GB2159534A

GB2159534A - Antistatic synthetic organic detergent composition

Info

Publication number: GB2159534A
Application number: GB08513935A
Authority: GB
Inventors: Gary M Freeman
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1984-06-01
Filing date: 1985-06-03
Publication date: 1985-12-04
Also published as: MX161833A; BE902555A; SE8502352D0; AU4278985A; PH20709A; DK245985A; NL8501576A; ATA161185A; IT1182728B; AU570561B2; ZA853572B; FR2565246B1; PT80560B; IT8548155A0; KR920006027B1; GB8513935D0; JPS612799A; NZ212083A; SE8502352L; FR2565246A1

Abstract

Antistatic built anionic synthetic organic detergent compositions to remove soils and stains from fibrous materials, comprise an anionic synthetic organic detergent, a polyacetal carboxylate builder for such detergent(s) and a cationic antistatic agent.

Description

SPECIFICATION Antistatic synthetic organic detergent composition This 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 cationic antistatic agent. Also within the invention is a process 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 a multitude of compositions has been described for accomplishing that result. Whereas once soap was the universal detergent today almost all home laundry detergent compositions are based on one or more synthetic organic detergents. Of such detergents the anionic and non ionic detergents are the most effective and the anionic detergents are the most used. Ampholytic or amphoteric and cationic detergents may also be employed. Cationic compounds which possess detersive activity are often also germicidal and act as antistatic agents (antistats), which is especially important because they decrease static cling of washed items of synthetic organic polymeric plastics, e.g.

nylons, polyesters and acrylics. The cationic compounds also have fabric softening properties.

However, a detriment of the cationic detergents is their reactivity with anionic materials, such as anionic detergents, which can cause severe decreases in detersive action. In recent years, cationic detergents, such as quaternary ammonium halides, have been used in detergent compositions to impart antistatic and fabric softening properties to synthetic organic polymeric plastic washed materials or laundry, without seriously adversely affecting the detersive activities of the compositions. Also 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 plus for such builders is their ready degradability in normal acidic waste waters.

Although the main components of the present detergent compositions have been employed in other such compositions the present compositions 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 various stains and soils from synthetic textile materials and to impart antistatic and fabric softening 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 detergent composition comprises a detersive proportion of a synthetic organic detergent or a mixture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) or a building proportion of a mixture of such polyacetal carboxylate builder and zeolite builder, and an antistatic proportion of an antistatic cationic component.Preferred such compositions comprise about 5 to 30% of sodium linear higher alkylbenzene sulphonate wherein the higher alkyl is of 1 2 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 10% of distearyl dimethyl ammonium chloride, about 2 to 20% of moisture, and the balance of filler(s) and/or other builder(s) and/or other adjuvant(s).Also within the invention is a process for removing mixed soils and stains from fibrous materials, especially cellulose acetate, which comprises washing such soiled and stained fibrous materials in wash water which contains a detergent composition including a detersive proportion of a synthetic organic detergent or a mixture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) and an antistatic proportion of a cationic antistat at a concentration of such detergent composition in the wash water in the range of 0.05 to 0.5%. Additionally within the invention is a process for manufacturing the described compositions.

The anionic synthetic organic detergent of the present invention will normally be sulphated and/or sulphonated lipophilic material(s) having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to 18 and 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 alkylbenzene sulphonates of 10 to 1 8 carbon atoms making up the alkyl chain, preferably 1 2 to 1 6 and most preferably about 1 2 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 1 8 carbon atoms.

Some such alkyl groups may be branched to a slight degree but will still be of a carbon chain length within the described range.

The cationic antistats that may be employed, usually in limited proportion, e.g. no more than 20% and preferably only up to 15%, are preferably di-higher alkyl, di-lower alkyl ammonium halides, wherein the higher alkyl moieties are of 10 to 18, preferably 1 6 to 1 8 carbon atoms, the lower alkyls are of 1 to 3, preferably 1 carbon atom(s) and the halogens are chlorine or bromine. Among such materials there may be mentioned distearyl dimethyl ammonium chloride, di-tallow dimethyl ammonium chloride (wherein the alkyl is obtained from animal fats) and dihydrogenated tallow dimethyl ammonium bromide. However, various other such cationic materials, including N-cetyl-ethyl morpholinium ethosulphate, which also often have deodorant and germicidal properties, may also be employed.Descriptions of the various suitable anionic and cationic detergents are given in various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example, in that issued in 1 969. Also such cationics form a well known class and are described at length in the literature (as are the anionic detergents) and therefore such do not have to be further detailed here. Additionally nonionic and amphoteric detergents, also described in the McCutcheon texts, can be present with the anionic detergent and cationic antistat, usually in proportions less than that of the anionic detergent, and usually also in proportions less than that of the cationic antistat present.

The preferred -polyacetal carbocylates are those 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 ion or an ammonium or alkyl group of 1 to 4 carbon atoms, a tetraalkylammonium group or an alkanolamine group, both of 1 to 4 carbon atoms in the alkyl moieties thereof, n averages at least 4, and R' and R2 are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. Preferably the polyacetal carboxylate will be one wherein M represents an alkali metal ion, e.g. sodium, n is from 2 to 200, R1 represents

or a mixture thereof, R2 represents

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 or 4,000 to 10,000 and more preferably 5,000 to 9,000, e.g. about 8,000.

The calculated weight average molecular weight can be determined by proton magnetic resonance (pmr) scanning or by light scattering techniques.

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 a number of 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 referred to Monsanto patents, 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.

Thus it is only necessary that the chemically reactive group stabilises the polyacetal carboxylate against rapid depolymerisation in an alkaline solution, and the specific nature of the chemically reactive group is not important in the proper function of the polymer in its intended use. As an example, suitable chemically stable end groups include stable substituent moieties derived from otherwise stable compounds such as: alkanes, such as methane, ethane, propane, butane and higher alkanes such as decane, dodecane, octadecane and the like; alkenes such as ethylene, propylene, butylene, decene, dodecene and the like; branched chain hydrocarbons, both saturated and unsaturated, such as 2-methyl butane, 2-methyl butene, 4-butyl-2,3 dimethyl octane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; cycloalkanes and cycloalkenes such as cyclohexane and cyclohexene and the like; haloalkanes such as chloromethane, chlorobutane, dichloropentane and the like; alcohols such as methanol, ethanol, 2-propanol, cyclohexanol, sodium phenate and the like; polyhydric alcohols such as 1,2methane diol, 1,4-benzene diol and the like; mercaptans such as methane thiol, 1,2-ethanedithiol and the like; ethers such as methoxyethane methyl ester, ethyl ether, ethoxy propane and cyclic ethers such as ethylene oxide, epichlorohydrin, tetramethylene oxide and the like; aldehydes and ketones such as ethanal, acetone, propanal, methylethyl ketone and the like; and carboxylate-containing compounds such as the alkali metal salts of carboxylic acids, the esters of carboxylic acids and the anhydrides. The above listing is intended to be instructive and is not intended to be limited since chemically stable end groups that stabilise the polymer against rapid depolymerisation in an alkaline solution include nitrilo groups and halides such as chlorides, bromides and the like.

Particularly suitable end groups include alkyl groups, alkyl groups containing oxygen and cyclic alkyl groups containing oxygen: such as oxyalkyl groups like methoxy, ethoxy and the like; carboxylic acids such as -CH2COOM,

and the like; aldehydes, ethers and other oxygen-containing alkyl groups such as -OCHCH30C2H5, -(OCH2CH2), 4-OH, -(CH2CH2O)14-H,

and the like. In the above examples of suitable end groups, M is alkali metal, ammonium, alkanol amine, alkyl group of 1 to 4 carbon atoms and R is hydrogen or alkyl group of 1 to 8 carbon atoms. As will occur to those skilled in the art in light of the present disclosure, the chemically stable end groups at the polymer termini can be alike or unlike.

Other polyacetal carboxylates, which do not require specific end groups, are disclosed in U.S.

Patent No. 4,315,092, which is incorporated herein by reference.

The zeolite component will usually be of the formula (Na2O)x. (A1203)y (SiO2) . w H20, wherein x is 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 from about 200 to 400 or more milligram equivalents of calcium carbonate hardness per gram. They will preferably 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 of such zeolite type 4A is most preferred.Particle sizes of the zeolite(s) will usually be 100 to 400 mesh (or sieve number) (having openings from 140 to 37 microns across), preferably 140 or 200 to 325 mesh (having openings from 105 or 74 to 44 microns across) 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 by John Wiley 8 Sons, especially at pages 747-749 thereof.

In the compositions of the invention other builders than the polyacetal carboxylate may also be present although such are not necssary. Often it will be desired to avoid the presence of phosphorus in the detergent composition to 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, 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, zeolites, e.g.Zeolite A, 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. Of the builders it is considered that the zeolites are especially effective in these compositions, as has been previously indicated, and of the fillers that are preferred will usually be sodium sulphate.

Among the various adjuvants that may be employed are colourants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators, fluorescent brighteners, buffers, fungicides, germicides 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 with other ingredients. For example, it is known that sodium carbonate and water are often present with polyacetal carboxylate in Builder U, the product which is the preferred present source of polyacetal carboxylate.

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

The proportions of components of the invented compositions 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 (having openings from 2.38 mm or 2 mm to 149 microns or 105 microns). 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 preparations. However, because of their relatively low stability (due to interactions between anionic and cationic components) aqueous liquid preparations should be used relatively soon after manufacture.Also, while the ratios between pairs of components, except water, may be about the same as liquid or paste preparations as in solids, the liquid products are often much more dilute, so that the proportion of water or other solvent or mixture of solvents present may be much greater. In some aspects of the invention the components may be added directly to the wash water, in which case it may be considered that the detergent composition is the wash water containing the various active and other components.

In the particulate solid and other solid detergent compositions of this invention the total proportion of detergent present will normally be from 5 to 40%, preferably from 5 to 30%, more preferably 10 to 25% and most preferably 1 3 to 23%, e.g. about 19%. 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 anionics. The proportion of polyacetal carboxylate builder will usually be within the range of 5 to 50%, preferably 5 to 40%, more preferably 1 5 to 30%, and most preferably 1 7 to 23%, e.g.

about 19%, when it is the only builder present or when up to 50% of other builder(s) than zeolite are also present. When zeolite is present 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 5% of the detergent composition. Also, the ratio of polyacetal carboxylate to zeolite will be in the range of 1:3 to 3:1, preferably 2:3 to 2:1 and more preferably, about 3 :4 to 7 :4, e.g. about 1:1 to 3 :2. The cationic compound that functions as an antistat (and also has fabric softening properties) will be present in an antistatic proportion in the invented compositions, at least with respect to certain materials. The present detergent compositions have been found to be especially effective in reducing electrical charges (and consequent static cling) on acetate materials, but are also effective against other types of synthetic fabrics, such as acrylics and polyesters. The proportion of cationic antistat will usually be in the range of 2 to 10%, preferably 3 to 8% and more preferably 4 to 6%, e.g.

about 4 or 5%. The percentage of moisture will normally be from 2 to 20%, preferably 3 to 15%, and more preferably 5 to 12%, e.g. about 6 to 8%. Such percentages include moisture in hydrate form that is released during heating for two hours at 105"C (the standard moisture analyzer method). The proportions of other components, such as fillers, will normally be limited to no more than 50% and often will be in the range of 5 to 35%. Similarly, contents of nonphosphate builders other than the polyacetal carboxylate will be limited, generally being less than 40%, such as 3 to 30% or 5 to 25%, but such supplemental builders are not required.

However, the presence of other builders and fillers 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, 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 18% and more preferably 10 to 15%, and 2 to 15%, preferably 5 to 10% and more preferably 6 to 9%, respectively. The proportion of filler, when present, will usually be 5 to 35%, preferably 20 to 35% and more preferably 22 to 30%.

The total adjuvant content will usually not exceed 10% or 20%, and preferably will be less than 5%, with the individual contents of the usual 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 present within the range of 0.3 to 3%, preferably 0.5 to 2%, e.g. 1%, of the composition, when included.

In preferred forms of the invention, particulate solid compositions 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. Because the cationic antistat may react with anionic materials, such as the anionic detergent, it will normally be postadded to the rest of the composition. To prevent segregation during shipping and storage of the final product it is desirable that any post-added components, such as the cationic compound, polyacetal carboxylate and enzyme, 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 1 60 to 325 mesh (i.e. 94 to 44 microns across) 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 seive size) (2 mm to 1 49 microns across) range. The polyacetal carboxylate may sometimes be spray dried with the detergent composition providing that care is exercised to prevent it from being decomposed by heat. In an alternative method of manufacture the various component, in finely divided form, may be merely mixed together.Also, when the initial particle sizes of the various components or some of them are less than desired, such as in the 1 40 to 325 mesh range (104 to 44 microns), particles thereof may be agglomerated to the desired size, sometimes with the aid of agglomerating agents, such as a dilute aqueous solution of sodium silicate, and at other times with only water to assist in agglomeration.

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 counter-current or co-current spray drying tower with drying air entering at about 200 to 600'C (preferably 1 50 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 mixed with the spray dried beads.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, etc., and other stable materials that are to be present can also be incorporated in the crutcher and then spray dried with the anionic detergent. However, when more than about 4 or 5% (sometimes more than 2%) of anionic detergent is present in the formula any additional proportion will usually be post-added, as by spraying onto tumbling particles of detergent beads. Then the polyacetal carboxylate and antistat may be post-added.In some instances the polyacetal carboxylate may be dispersed and/or dissolved in the nonionic detergent, which is heated so as to be in liquid state (or may be dissolved in a solvent) and the combination of non ionic detergent and polyacetal carboxylate may be sprayed onto the detergent beads or base beads, followed by addition of the cationic antistat. Desirably, the particulate material made will be of particle sizes in the 8 to 1 20 or 10 to 100 mesh range (having diameters from 2.38 mm to 125 microns or 2 mm to 149 microns) 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 (2.38 mm to 1 77 microns)).

To manufacture the present products into bar, cake or briquette form the compositions may be extruded or pressed or moulded to shape in known -manners. To convert them to liquid 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 isopropanol.

To practice the soil and stain removing processes of the invention, which leave the washed items non-clinging and clean (and also soft) one of the described compositions may be added to a wash water or the various components may be so added. Normally the concentration of the compositions employed will be in the range of 0.05 to 0.1 to 0.4 or 0.5%, preferably 0.1 to 0.35%, and more preferably 0.15 to 0.25 or 0.35%. Higher concentrations, as from 0.25 to 0.45% or more (and less wash water), are often employed in machine washings according to European practice, which normally has a higher temperature wash water. In American practice lower concentrations, such as from 0.05 to 0.25%, often preferably about 0.1 to 0.2% of the compositions are employed.Usually the washing temperature in America will be in the range of 10 to 55"C, preferably from 35 to 55"C, compared to 60 to 99 , often 70 to 90 or 95"C in Europe. However, it is considered that the compositions of the present invention are useful to remove soils and stains from laundry of different fabric types and materials, and to leave such laundry static-free and soft, whichever washing procedure is employed.

In practising the process of the present invention, sufficient detergent composition in accordance with the 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. 0.2% (130 grams per 65 litres of wash water), to wash water of normal washing temperature, e.g. 49"C, and normal hardness (about 50 to 250 or 300 p.p.m., as calcium carbonate). The laundry is then added, with the normal weight charged being from 2.7 to 4.5 kg, e.g. 3.6 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, as desired, usually depending on the dirtiness of the laundry.Surprisingly, the compositions of this invention are about the same in soil and stain removal properties in relatively soft and medium hardness water, of about 50 and 1 50 p.p.m. hardness, but are noticeably better at higher hardnesses (250 p.p.m.) than control compositions in which the polyacetal carboxylate is replaced by an equal (even greater) proportion of sodium tripolyphosphate. Also, terrycloth towels washed with either a composition in accordance with the present invention or a control composition (the invented composition contains polyacetal carboxylate and zeolite and in the control these are replaced by an equal weight of sodium tripolyphosphate) appear to be of about the same softness and overall static charges.However, such invented compositions are noticeably superior to the control in static charge reduction (and fabric cling reduction) for acetate fabrics.

The following examples illustrate but do not limit the invention. Unless otherwise indicated all parts are by weight and all temperatures are in "C in these examples, the rest of the specification and the claims.

EXAMPLES 1A to IF Examples IA to lC Component Percent Sodium linear tridecylbenzene sulphonate 19.0 Builder U (79.7% sodium polyacetal carboxy- 23.8 late, supplied by Monsanto Co. ELot No.

2538422, of calculated weight average molecular weight of 8034]) Sodium carbonate (anhydrous) 12.4 Sodium silicate (Na20:SiO2 = 1:2.4) 7.6 Sodium sulphate (anhydrous) 26.7 Water 5.7 Distearyl dimethyl ammonium chloride 4.8 (Arosurf TA-100, about 90% active, obtained from Sherex Chemical Company) ~~~~~~ 100.00 A particulate detergent in spray dried bead form is made of all the above components except the cationic compound by preparing an aqueous crutcher mix (55% solids concentration) of the listed components at a temperature of about 55"C and spray drying such crutcher mix.The spray tower used is a countercurrent tower operating under mild conditions, with drying air at about 300 inlet temperature, and with other provisions to prevent charring of the beads and decomposition of the sodium polyacetal carboxylate (by prevention of buildups on tower walls, utilization of cooling air, and controlled spraying to prevent contact with 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 (having diameters in the range of from 2 mm to 149 microns), is of a bulk density of about 0.3 g/ml and is of a moisture content of about 8%. With 20 parts of the detergent composition thus made there is admixed one part of the described Sherex Chemical Co. product.Desirably such product is of particle sizes like those of the base detergent composition but even when it is more finely powdered, with particle sizes in the range of 100 to 325 mesh (149 to 44 microns across); the antistat is well distributed throughout the detergent composition and adheres to the particles thereof, yielding a product which is still in the 10 to 100 mesh size range (2 mm to 1 94 microns) and is still of a bulk density of about 0.3 g/ml.

The product made is tested for soil and stain removal, utilizing a Tergotometer laboratory type test washing machine in which standard swatches of various materials, soiled and stained in a standard manner, are washed in wash water at 0.21% composition concentration, at a washing temperature of 49"C and over a ten minute wash period, with the agitator turning at 100 r.p.m.

Hardnesses of water used are calcium and magnesium hardnesses in 3:2 Ca: Mg ratio, at hardnesses of 50 ppm (Example 1A), 150 (Example 1B) and 250 ppm (Example 1C).

Reflectance readings of the washed and dried swatches are taken and indexes indicative of the weighted sums of the reflectances are calculated, which indexes, based on experience, have been found to be indicative of the soil and stain removal capability of a tested detergent composition (the higher the index, the better the detergency). At 50, 1 50 and 250 p.p.m.

hardness levels the previously described experimental product of this example yields indexes of 256, 242 and 234, respectively.

Examples 1D to 1F When the same composition is made with sodium tripolyphosphate replacing the Builder U in the formula (which makes a product having a higher active builder content then the experimental formula) the indexes are 254 (Example 1 D), 240 (Example 1 E) and 222 (Example 1 F), respectively, Thus, it is seen that the cleaning and stain removal effectiveness in hard water (250 p.p.m. hardness) of a composition in accordance with this invention is superior to that of a control composition which incorporates pentasodium tripolyphosphate, the most successful commercial builder knawn to the art, and even when more polyphosphate is employed in the control.

EXAMPLES 2A and 2B Example 2A When in the formula of Example 1A half of the Builder U is replaced by Zeolite 4A (20% hydrate), which is added to the crutcher as a finely divided powder, having a particle size in the range of 100 to 325 mesh (149 to 44 microns across), and the quaternary ammonium halide is admixed with the spray dried beads, in the manner described in Example 1A, the resulting antistatic detergent composition is of essentially the same cleaning properties (as measured by the same stain and soil removing index) as a control that is based on sodium tripolyphosphate builder instead of Builder U and zeolite.Also, when tested for static charge, indicative of "cling" of washed materials essentially the same improvement results for the invented product, containing Builder U and zeolite, as results for the "control", compared to detergent compositions which do not contain the cationic compound. Superiority in static charge reduction for acetate fabrics is noted with the experimental formula, compared to a control containing sodium tripolyphosphate builder and the mentioned cationic compound (but no Builder U and zeolite).

Thus, after washing with the compositions being compared, and drying in an automatic laundry dryer, the acetate swatch has a static charge of 5.5 kv after washing with the control, and 1.6 kv after washing with the experimental product of this invention, and such drying. When tested for softening properties, the mentioned control composition and the mentioned experimental composition rate about the same, in a test in which six panelists ranked, from softest to harshest, sets of terrycloth towels washed by one or the other composition. The test conditions are the same as those for detergency, previously described, except that light wash loads are employed (about 0.5 kg of charge to 65 litres of wash water) and the concentration of the detergent composition is reduced to 0.15% (100 g in 65 1 of wash later).

Example 2B In a further variation the proportions of Builder U and zeolite are changed to 3:2. The soil and stain removal indexes obtained are essentially the same as those for the control in which polyphosphate builder is present instead.

From the above experiments it is apparent that the experimental compositions of these examples are equal or superior in important soil and stain removal, static charge reduction and softness properties, compared to a control composition in which sodium tripolyphosphate is employed instead of Builder U or instead of a mixture of Builder U and zeolite.

Such results are also considered to be obtainable when modifications of the experimental formula are made and/or when changes are effected in the manufacturing and/or washing processes. Thus, the mentioned antistat may be replaced with other such materials, such as dihydrogenated tallow dimethyl ammonium chloride, and corresponding quaternary ammonium bromides and other known antistatic agents. Similarly, when the sodium tridecylbenzene sulphate is replaced by other water soluble higher alkylbenzene sulphonates, such as sodium dodecylbenzene sulphonate or mixtures of sodium linear tridecylbenzene sulphonate and sodium lauryl sulphate (in equal parts), or with other anionic detergents, are previously described, satisfactory products within the invention are also obtainable.The particular sodium polyacetal carboxylate may be replaced by other such compounds of different molecular weights, for example, that of a molecular weight of 5,250 (Monsanto Lot No. 2547321) or by other such compounds within the molecular weight ranges given, and with end groups described, and useful antistatic detergents will be obtained. Similarly, the builders, fillers and adjuvants may be changed, as described in the specification. For example the Zeolite 4A may be changed to other Zeolite As, or to Zeolites X and/or Y. Furthermore, the proportions of the various components can also be changed, usually + 10 or + 25%, without losing the benefits of the present invention, so long as the proportions remain within the ranges previously described.

In modifications of the manufacturing procedure, the described compositions are made by post-addition of the Builder U powder, in particles the size of spray dried beads, or more finely divided (100 to 325 mesh (149 microns to 44 microns)) to the spray dried beads before, after or together with similarly sized antistatic particles or finely divided powder. The polyacetal carboxylate may be pre-mixed with the antistat for subsequent admixing with the spray dried material. In some embodiments of the invention the individual components may be blended together without preliminary spray drying of the major proportion thereof. In some instances the various components may be added to the wash water as individual charges.In a preferred method the polyacetal carboxylate will be post-added, rather than spray dried with various other components of the final product, so as better to maintain all the detergency building and static charge reducing effectiveness thereof (by avoiding subjecting such builder to possible excessive heat, and thereby causing degradation thereof). When such a charge is made in the manufacturing procedure described the product obtained is equal or superior in the described characteristics to that previously discussed herein.In the processes described the products obtained are of bulk density in the range of 0.25 to 0.5 g/ml, as are the spray dried beads, and both are of particle sizes in the No's. 10 to 100 sieve range (2 mm to 149 microns across), whereas the polyacetal carboxylate builder and antistat distearyl dimethyl ammonium chloride are usually higher in bulk density (0.6 to 0.9 g/ml), and smaller in particle sizes (No's. 100 to 325 sieves (149 to 44 microns across)). Yet, in the final compositions the smaller particles satisfactorily hold to the larger ones, to produce the desired product.

The washing method of this example may also be changed, so as to utilize water of various mixed calcium/magnesium hardnesses in the range of 50 to 250 p.p.m., and even higher, sometimes to 300 p.p.m. or more, and washing may be conducted in the temperature range of 10 to 55"C, and at concentrations in the range of 0.05 to 0.5% of the detergent composition, and satisfactory antistatic effects will be obtained, without excessive loss of detergency, and the products made will be equal or superior to "controls" containing sodium tripolyphosphate in place of the polyacetal carboxylate builder or in place of a combination of such builder and zeolite.

EXAMPLES 3A to 3C Example 3A 1 5 Parts of sodium linear dodecylbenzene sulphonate and 25 parts of sodium tripolyphosphate are mixed with 4.5 parts of Arosurf TA-1 00 (90% active distearyl dimethyl ammonium chloride), all the components being as finely divided powders, of particle sizes in the range of about 100 to 200 mesh (149 to 74 microns across). Such material, the control, is employed to wash terrycloth towels, using essentially the same method as described in Examples 1 A and 2A.

Subsequently the towels are evaluated by a skilled evaluator and given a rating of 9 for softness, on a standard scale of 1 to 10, 10 being for the softest.

Example 3B In another control experiment 3 parts of the Arosurf TA-100 are used, with the 1 5 and 25 parts of the other constituents, and similar softness testing is undertaken. The washed towels are rated 8 on this scale of softness.

Example 3C When instead of the 25 parts of sodium tripolyphosphate there are incorporated in such a composition 25 parts of Builder U (Lot 2538422), and the test is repeated the softness rating obtained is 10 and such rating is also obtained when the Arosurf TA-100 content is reduced to 3 parts in the mentioned formula.

The invented compositions described are all satisfactory detergents and possess good antistatic and fabric softening properties.

Instead of the dry mixing of the various components other compositions of this example may be produced by spray drying and other procedures described in Example 1 and in the foregoing specification. Also, the mentioned compositions may be employed for washing soiled and stained laundry and for softening it, and for reducing the static cling that normally results after washing such laundry, from drying it in an automatic laundry dryer. Instead of using sodium linear dodecylbenzene sulphonate, sodium linear tridecylbenzene sulphonate, sodium lauryl sulphate and higher fatty alcohol polyalkoxy sulphates may be substituted, and Zeolite A or Zeolite X may be used to replace half of the Builder U. Also, others of the mentioned antistatic agents may be used in place of the Arosurf TA-100, and the various proportions may be varied as previously described, and the results will be satisfactory detergents of good softening and antistatic properties.

The invention has been described with respect to 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

1. An antistatic built particulate detergent composition comprising a detersive proportion of a synthetic anionic 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 an antistatic cation compound.

2. A detergent composition according to Claim 1 wherein the antistatic cationic compound is a quaternary ammonium compound.

3. A detergent composition according to Claim 1 or 2 which is essentially free of phosphate.

4. A detergent composition as claimed in Claim 1, 2 or 3, wherein the synthetic anionic organic detergent is a sulphated or sulphonated detergent.

5. A detergent composition as claimed in any one of Claims 1 to 4, wherein the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 3,500 to 10,000.

6. A detergent composition as claimed in any one of Claims 1 to 5, wherein the zeolite builder is a hydrated zeolite of Type A, Type X or Type Y.

7. A detergent composition as claimed in Claim 2, wherein the quaternary ammonium salt is a di-higher alkyl, di-lower alkyl ammonium halide wherein the higher alkyl moiety is of 10 to 1 8 carbon atoms and the lower alkyl moiety is of 1 to 3 carbon atoms.

8. A detergent composition according to any one of Claims 1 to 7, wherein the synthetic anionic organic detergent is a higher alkylbenzene sulphonate in which the alkyl group is of 10 to 1 8 carbon atoms.

9. A detergent composition as claimed in any one of Claims 1 to 8, wherein the polyacetal carboxylate is one wherein the carboxylate is sodium carboxylate.

10. A detergent composition as claimed in any one of Claims 1 to 9, wherein the zeolite is a Type A zeolite of the formula (Na2O),. (Al203)y. (SiO2)2 . w H20 wherein x is 1, y is from 0.8 to 1.2, z is from 1.5 to 3.5 and w is from 0 to 9.

11. A detergent composition as claimed in Claim 10, wherein y is about 1, z is from 2 to 3 and w is from 2.5 to 6.

12. A detergent composition as claimed in Claim 11, wherein z is about 2.

1 3. A detergent composition as claimed in Claim 2, wherein the quaternary ammonium salt is a di-higher alkyl dimethyl ammonium halide wherein the higher alkyl moiety is of 10 to 18 carbon atoms.

14. A detergent composition according to any one of Claims 1 to 13, which comprises about 5 to 30% of synthetic anionic detergent.

1 5. A detergent composition as claimed in any one of Claims 1 to 13, wherein the synthetic anionic detergent is a sodium linear higher alkylbenzene sulphonate wherein the higher alkyl is of 1 2 to 14 carbon atoms.

1 6. A detergent composition as claimed in any one of Claims 1 to 15, comprising 5 to 40% of polyacetal carboxylate builder or a mixture of such builder and zeolite builder.

1 7. A detergent composition as claimed in any one of Claims 1 to 16, comprising 2 to 10% of distearyl dimethyl ammonium chloride.

1 8. A detergent composition as claimed in any one of Claims 1 to 17, comprising 2 to 20% of moisture and the balance, if any, of-filler(s) and/or other builder(s) and/or adjuvant(s).

1 9. A detergent composition according to any one of Claims 1 to 18, which comprises 10 to 25% of synthetic anionic organic detergent.

20. A detergent composition according to any one of Claims 1 to 19, wherein the synthetic anionic organic detergent is sodium linear tridecylbenzene sulphonate.

.

21. A detergent composition according to any one of Claims 1 to 20, comprising from 1 5 to 30% of polyacetal carboxylate builder of a calculated weight average molecular weight in the range of from 5,000 to 9,000, or a mixture of such builder and zeolite builder, with at least 5% of the composition being polyacetal carboxylate builder.

22. A detergent composition as claimed in any one of Claims 1 to 21, comprising from 3 to 8% of distearyl dimethyl ammonium chloride.

23. A detergent composition as claimed in any one of Claims 1 to 22 comprising from 3 to 15% of moisture.

24. A detergent composition as claimed in any one of Claims 1 to 23, comprising from 8 to 18% of sodium carbonate.

25. A detergent composition as claimed in any one of Claims 1 to 24, comprising from 5 to 10% of sodium silicate of Na2O:SiO2 ratio in the range of 1:1.6 to 1:3.0.

26. A detergent composition as claimed in any one of Claims 1 to 25, comprising from 20 to 35% of sodium sulphate.

27. A detergent composition according to Claim 1 comprising from 1 3 to 23% of sodium linear tridecylbenzene sulphonate.

28. A detergent composition as claimed in Claim 1 or 27 comprising from 1 7 to 23% of sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000.

29. A detergent composition as claimed in Claim 1, 27 or 28 comprising from 4 to 6% of distearyl dimethyl ammonium chloride.

30. A detergent composition as claimed in Claim 1, 27, 28 or 29 comprising from 10 to 15% of sodium carbonate.

31. A detergent composition as claimed in Claim 1 or any one of Claims 27 to 30, comprising from 6 to 9% of sodium silicate of Na2O:SiO2 ratio in the range of 1:2.0 to 1 :2.6.

32. A detergent composition as claimed in Claim 1 or any one of Claims 27 to 31 comprising from 22 to 30% of sodium sulphate.

33. A detergent composition as claimed in Claim 1 or any one of Claims 27 to 32 comprising from 5 to 12% of moisture.

34. A detergent composition according to Claim 1 or 21 comprising from 17 to 23% of a mixture of sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000, and Type A zeolite wherein x is 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 from 2:3 to 2:1.

35. A process for the manufacture of an antistatic built particulate detergent composition that includes a detersive proportion of synthetic anionic organic detergent, a building proportion of a polyacetal carboxylate builder for such detergent or a building proportion of mixture of such polyacetate carboxylate builder and zeolite builder, and an antistatic proportion of an antistatic quaternary ammonium salt, which comprises spray drying an aqueous slurry of synthetic anionic organic detergent, builder for such detergent, water and optionally a filler to essentially globular beads having particle sizes in the range of No. 10 to 100 sieves, U.S. Sieve Series, (i.e. having diameters of from 2 mm to 149 microns), and mixing with such spray dried beads polyacetal carboxylate builder and an antistatic proportion of antistatic quaternary ammonium salt.

36. A process according to Claim 35 wherein the synthetic anionic organic detergent is sodium linear higher alkylbenzene sulphonate in which the higher alkyl is of 1 2 to 14 carbon atoms, the polyacetal carboxylate builder is a sodium polyacetal carboxylate of a calculated weight average molecular weight in the range of 5,000 to 9,000, the builder in the crutcher mix includes a 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 polyacetal carboxylate builder and the antistatic quaternary ammonium halide are pre-mixed and are admixed together with the spray dried beads, and the detergent composition resulting comprises 1 3 to 23% of sodium linear tridecylbenzene sulphonate, 1 7 to 23% 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 2:3 to 2:1, 4 to 6% of distearyl dimethyl ammonium chloride, 5 to 12% of moisture, 10 to 15% of sodium carbonate, 6 to 9% of sodium silicate of Na2O: :Si02 ratio in the range of 1 :2.0 to 1:2.6, and 22 to 30% of sodium sulphate.

37. A process according to Claim 35 or 36, wherein the bulk density of the spray dried beads is in the range of from 0.25 to 0.5 g/ml, the bulk density of the mixture of sodium polyacetal carboxylate builder and antistatic distearyl dimethyl ammonium chloride being higher than the bulk density of the spray dried beads, and such mixture being of particle sizes in the range of No's. 100 to 325 sieves, U.S. Sieve Series (i.e. having diameters from 149 to 44 microns across).

38. A method for removing hard-to-remove soils and stains from fibrous materials which comprises washing such soiled and stained materials in water 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 an antistatic cationic compound.

39. A method for removing hard-to-remove soils and stains from fibrous materials which comprises washing such soiled and stained materials in water with a composition as claimed in any one of Claims 2 to 34.

40. A method as claimed in Claim 38 or 39, wherein the water is of mixed calcium and magnesium hardness in the range of 50 to 250 ppm, as calcium carbonate.

41. A method as claimed in Claim 38, 39 or 40, wherein the washing is carried out at a temperature in the range of from 10 to 55 C.

42. A method as claimed in Claim 38, 39 or 40, wherein the washing is carried out at a temperature in the range of from 35 to 55"C.

43. A method as claimed in any one of Claims 38 to 42, wherein the concentration of the composition is in the range of from 0.05 to 5% by weight.

44. A method as claimed in any one of Claims 38 to 42, wherein the concentration of the composition is in the range of from 0.1 to 0.35% by weight.

45. A method according to Claim 38 wherein the wash water temperature is in the range of 35 to 55"C, the concentration of the detergent composition in the wash water is in the range of 0.1 to 0.35%, and the detergent composition comprises 13 to 23% of sodium linear tridecylbenzene sulphonate, 1 7 to 23% of a mixture of sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8,000, and Type A zeolite wherein x is 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 2:3 to 2::1, 4 to 6% of distearyl dimethyl ammonium chloride, 5 to 12% of moisture, 10 to 15% of sodium carbonate, 6 to 9% of sodium silicate of Na20:SiO2 ratio in the range of 1:2.0 to 1 :2.6, and 22 to 30% of sodium sulphate.

46. A method according to any one of Claims 38 to 45 wherein the materials washed are of cellulose acetate.

47. A detergent composition substantially as herein described with reference to any one of the Examples other than comparative examples.

48. A process for the manufacture of an antistatic built particulate detergent composition substantially as herein described with reference to any one of the Examples other than comparative examples.

49. A method for removing hard-to-remove soils and stains from fibrous materials substantially as herein described with reference to any one of the Examples other than comparative examples.