considered that N-alkylisostearamides other than CISA are inferior in antistatic effect to CISA and hence, if they are employed at all, such employment will preferably be in a minor proportion with respect to CISA.In some cases the hydrogen atom on the amide nitrogen may be replaced by suitable radicals, such as lower alkyl e.g. methyl, provided that a desired antistatic effect is still obtained, but it has been found that the tertiary isostearamides usually are of little antistatic activity.

Among the various adjuvants that may be present in the compositions of the present invention are colourants such as dyes and pigments, perfumes, enzymes, stabilizers, activators, fluorescent brighteners, bleaches, buffers, fungicides, germicides, antifoam agents and flow promoting agents. also included among adjuvants, builders and fillers, unless in other classes that are mentioned, are various additional components or impurities present in the components of the compositions. For example, it is known that sodium carbonate and water are often present with polyacetal carboxylate in Builder U, the product which is the present source of polyacetal carboxylate.

Moisture will usually be present in the compositions of the present invention, either as free moisture or in one or more hydrates. While moisture is not an essential component of the solid detergent compositions of the present invention it will normally be present due to the use of water in manufacturing, and it may help to solubilize components of the composition and help to bind them together.

The proportions of components of the compositions of the present invention given below are those for particulate products, which are usually of particle sizes in the 8 or 10 to 100 or 140 sieve (or mesh) range, U.S.

Sieve Series (which have openings 2380,2000, 149, and 105 microns across repsectively). However, such proportions also apply to other solid forms, such as bars or cakes, more finely divided or coarser powders, granular compositions and agglomerates. They may also apply to liquid, gel and paste preparations. The ratios between pairs of components, except water, may be about the same in liquid, gel and paste preparations as in solids but because the liquid products will often be much more dilute, the proportion of water or other solvent or mixture of solvents present will usually be much greater. In some aspects of the present invention product components may be added directly to the wash water, in which case it may be considered that the wash water, containing the various active and other components is the "detergent composition".

In the particulate solid and other solid detergent compositions of the present invention the total proportion of detergent present will normally be from 5 to 40%, preferably from 5 to 30%, more preferably lotto 25% and most preferably 13 to 23%, e.g. about 18%. Such detergent will normally be an anionic detergent and of these the higher alkylbenzene sulphonates are preferred, e.g. sodium linear tridecylbenzene sulphonate.

However, such may be present with other anionic detergents or may be replaced wholly or in part by one or more of such other anionic detergents. The proportion of polyacetal carboxylate builder will usually be within the range of 5 to 50%, preferably 5 to 40%, more preferably 12 to 30%, and most preferably 13 to 26%, e.g. about 17%, when it is the only builder present or when up to 50% of other builder(s) than zeolite, such as 15 to 40%, is also present. When zeolite is employed the sum of the polyacetal carboxylate and zeolite will be of the proportions previously given for the polyacetal carboxylate alone and if zeolite is present the polyacetal carboxylate will be at least 4% of the detergent composition.Also, the ratio of polyacetal carboxylate to zeolite will be in the range of 1:2 to 4:1, preferably 1:2 to 3:1, and more preferably about 2:3 to 3:2, e.g. about 1:1.CISA antistat, which also has fabric softening properties, in the described compositions, will be present in an antistatic proportion in the compositions of the present invention, so that it will substantially reduce static, at least with respect to certain synthetic fibres and fabrics. The present detergent compositions have been found to be especially effective in reducing electrical charges (and consequent static cling) on polymeric materials, but are also effective to reduce such undesirable effects of machine drying on fabrics made from natural fibres and natural-synthetic blends.The proportion of antistatwill usually be in the range of to 20%, preferably 3 to 15% and more preferably 4to 13%, e.g. about 9%.

The percentage of moisture will normally be from 2to 20%, preferably 3 to 15%, and more preferably 4to 12%, e.g. about 5 or 6%. such percentages include moisture in hydrate form that is released during heating for two hours at 105 C (the standard moisture analysis method). The proportion(s) of filler(s), will normally be limited to no more than 50% and often will be in the range of 5 to 40%, preferably 15 to 35%, e.g. about 25%. Contents of non phosphate builders other than the polyacetal carboxylate and any zeolite that may be present will be limited, generally being less than 40%, such as 3 to 30% or 5 to 25%. Such supplemental builders are not required but their presence, often with filler salt, too, is often desirable.Thus, sodium carbonate is a preferred non-phosphate builder, as is sodium silicate. Preferred silicates are the sodium salts wherein the Na2O:SiO2 ratio is in the range of 1:1.6 to 1:3.0, more preferably 1:2.0 to 1:2.6, e.g. 1:2.4.

Proportions of the carbonate and silicate, if present, may be from 3 to 25%, preferably 8 to 20% and more preferably 10 to 18% for the carbonate, and 2 to 15%, preferably 5 to 10% and more preferably 6 to 9%, for the silicate.

The total adjuvant content will usually not exceed 10% or 20%, and preferably will be less than 5%, with the contents of the usual individual adjuvants generally not exceeding 3% or 5%, and often preferably being less than 1 or 2%. For example, sodium carboxymethyl cellulose, which is a desirable antiredeposition agent, will usually be of a proportion within the range of 0.3 to 3%, preferably 0.5 to 2%, e.g. 1%, of the composition, if present.

In preferred forms of the particulate solid compositions of the present invention of particle sizes such as those previously described, it is often preferred to spray dry as much of the formulation as feasible so as to obtain substantially uniformly shaped globular particles. The antistat may be post-added to the rest of the composition, as by spray coating of it, in liquid form, onto tumbling spray dried detergent base beads. To prevent segregation during shipping and storage of the final product it is desirable that any post-added components, such as enzyme, bleach, bentonite (if not spray dried) and polyacetal carboxylate (if not spray dried) be of shape, particle sizes and bulk density like that of the rest of the composition.However, even when such is not the case, and when the post-added materials are in finely divided form, such as of particle sizes in the range of 140, 160 or 170 to 325 mesh U.S. Sieve Series (which have openings 105, 105 and 44 microns across, respectively) and of higher bulk density, they may be post-added to spray dried beads or other particles of the basic detergent composition, which is of larger particle size, and often will adhere to such particles to produce a desired product of sizes in the 10 to 100 mesh (or sieve size) range (which have openings 2000 to 149 microns across). The polyacetal carboxylate may be spray dried with the detergent composition providing that car is exercised to prevent it from being decomposed by heat. In an alternative method of manufacture the various components, in finely divided form, may be mixed together. Also, when the initial particle sizes of the various components, or some of them are less than desired, such as in the 140, 160 or 170 to 325 mesh range, particles thereof may be agglomerating agents, such as a dilute aqueous solution of sodium silicate, and at othertimes with only water to assist in agglomeration. Such agglomeration may be of the undersize particles only or such particles may be agglomerated with the larger spray dried beads or with larger particles of composition components or mixtures of such components.

The anionic detergent or mixture of such detergents, which is/are the primary detergent(s) of the desired compositions, may be spray dried with fillers, such as sodium sulphate, builders, such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and adjuvants, such as fluorescent brighteners, pigments and dyes, in the normal manner, utilizing a conventional countercurrent or concurrent spray drying tower, with drying air entering at about 200 to 600tC (preferably 150 to 300 or 350 C when polyacetal carboxylate is present).Then the polyacetal carboxylate and antistat may be admixed, in either order or conjointly, or the antistat and polyacetal carboxylate may be pre-blended and then sprayed or dripped onto the spray dried beads, or mixed with them or the antistat alone may be sprayed onto the beads or mixed with them when the polyacetal carboxylate is in the spray dried base.In some instances, the polyacetal carboxylate and/or the antistat may be spray dried with other components that are sufficiently stable to withstand the spray drying conditions employed, which conditions will preferably be mild. often, however, the crutching and spray drying operations diminish the antistat activity of the isostearamide and therefore it is preferred that polyacetal carboxylate and/or the CISA be post-added, often by being coated onto composition components that are in particulate form, or onto the spray dried base beads. When CISA is coated onto, mixed with or agglomerated with a product component, such as borax beads, agglomerated zeolite, Microcel C (a synthetic calcium silicate) or bentonite, the flowable product made is readily admixable with the spray dried beads to make the finished product.

When a relatively small proportion of nonionic detergent is to be present with the anionic detergent it may be spray dried with such anionic detergent, fillers and other stable materials. However, when more than about 4 or 5% (sometimes more than 2%) of anionic detergent is to be present in the final formula any additional proportion will usually be post added, as by spraying onto tubling detergent beads, with or without the CISA and/or polyacetal carboxylate and any other suitable liquids, such as perfume, although perfume is usually applied last.In some instances the polyacetal carboxylate may be dispersed and/or disolved in the nonionic detergent to be post sprayed onto the base beads, which nonionic detergent will be heated so as to be in liquid state (or it may be dissolved in a solvent), and the combination of nonionic detergent and polyacetal carboxylate may be sprayed onto the detergent beads or base beads, followed by addition of the antistat, preferably by spray coating of the spray dried detergent composition beads.

Desirably, the particulate material made will be of particle sizes in the 8 to 120 or 10 to 100 mesh range (U.S.

Sieve Series) (which have openings 2380 to 125 microns across and 2000 to 149 microns across respectively) and the manufacturing process will be designed accordingly. However, screening may be employed to remove under and over-sized particles, which may be reworked, ground, agglomerated or otherwise processed to sizes desired (sometimes 8 to 80 mesh) (which have openings 2380 to 177 microns across). The bulk densitites of the spray dried beads and the final beads are often in a range of about 0.2 to 0.6 g/ml, preferably 0.25 to 0.5 g/ml, e.g. about 0.3 or 0.4 g;ml.

To manufacture the present products into bar, cake or briquette form the compositions may be extruded or pressed or moulded to shape in known manner. To convert them to liquid, gel or paste preparations the components may be dissolved and/or dispersed in liquid media, such as water and/or suitable solvent(s), such as ethanol, glycerol and/or isopropanol, and a gelling agent may be employed. Sometimes dissolving of the CISA or similar isostearamide in alcohol or other similarly acting solvent will be avoided because such sometimes will act to reduce antistatic action thereof.

To practice the soil and stain removing processes of the present invention, which leave the washed items non-clinging and clean (and also of improved softness, compared to a control), one of the described compositions may be added to a wash water or the various components thereof may be so added. Normally the concentrations of the compositions employed will be in the range of 0.05 or 0.1 to 0.4 or 0.5%, preferably 0.1 to 0.35%, and more preferably 0.1 to 0.2% of the wash water. Higher concentrations, as from 0.25 to 0.45% or more (and less wash water), are often used in machine washings according to European practice, which normally utilizes a higher temperature wash water. In American practice lower concentrations of the detergent compositions, such as from 0.05 to 0.25%, often preferably about 0.1 to 0.2%, are normally employed.Usually the washing temperature in America will be in the range of 10 to 55no. While the higher range of such temperatures, such as 35 to 55"C, may be best for cleaning effectiveness lower temperatures such as 10 to 35"C and 15 to 25"C are best for washing delicate fabrics and some dyed fabrics and for energy conservation so good cleaning at such lower temperatures is important. The compositions of the present invention are useful to remove soils and stains from laundry of different fabric types and materials, and leave such laundry static free and of improved softness, even after low temperature washing.

In practicing the present invention sufficient of the detergent composition according to the present invention is added to wash water in a conventional home laundry washing machine (commercial machines may also be used) in desired proportion within the ranges given e.g. 0.15% (100 grams per 65 litres of wash water), with the wash water being of normal washing temperature e.g. 21"C and normal hardness (about 50 to 250 ppm as calcium carbonate, e.g. 150 ppm) The laundry is then added, with the normal weight charged being from 2.7 to 4.5 kg, e.g. kg. Washing of the laundry is effected in a normal cycle over a period of time from 2 minutes to 30 minutes, such as 5 to 20 minutes e.g. about ten minutes, usually depending on the dirtiness of the laundry. Surprisingly, the compositions of the present invention are about the same as a control (from which CISA was omitted) in detergency in medium hardness water, of about 150 ppm hardness, when the wash water is at 41"C but are noticeably better than such control at lower temperatures, such as 15 to 25"C. In such control compositions the polyacetal carboxylate or zeolite plus polyacetal carboxylate is replaced by an equal proportion of sodium tripolyphosphate.Also terrycloth towels washed with the composition of the present invention which contains polyacetal carboxylate, zeolite and CISA, appear to be softer than a non CISA control (in which the polyacetal carboxylate and zeolite are replaced by an equal weight of sodium tripolyphosphate), and such composition according to the present invention is clearly superior with respect to non clinging properties especially for acrylic fabrics.

The advantages of the present invention are significant. Employment of CISA allows the production of an antistatic non- phospate or essentially non phosphate detergent composition which is of essentially the same detersive activity as phosphate containing detergent compositions. Unlike detergent compositions now on the market, which include polyphosphate builder and quaternary ammonium halide as an antistatic agent (and softener), in which the quaternary ammonium halide reacts with the anionic detergent and thereby diminishes its detersive activity, ClSA does not adversely affect the anionic detergent (or the phosphate) Thus using CISA in detergent compositions in which polyacetal carboxylate builder or a mixture of polyacetal carboxylate and zeolite builders is employed, usually as primary builder(s), one may make an antistatic non phosphate detergent composition of cleaning power equal to that of a non CISA product in which the primary builder is of a similar proportion of pentasodium tripolyphosphate or other sodium tripolyphosphate (equal to the total of polyacetal carboxylate and water softening or cation exchanging zeolite present). The antistatic activity of the present compositions is comparable to that of rinse cycle softeners. Additionally, the detergent compositions of the present invention measurably soften laundry washed with them.Among the important effects noted in various washing tests are the following: 1) In a washing machine test, in which a 9% CISA anionic detergent composition based on polyacetal carboxylate and zeolite builders for the anionic detergent was employed, it cleaned as well as a control detergent without CISA and with sodium tripolyphosphate replacing the polyacetal carboxylate zeolite mixture of builders. It also cleaned significantly better than such a phosphate built control composition containing 5% of distearyl dimethyl ammonium chloride, and it would be expected that the use of 9% of the disteryl dimethyl ammonium chloride would adversely affect the detergency of such a control composition even more.

2) In Tergotometertestings, compositions of the present invention were equal to or better than control compositions in which polyphosphate was employed as a builder in cold water washing in medium hardness water (normal wash conditions) 3) Compositions of the present invention are far superior to control compositions in controlling static, especially with respect to fabrics of polyester cotton blends and double knit polyester. The compositions of the present invention also control static better than a control having added to it 5% of quaternary ammonium halide, when polyester cotton blend fabrics are washed.The non phosphate compositions of the present invention, containing CISA, are significantly better than similar compositions in which polyphosphate builder is substituted for the polyacetal carboxylate-zeolite mixture, with respect to limiting static charges on acrylic materials 4) The non phosphate compositions of the present invention noticeably soften washed cotton polyester blend towels more than a ClSA-free polyphosphate built detergent control.

The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples. Unless otherwise indicated, all parts are by weight and all temperatures are in C in the examples in this specification and in the appended claims.

Example 1 A detergent composition is made having the ingredients and proportions given in Table 1 below.

TABLE 1 Component Percent Sodium linear tridecylbenzene sulphonate 18.2 Builder U (79 7% sodium polyacetal carboxy- 10.9 late, supplied by Monsanto Co. [Lot No.

2538422], of calculated weight average molecular weight of about 8030) Zeolite 4A (20% hydrated) 10.9 Sodium carbonate (anhydrous) 12.7 Sodium silicate (Na2O SiO2 = 1:2.4) 7.3 Sodium sulphate (anhydrous) 25.4 CISA (N-cocoisostearamide) 9.1 Moisture 5.5 100.0 The detergent is particulate and is made in spray dried bead form of all the above components except the CISA by preparing an aqueous crutcher mix (55% solids concentration) of the materials listed in Table 1 at a temperature of about 50"C and spray drying such crutcher mix under mild conditions, taking care to prevent deterioration of the polyacetal carboxylate, and keeping the walls of the spray tower as clean as possible during the spraying operation.The spray tower employed is a countercurrent tower which operates under mild conditions, with drying air 91 about 220"C inlet temperature and with other provisions to prevent charring of the beads and decorciposition of the polyacetal carboxylate (by prevention of buildup on tower walls, utilization of cooling air and/or controlled spraying to prevent contact of the spray with the tower walls).

The product resulting is of particle sizes in the range of No's. 10 to 100 sieves, U.S. Sieve Series (which have openings 2000 to 149 microns across), a bulk density of about 0.3 g/ml and a moisture content of about 6%. Ten parts of the detergent composition thus made are sprayed with one part of CISA in liquid form, so that the CISA coats the particles. the temperature at which the CISA is applied is normally about 5"C above its melting point or 5" above the highest part of its solid-liquid transition range.Such a temperature is employed so that upon contacting the cooler detergent particles, normally at about room temperature (but they may be of higher temperatures too), the CISA will solidify quickly, without agglomerating the spray dried beads into undesirably larger aggregates. alternatively, the CISA of the desired particle sizes, in the range of No s. 10 to 100 sieves may be mixed with the spray dried particles. Even when it is more finely powdered, with particle sizes in the range of 100 to 325 mesh (which have openings 149 to 44 microns across), the antistat may be well distributed through the detergent composition and normally will adhere sufficiently to the particles thereof, yielding a product which is in the desired size range and which is of desired bulk density, usually in the range of 0.3 to 0.4 g/ml, like that of the coated product, too.

The coated product made is tested for soil and stain removal, utilizing a Tergotometer laboratory type washing machine in which standard swatches of various materials, soiled and stained in a standard manner, are washed for ten minutes in water, of a hardness of 150 ppm, as calcium carbonate, using a detergent composition concentration of 0.15% on the basis of the wash water, at a washing temperature of 21 C. The water hardness is a mixed calcium and magnesium hardness in a 3:2 Ca:Mg ratio.Reflectance readings of the washed and dried swatches of various materials with various stains thereon, according to a standard soil removal index (SRI) test, are taken, and indeces indicative of the weighted sums of the reflectances are calculated, which indeces, based on experience, have been found to be measures of the soil and stain removal capability of a tested detergent composition (the higher the index, the better the detergency).

Similar compositions are made in which the 21.8% total of polyacetal carboxylate and zeolite is kept but the weight ratio of the polyacetal carboxylate to zeolite is changed to 3:2 (Example 2) and 2:1 (Example 3), respectively. The SRl's obtained are +6, +12 and t9, respectively, compared to a control detergent composition of formula like that of the base detergent (without CISA), with the polyacetal carboxylate and zeolite replaced by sodium tripolyphosphate. When the same tests are repeated, with the only change being in the temperature of the wash water, 41"C, the indexes are 0,4 and 3, respectively.It is considered that the index differences noted when washing is conducted at 219C are significant, showing that the present compositions are superior to the control in soil and stain removal at such lower temperatures.

Examples 4, 5, 6, 7 and 8 In other experiments described below, detergent composition systems were employed to wash two swatches each (36 cm x 36 cm) of fabrics of the following compositions: polyester-cotton blend; acetate; acrylic; and double knit polyester. The detergent systems employed are: Example 4 - 100 grams of 24% polyphosphate built anionic detergent, without CISA (Base bead [BBj); Example - 100 g polyphosphate BB plus 10 g CISA (CISA overcoated on BB); Example 6 - 100 g 12% polyacetal carboxylate plus 12% zeolite (instead of 24% polyphosphate) BB plus 10 g CISA (CISA overcoated on spray dried product); Example 7-100 g polyphosphate BB plus rinse-cycle softener rinse (with Downy (Registered Trade Mark) fabric softener); and Example 8 - 100 g polyphosphate BB plus 5 g dimethyl distearyl ammonium chloride.

The given amounts of detergent composition are used to wash test fabrics in 60 litres of 150 ppm hardness water in a General Electric Company washing machine at 43"C for ten minutes. static charge measurements were made by detecting the static charge buildup generated by rubbing the respective test fabrics against a wool swatch in a controlled manner for 5 seconds. Static charge measurements were made in a controlled environment room (i.e. of constant temperature and low humidity) using an electrostatic voltmeter. The following Table 2 shows the static charge measurements, after machine drying.

Examples 4, 57 and 8 are comparison examples.

TABLE 2 Static charge readings (kilo volts) Polyester cotton Double knit Example blend Acetate Acrylic polyester Total 4 12.0 5.0 18.0 10.2 45.2 5 0.6 4.0 15.0 1.8 21.4 6 0.8 4.0 9.8 1.5 16.1 7 4.7 4.0 4.5 0.7 13.9 8 8.5 0.8 2.1 0.9 12.3 From the above table it is seen that compositions of the present invention (Example 6) provide results comparable to a rinse-cycle softener with respect to static control. Also, note that the composition of Example 6 is significantly better than the composition of Example 5 in this respect, with the difference being most pronounced with respect to static or acrylics. Furthermore, the static charge on mixed polyester-cotton fabrics is much lower after washing with the compositions of the present invention than after washing with a polyphosphate-containing detergent plus quaternary ammonium halide (Example 8).In interpreting the above data charge differences greater than 4 kilovolts are considered significant.

In the wash waters in which the above detergent composition systems and/or treatments were used such were also tested for detergency. A set of standard SRI swatches was included in each wash and the swatches were read for reflectance, after washing. Four swatches each of Test Fabric Nylon, Test Fabric Cotton Piscataway (N.J.) clay on cotton, Piscataway clay on Dacronicotton blend, and EMPA 101 were in each set of swatches. The highest reading obtained was that of the composition of the present invention (Example 6), containing polyacetal carboxylate, zeolite and CISA, with all the other treatments being essentially the same except treatment using Example 8, which was significantly inferior.

Terrycloth towels that were washed in the same wash water as the test fabrics were softer when washed with the detergent composition of Example 6, compared to a non-CISA control (Example 4) in which the builder was sodium tripolyphosphate.

This example shows that heavy duty detergent compositions of the present invention, containing CISA, polyacetal carboxylate and Zeolite A with a non-phosphate anionic detergent that is built with carbonate and silicate, are of detersive effect like that of phosphate detergents and are of antistatic effect far superior to that of a control phosphate detergent. Cloths washed with the composition of the present invention are softer than the control and best cleaning, compared to the control, occurs in cold water. Furthermore, when CISA is included in the present composition instead of a quaternary ammonium halide detergency is significantly better for the product of the present invention.

EXAMPLE 9 In Examples 1,2 and 3 data were given for CISA containing detergent composition having polyacetal carboxylate to zeolate ratios from 1:1 (Example 1) to 2:1 (Example 3). When the polyacetal carboxylate completely replaces the zeolite similar results are obtainable, with the CISA contributing antistatic activity and the polyacetal carboxylate acting as an effective builder. Also, such compositions cause an improvement in softness of washed towels, compared to a control in which the builder is sodium tripolyphosphate and in which no CISA is present.

EXAMPLE 10 When the compositions of the present invention, as described in Examples 1 to 9, are modified by replacement of the Builder U Lot No. 2538422 material with Builder U Lot No. 2547312 materials, essentially the same results will be obtained. The replacement Builder U has a weight average molecular weight of 5,200 for the polyacetal carboxylate, of which it contains about 83%. In such experiments, utilizing the lower molecular weight polyacetal carboxylate, and in experiments of Examples 1 to 9 when other N-higher alkylisostearamides are utilized, such as those derived from N-tallowamine or N-octylamine, or mixtures thereof, with either or both Builder U types, useful antistatic activity, softening and cleaning, without loss of cleaning power due to the presence of the amide, will be obtained.However, it is considered that the results are not as good, on the whole, when the other amides are used, as they are when CISA is employed. Also, when some of the anionic detergent in Examples 1 to 9 is replaced by nonionic detergent, such as Neodol (Registered Trade Mark) 23-6.5, Neodol 25-7 or Neodol 45-11, all of which are condensation products of ethylene oxide and higher fatty alcohols, comparable desirable results are obtained. In such experiments the proportion of sodium linear tridecylbenzene sulphonate may be diminished proportionately in view of the addition of 2,4 and 6% of the nonionic detergent. Such results are also obtainable when the CISA or similar amide is mixed with the rest of the composition, rather than being coated onto the surfaces of particles thereof.

EXAMPLE 11 The various proportions of components of the compositions of Examples 1 to 10 may be modified by +10% and +30% of the proportions given, while keeping such proportions within the ranges mentioned in this specification, and useful products having the desired cleaning and antistatic properties will be obtained.

similarly, manufacturing and use methods may be modified, and spray drying, spray coating and washing operations may be changed, while being kept as described herein, and useful products will be obtained, made, and satisfactorily, employed, respectively.

The invention has been described with respect to working examples and various illustrations and embodiments thereof but it is not to be limited to these because it will be evident that one of skill in the art, with the present specification before him or her, will be able to utilize equivalents and substitutes without departing from the invention.

Claims (39)

1. An antistatic built particulate detergent composition comprising a detersive proportion of a synthetic organic detergent, a building proportion of a polyacetal carboxylate builder for such detergent or a building proportion of a mixture of such polyacetal carboxylate builder and zeolite builder, and an antistatic proportion of N-higher aliphatic isostearamide.

2. A detergent composition as claimed in Claim 1 which is essentially free of phosphate.

3. A detergent composition as claimed in Claim 1 or Claim 2 in which the synthetic organic detergent is an anionic detergent sulphate or sulphonate.

4. A detergent composition as claimed in Claim 3 in which the synthetic anionic organic detergent is a higher alkylbenzene sulphonate in which the alkyl group is of 10 to 18 carbon atoms.

5. A detergent composition as claimed in Claim 4 in which the synthetic anionic organic detergent is a higher alkylbenzene sulphonate in which the alkyl group is linear and of 12 to 16 carbon atoms.

6. A detergent composition as claimed in Claim 5 in which the synthetic anionic organic detergent is a sodium linear higher alkylbenzene sulphonate wherein the higher alkyl is of 12 to 14 carbon atoms.

7. A detergent composition as claimed in Claim 6 in which the anionic detergent is sodium linear tridecylbenzene sulphonate.

8. A detergent as claimed in any one of Claims 1 to 7 which contains 5 to 30% of the synthetic detergent.

9. A detergent composition as claimed in Claim 8 which contains 10 to 25% of the synthetic detergent.

10. A detergent composition as claimed in Claim 9 which contains 13 to 23% of the synthetic detergent.

11. A detergent composition as claimed in any one of Claims 1 to 10 in which the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 3,500 to 10,000.

12. A detergent composition as claimed in Claim 11 in which the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 5,000 to 9,000.

13. A detergent composition as claimed in Claim 11 or Claim 12 in which the polyacetal carboxylate is one wherein the carboxylate is sodium carboxylate.

14. A detergent composition as claimed in Claim 13 in which the polyacetal carboxylate builder is of a calculated weight average molecular weight of about 8,000.

15. A detergent composition as claimed in any one of Claims 1 to 14 in which the builder is a mixture of polyacetal carboxylate builder and zeolite builder, with at least 4% of the composition being polyacetal carboxylate builder.

16. A detergent composition as claimed in any one of Claims 1 to 15 in which the builder is a mixture of polyacetal carboxylate builder and zeolite builder, in which mixture the ratio of polyacetal carboxylate builder to zeolite builder is within the range of 1:2 to 4:1.

17. A detergent composition as claimed in any one of Claims 1 to 16 in which the polyacetal carboxylate builder or the mixture thereof with zeolite builder is 5 to 40% of the detergent composition.

18. A detergent composition as claimed in Claim 17 in which the amount of the said builder is 12 to 30%.

19. A detergent composition as claimed in any one of Claims 1 to 18 which contains zeolite builder which is a hydrated zeolite of Type A, Type X or Type Y.

20. A detergent composition as claimed in Claim 19 in which the zeolite is a Type A zeolite of the formula (Na2O)x (Ai203)y (SiO2)z w H20, wherein xis I, y is from 0.8 to 1.2, z is from 1.5 to 3.5, and w is from 0 to 9.

21. A detergent composition as claimed in Claim 20 in which the zeolite is of the formula given wherein y is about 1, z is in the range of 2 to 3 and w is in the range of 2.5 to 6.

22. A detergent composition as claimed in any one of Claims 1 to 21 in which the amide is an N-higher alkylisostearamide in which the alkyl group is of 7 to 18 carbon atoms.

23. A detergent composition as claimed in Claim 22 in which the amide is cocoisostearamide (CISA).

24. A detergent composition as claimed in Claim 23 which contains 2 to 20% of CISA.

25. A detergent composition as claimed in Claim 24 which contains 3 to 15% of CISA.

26. A detergent composition as claimed in Claim 1 which is essentially free of phosphate, and wherein the amide in N-higher alkylisostearamide in which the alkyl group is of 7 to 18 carbon atoms, the synthetic organic detergent is an anionic detergent sulphate or sulphonate, the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 3,500 to 10,000, and the zeolite builder is a hydrated zeolite of Type A, Type X or Type Y.

27. A detergent composition as claimed in Claim 26 wherein the amide is cocoisostearamide (CISA), the synthetic anionic organic detergent is a higher alkylbenzene sulphonate in which the alkyl group is of 10 to 18 carbon atoms, the polyacetal carboxylate is one wherein the carboxylate is sodium carboxylate, and the zeolite is a Type A zeolite of the formula (Na2O)x (AI203)y (SiO2)z w H20, wherein xis 1, y is from 0.8 to 1.2, z is from 1.5 to 3.5, and w is from 0 to 9.

28. A detergent composition as claimed in Claim 27 wherein the synthetic anionic organic detergent is a higher alkylbenzene sulphonate in which the alkyl group is linear and of 12 to16 carbon atoms, and the zeolite is of the formula given wherein y is about 1, z is in the range of 2 to 3 and w is in the range of 2.5 to 6.

29. A detergent composition as claimed in Claim 28 which comprises about 5 to 30% of sodium linear higher alkylbenzene sulphonate wherein the higher alkyl is of 12 to 14 carbon atoms, 5 to 40% of polyacetal carboxylate builder or a mixture of such builder and zeolite builder, 2 to 20% of CISA, 2 to 20% of moisture and the balance, if any, of filler(s) and/or other builder(s) andlor adjuvant(s).

30. A detergent composition as claimed in Claim 29 which comprises 10 to 25% of sodium linear tridecylbenzene sulphonate, 12 to 30% of polyacetal carboxylate builder of a calculated weight average molecular weight in the range of 5,000 to 9,000, or a mixture of such builder and zeolite builder, with at least 4% of the composition being polyacetal carboxylate builder, 3 to 15% of CISA, 3 to 15% of moisture, 8 to 20% of sodium carbonate, 5 to 12% of sodium silicate of Na2O:SiO2 ratio in the range of 1:1.6 to 1:3.0, and 20 to 35% of sodium sulphate.

31. A detergent composition as claimed in Claim 30 comprising 13 to 23% of sodium linear tridecylbenzene sulphonate, 13 to 26% of sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000, 4to 13% of CISA, to 12% of moisture, 10 to 18% of sodium carbonate, 5 to 10% of sodium silicate of Na2O:SiO2 ratio in the range of 1:2.0 to 1 :2.6, and 20 to 30% of sodium sulphate.

32. A detergent composition as claimed in Claim 30 comprising 13 to 23% of sodium linear tridecylbenzene sulphonate, 13 to 26% of a mixture of sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000, and Type A zeolite, in which mixture the ratio of polyacetal carboxylate builder to zeolite builder is within the range of 1:2 to 4:1, 4to 13% of CISA, 4to 12% of moisture, 10 to 18% of sodium carbonate, 5 to 10% of sodium silicate of Na2O:SiO2 ratio in the range of 1 :2.0two to 1:2.6, and 20 to 30% of sodium sulphate.

33. A detergent composition as claimed in Claim 1 substantially as specifically described herein with reference to the Examples.

34. A process for the manufacture of an antistatic built particulate detergent composition that includes a detersive proportion of synthetic organic detergent, a building proportion of a polyacetal carboxylate builder for such detergent or a building proportion of a mixture of such polyacetate carboxylate builder and zeolte builder, and an antistatic proportion of N-higher aliphatic isostearamide, which comprises spray drying an aqueous slurry of synthetic organic detergent, polyacetal carboxylate or polyacetal carboxylate and zeolite builder (s), filler andfor other builder for such detergent, and water, to essentially globular beads having particle sizes in the range of No. 10 to 100 sieve, U.S.Sieve Series (which have openings 2000 to 149 microns across), and then coating such spray dried beads with an antistatic proportion of the N-higher aliphatic isostearamide.

35. A process as claimed in Claim 34 in which the synthetic organic detergent is an anionic detergent which is a sodium linear higher alkylbenzene sulphonate in which the higher alkyl group is of 12 to 14 carbon atoms, the polyacetal carboxylate builder is a sodium polyacetal carboxylate of a calculated weight average molcular weight in the range of 5,000 to 9,000, the aqueous slurry includes sodium linear higher alkylbenzene sulphonate, polyacetal carboxylate, hydrated Zeolite A, sodium silicate of Na2O:SiO2 ratio in the range of 1:2.0 to 1::2.6, sodium carbonate and sodium sulphate, the amide is N-higher alkylisostearamide in which the alkyl group is of 7 to 18 carbon atoms, and is spray coated onto the spray dried beads, and the detergent composition resulting comprises 13 to 23% of sodium linear tridecylbenzene sulphonate, 13 to 26% of a total of polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000, and Zeolite A builder, with the ratio of polyacetal carboxylate to zeolite being in the range of 1:2 to 4:1.

4to 13% of N-higher alkylisostearamide, 4to 12% of moisture, 10 to 18% of sodium carbonate, 5to 10% of sodium silicate of Na20:SiO2 ratio in the range of 1:2.0 to 1:2.26, and 20 to 30% of sodium sulphate.

36. A process as claimed in Claim 35 in which the amide is N-cocoisostearamide and the bulk densities of the spray dried beads and of the product are in the range of 0.25 to 0.5 g/ml.

37. A method for removing hard to remove soils and stains from fibrous materials which comprises washing such soiled and stained materials in water of mixed calcium and magnesium hardness in the range of 50 to 250 ppm, as calcium carbonate, at a temperature in the range of 10 to 350C and at a concentration in the range of 0.05 to 0.5%, with a composition comprising a detersive proportion of anionic detergent, a building proportion of a polyacetal carboxylate builder for such detergent or a building proportion of a mixture of such polyacetal carboxylate builder and zeolite builder, and an antistatic proportion of CISA.

38. A method as claimed in Claim 37 in which the wash water temperature is in the range of 15 to 25"C, the concentration of the detergent composition in the wash water is in the range of 0.1 to 0.2%, and the detergent composition compises 13 to 23% of sodium linear tridecylbenzene sulphonate, 13 to 26% of a mixture of sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000 and Type A zeolite of the formula (Na2O)x.(Al2O3)##(SiO2)2#wH2O wherein xis 1, y is 1, z is 2 to 3 and w is from 2.5 to 6, in which mixture the ratio of polyacetal carboxylate builder to zeolite builder is within the range of 1:2 to 4: :1, 4to 13% of CISA, 4to 12% of moisture, 10 to 18% of sodium carbonate, 5 to 10% of sodium silicate of Na20:SiO2 ratio in the range of 1:2.0 to 1 :2.6, and 20 to 30% of sodium sulphate.

39. A method as claimed in Claim 38 in which the detergent composition comprises about equal proportions of polyacetal carboxylate and Type A zeolite builders.