GB2160217A

GB2160217A - Bleaching synthetic detergent composition

Info

Publication number: GB2160217A
Application number: GB08513936A
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: 1985-12-18
Also published as: PT80558A; GB8513936D0; KR860000364A; FI852194L; FR2565245A1; PH21670A; AU4279185A; CA1284926C; MX162747A; DK237685D0; ES543669A0; DK237685A; IT1182249B; JPS612800A; AU573832B2; DE3518656A1; GB2160217B; KR920006028B1; FI852194A0; LU85930A1

Abstract

Bleaching detergent compositions to remove particulate and sebum stains from fibrous materials, such as those of polyester, in high temperature washing processes comprise a synthetic organic detergent or a mixture of such detergents, a polyacetal carboxylate builder and a perborate.

Description

SPECIFICATION Bleaching synthetic detergent composition This invention relates to detergent compositions. More particularly, it relates to bleaching detergent compositions comprising a synthetic organic detergent or mixture of such detergents, a polyacetal carboxylate builder for such detergent(s) and a perborate. Also within the invention is a process for washing stained fibrous polyester materials that had been stained with particulate soil and sebum.

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. One kind of preparation which has been employed to test the detersive and stain removing activity of detergent compositions is a mixed sebum and particulate soil, which severely stains fibrous materials contacted with it, especially those incorporating polyester fibres, such as polyester knits and polyester-cotton blends. Such soil is often employed to produce an artificial "collar staining soil". As is well known, "collar soil" is considered to be difficult to remove from shirt collars (and cuffs) during automatic washing operations.It is difficult to remove whether washing is conducted at a relatively low temperature, such as from 10 to 30"C or at higher temperature, as in accordance with European practice, such as 50 to 90 or 95"C, or higher.

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 considered to be most effective, although ampholytic or amphoteric and cationic detergents may also be employed. Sodium perborate has long been used in detergent compositions for its bleaching effect. 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 normally acidic waste waters.

Although the main components of the present detergent compositions have been employed in other such compositions, they are considered to be novel and unobvious and to possess unexpectedly beneficial stain removing properties. Particularly important is the greatly improved capacity of the present compositions to remove a combination of sebum and particulate stains from polyester-containing fibrous material which such material is washed in hot wash water containing the invented detergent composition. Such effect is even obtained when hard wash water is used.

In accordance with the present invention a bleaching 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) and a bleaching proportion of a perborate. In wash water at elevated temperature (e.g. 60"C), the perborate is especially effective to remove particulate and sebum stains from polyester fabrics and may be so at lower temperature (e.g. 30"C) when a suitable perborate activator is present.

Preferred such compositions comprise about 4 to 20% of sodium higher alkylbenzene sulphonate wherein the higher alkyl moiety has 10 to 1 8 carbon atoms, about 2 to 10% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol has 10 to 1 8 carbon atoms and the nonionic detergent contains 3 to 20 moles of ethylene oxide per mole, about 10 to 30% of sodium polyacetal carboxylate builder of a calculated weight average molecular weight in the range of 5,000 to 9,000, about 10 to 40% of sodium perborate tetrahydrate, about 3 to 20% of moisture, including hydrate moisture which is removable at 105"C, 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 particulate and sebum stains from fibrous polyester materials which comprises washing such stained fibrous materials in wash water at a temperature in the range of 50 to 99"C 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 a bleaching proportion of a perborate, at a concentration of such detergent composition in the wash water in the range of 0.05 to 1.5%.

The synthetic organic detergent which is primarily employed for its cleaning characteristics in the present compositions will normally be an anionic detergent. Of the anionic detergents, the sulphated and/or sulphonated lipophilic materials having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to 1 8 and more preferably 1 2 to 16, will usually be those of choice. 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 in the alkyl chain, preferably 1 2 to 16 and most preferably about 1 2 or 13, are considered most suitable for the practice of the invention. 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.

The nonionic detergents, which are often employed to supplement the detersive action of the primary anionic detergents, but in some instances may be the primary detergent(s), are preferably normally solid materials (especially when being incorporated in solid or particulate solid products) and will preferably be condensation products of ethylene oxide and higher fatty alcohol, with the higher fatty alcohol usually being of 10 to 18 carbon atoms, preferably averaging 1 2 to 1 5 carbon atoms, e.g. about 12 to 1 3 carbon atoms, and with the ethylene oxide content being within the range of 3 to 20 moles, preferably 3 to 1 2 moles and more preferably 5 to 9 moles, e.g. about 6.5 or 7 moles of ethylene oxide, per mole of fatty alcohol.

Among other nonionic detergents that are also useful are the ethylene oxide condensation products of alkyl phenols of 5 to 1 2 carbon atoms in the alkyl groups, such as nonylphenol, in which the ethylene oxide content is from 3 to 30 moles per mole. Additionally, condensation products of ethylene oxide and propylene oxide, such as those sold under the trademark Pluronic, may be employed, as may be various others of the well known group of nonionic detergents.

The cationic detergents that may be employed, usually in limited proportion, e.g. no more than 10% and preferably less than 5%, are preferably di-higher alkyl, di-lower alkyl ammonium halides, wherein each higher alkyl moiety independently has 10 to 18, preferably 1 6 to 1 8 carbon atoms, each lower alkyl moiety independent has 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, often classified as anti-static agents (they also often have deodorant and germicidal properties), may also be employed.Of the amphoteric materials the Miranols may be mentioned as examples, such as that which has been marketed under the designation Miranol C2M Conc. The word MIRANOL is a trademark. Other such detergents, including anionic, nonionic, amphoteric and cationic detergents, are all described in the various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example, in that issued in 1 969.

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 ion, an ammonium ion, an alkyl group having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups, the alkyl groups of both of which independently have from 1 to 4 carbon atoms, n average at least 4, and R' and R2 are 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 20 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 desirably 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, such as 7,000 to 9,000, specifically, about 8,000. The calculated weight average molecular weight may be determined, as described in U.S. 4,114,226, by proton magnetic resonance (pmr) techniques 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 various Monsanto Co. patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the various 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 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; branches chain hydrocarbons, both saturated and unsaturated, such as 2-methyl butane, 2-methyl butene, 4-butyl-2,3dimethyl 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 1,2-ethane 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, propanol, 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 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 -OCHCH30C2Hs,-(OCH2CH2),4-OH,-(CH2CH20)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. 4,315,097, which is incorporated herein by reference.

The perborate utilized is a water soluble perborate which is capable of releasing active bleaching oxygen in aqueous media, such as in wash water at elevated temperature. Such perborate is preferably an alkali metal or equivalent salt and most preferably is sodium perborate tetrahydrate. Usually the perborate is hydrated but that is not necessary. Generally the hydrate is the tetrahydrate but it has been found that the monohydrate is also useful and some perborates with contents of water of hydration less than one mole per mole may be especially useful in certain applications or when packaged in vapour-tight containers (wherein higher hydrates may tend to liquify, or cake the detergent composition).

While the ordinary higher fatty acid soaps, usually the sodium soaps, are detergents, they are not generally considered to be synthetic organic detergents, and accordingly are not to be taken as within the group of such detergents for the purpose of this invention. The soaps do have detersive properties but may be employed for other purposes too, such as for their foam limiting characteristics. Among the soaps that may be utilized in the present compositions, those of alkali metals, such as sodium, of 10 to 18 carbon atoms and preferably highly saturated, will be preferred. Among such are the sodium hydrogenated tallow soaps, sodium stearate and sodium palmitate, but soaps of tallow and mixtures of tallow with coconut oil may also be employed, e.g. 4:1 tallow: coco soaps, as composition components.

In the compositions of the invention other builders than the polyacetal carboxylate may also be present although such are not necessary. Often it will be desired to avoid the presence of phosphorus in the detergent compositions 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, at least in 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. In liquid compositions, which should usually be employed soon after making, solvents or extenders may be used, such as water, ethanol and isopropanol.

Among the various adjuvants that may be employed are colourants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators (especially activators for causing active oxygen release from perborates), fluorescent brighteners, buffers, fungicides, germicides and flow promoting agents. Also included among adjuvants, unless in other classes previously 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 of Monsanto Company which is a preferred 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 these bleaching detergent compositions it will normally be present due to the use of water in manufacturing, and it may help to solubilize other composition components and bind them.

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 diameters 2.38 mm or 2 mm to 149 microns or 105 microns across). However, such proportions also apply to other solid forms, such as bars or cakes, more finely divided or coarser powders, granular compositions and agglomerates, and also to liquid preparations, although because of their relatively low stability aqueous liquid preparations should be used relatively soon after manufacture. Also, while the proportions of all the components except water may be about the same in liquid preparations, such products are often much more dilute, so that the proportion of water or other solvent or a 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%, more preferably from 10 to 25% and most preferably about 12%. Such detergent will desirable include either sulphated or sulphonated anionic detergent or non ionic detergent but preferably will include both such detegents. The proportion of anionic detergent present will usually be from 3 to 30%, preferably 4 to 20% and more preferably 4 to 10%, e.g. about 8%, and the proportion of nonionic detergent will be about 2 to 25%, preferably 2 to 10% and more preferably 2 to 6%. The proportion of polyacetal carboxylate builder will usually be within the range of 4 to 50%, preferably 10 to 30%, and more preferably 10 to 25%, e.g. 18%. The perborate content is normally in the range of 10 to 50%, preferably being 10 to 40% and more preferably 1 5 to 30%, e.g. 22%, which percentages are on the basis of sodium perborate tetrahydrate and may be modified accordingly when the anhydrous salt or a different hydrate is employed. The proportion of soap, when it is present, will usually be in the range of 1 to 10%, preferably 2 to 6%, and the percentage of moisture will normally be from 3 to 20%, preferably 5 to 15%, e.g.

about 10%. 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 40% and usually will be in the range of O to 30% or 5 to 20%. Similarly contents of builders other than the polyacetal carboxylate will be limited, generally being less than 25%, such as 3 to 20% or 5 to 15%, but often no such supplemental builders will be present. The total adjuvant content will usually not exceed 10% or 20%, and preferably will be less than 5%, with the contents of individual adjuvants generally not exceeding 3% or 5%, and 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. 10m.

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 perborate is heat-unstable it will normally be post-added to the rest of the composition. Of course, to prevent segregation during shipping and storage of the final product it is desirable that the perborate be of shape and particle sizes like those of the rest of the composition. The polyacetal carboxylate may sometimes be spray dried with the detergent composition providing the care is exercised to prevent it from being decomposed by heat. However, it may also be post-added, and again the particle sizes for post-adding are desirably the same as those previously mentioned, to avoid product component segregations.In an alternative method of manufacture the various components, in finely divided form, may be merely mixed together. Also, when the initial particle sizes of the components are less than desired, such as in the 1 60 to 325 mesh range (having diameters from 94 to 44 microns across), 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.

When an anionic detergent is the primary detergent of the desired composition it 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, and may be spray dried in the normal manner, utilizing a convention countercurrent or concurrent 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 perborate may be admixed, in either order or conjointly, or the perborate 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 stable amphoteric and cationic 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 nonionic detergent is present in the formula any additional proportion will usually be post-added, as by spraying onto tumbling particles of detergent beads or base beads. Such base beads may be made from any builders, fillers and stable adjuvants of the final product. Then the polyacetal carboxylate and perborate may be post-added.In some instances the polyacetal carboxylate may be dispersed and/or dissolved in the non ionic detergent, which is heated so as to be in liquid state (or 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 perborate. Desirably, the particulate material made will be of particle sizes in the 8 to 120 or 10 to 100 mesh range (having diameters 2.38 mm to 125 microns or 2 mm to 149 microns across) 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 procesed to sizes desired.

To manufacture the present products into bar, cake or briquette form the compositions may be extruded, 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).

To practise the stain removing process of the invention the described composition may be added to "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 or 0.1 to 1.0 or 1.5%, preferably 0.1 to 1.3%, and more preferably 0.15 to 1.1 or 1.2%. Higher concentrations, as from 1.0 to 1.5% or more, are often employed in machine washing according to European practice, which utilizes high temperature to water, in which the perborate releases active bleaching oxygen. Usually the washing temperature in America will be in the range of 10 to 55"C, often being from 10 to 30"C, compared to 60 to 99"C, often 70 to 90 or 95"C, in Europe.In American practice lower concentrations, such as from 0.05 to 0.2%, often preferably about 0.07 to 0.1 5%, of the composition are employed. Following American practice perborate oxygen is not released to the same extent because the washing temperature is lower.

Consequently any bleaching effect is not as great as when higher wash temperature are used, unless an activator is also present to assist in the release of active oxygen from the perborate.

Various such activators are known for this purpose and may be employed to adapt the process invention to American practice. Among such activators are those known as TAED (tetraacetylethylene diamine), acyloxybenzene sulphonates, such as described in U.S. Patent 4,412,934, and TAGU (tetraacetyglycouril).

In the washing or stain removing operation conventional washing machines will be employed, such as GE automatic washers (top loading), following the American practice, and Miele machines, following European practice. While it is considered that the present compositions operate better than controls utilizing sodium tripolyphosphate in place of polyacetal carboxylate, whether washing is at high or low temperatures, providing that equivalent proportions of active oxygen are released from the perborate, it is often preferred to follow the European practice, which does not require the presence of an accelerator to promote the release of active oxygen from the perborate.Various hardnesses of water may be utilized and while it might be expected that the softer the water the better the stain removal, unexpectedly it has been found that even under hard water conditions the present compositions and stain removing processes are superior to controls wherein pentasodium tripolyphosphate is employed instead of the polyacetal carboxylate. This improved stain removing capacity is most pronounced at elevated temperatures (60 to 90"C) when the stain is a very critical stain, usually found in normal laundry, a combination of particulate and sebum stains, such as may be found on shirt collars and cuffs.

The good effect in removing such stains is obtained even when hard water is used, such as that of hardnesses that are quite high, such as in the 250-350 ppm range, as CaCO3. In addition to better removal of such stsains, which is even more evident at 90"C than at 60"C, it is found that the compositions and processes in accordance with this invention result in significant improvements with respect to removals of various other typical stains too.Surprisingly then, the present compositions, incorporating a builder which is stable during washing and stain treatment but is degradable in normally acidic waste waters, and omitting one of the best previously known builders, sodium tripolyphosphate, in combination with synthetic organic detergent (especially a mixture of anionic and nonionic detergents) and perborate bleach, give superior stain removal, which is apparently attributable to the particular unique combination of components employed. Such effect is obtained even in very hard water, which is unexpected in view of the excellent sequestering activity of the sodium tripolyphosphate builder and its known stability and widespread utility in washing and stain removal operations.

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

EXAMPLES 1A to 1D Example 1A Component Percent *Sodium linear tridecylbenzene sulphonate 8.0 Nonionic detergent (Neodol 25-7, a conden- 4.0 sation product of higher fatty alcohols averaging 1 2 to 1 5 carbon atoms, and 7 moles of ethylene oxide per mole of fatty alcohol, obtainable from Shell Chemical Co.) *Sodium hydrogenated tallow soap 4.0 *Sodium carboxymethyl cellulose 1.0 Sodium perborate tetrahydrate 22.0 Builder U (79.7% of sodium polyacetal 22.0 carboxylate, of calculated weight average molecular weight of about 8,000, obtained from Monstanto Co.) * Filler (sodium sulphate, anhydrous) 29.0 moisture 10.0 100.0 in spray dried beads A stain removing detergent composition of the above formula is made by spray drying a crutcher mix, containing about 55% of solids and 45% of water (tap water of hardness of about 100 ppm, as calcium carbonate) and at a temperature of about 50"C, into a countercurrent spray drying tower, wherein it is dried to a moisture content of about 10%. The tower inlet air is at about 450"C and at the outlet from the tower such air temperature has been reduced to about 150"C. The spray dried beads resulting are of particle sizes in the range of No's. 10 to 100, U.S. Sieve Series (having diameters from 2 mm to 149 microns across).With such beads there are admixed in an inclined tumbling drum the sodium perborate tetrahydrate and Builder U, also of particle sizes in the 10 to 110 sieve range. When the component materials are supplied as finer powders and none is spray dried they are (or may be) agglomerated to the desired sizes, alone or together. Such polyacetal carboxylate-perborate agglomerates may be of proportions in the range of 1:5 to 5:1 and may contain from 0.1 to 5% of sodium silicate (Na2O:SiO2 = 1:1.6 to 1:3), as a binder.

The product obtained is tested for stain removing action, utilizing a Miele/multi-stain light reflecting procedure wherein delta Rd's are measured for washed experimental and control swatches. In such procedure the experimental composition (Example 1A) and control detergent composition (Example 1 B) (containing trisodium polyphosphate instead of Builder U) are separately charged to a Miele washing machine at a concentration of about 1.1 % (225 grams per 20 litres of wash water) at 60"C, with water over 200 ppm, (i.e. 300 ppm) hardness as calcium carbonate, and having a hardness of a 4:1 ratio of calcium ion to magnesium ion. The test specimens employed are of different materials and have been stained with different stains.

A plurality of test cloths is employed for each combination of cloth and stain and average reflectance readings from the cloths are taken after normal washings and dryings with the experimental composition of this example and are compared to those for the control detergent composition, wherein 22% of sodium tripolyphosphate is present instead of the Builder U. Such procedures are repeated at 90"C with the exception that the washing procedure is modified so that half of the detergent composition and half of the control are employed in pre-wash steps and the other halves are employed in the main washings.

By the test method described, which is considered to be a standard for testing stain removal properties of detergent compositions, it is found that the composition of this invention (Example 1A) and use of the washing process of this invention result in significant improvements with respect to removals of various typical stains found on items to be laundered, including Spangler sebum/particulate stain on Dacron polyester double knit material, liquid makeup on cotton percale, on Qiana jersey and on Dacron double knit materials, Bic black pen ink on Dacroncotton blend material and French dressing on a Dacron double knit, at 60"C, and Spangler sebum/particulate stain on Dacron double knit material, liquid makeup on cotton percale. on Dacron-cotton blend and on Qiana jersey, and coloured shortening on Dacron double knit, at 90"C. (The words SPANGLER, DACRON, QIANA and BIC are trade marks.) The invented compositions and processes were found to be inferior in stain removal to tripolyphosphatecontaining controls only for brewed tea stain on polyester/cotton blend and for barbeque sauce on Dacron double knit (both at 60"C), and for liquid makeup on Dacron double knit and for French dressing on Dacron double knit (both at 90"C).

Results like those described above are also obtainable when the experimental formula is varied by increasing the alkylbenzene sulphonate content to 16%, omitting the nonionic detergent and soap, and replacing the 29% of sodium sulphate with a third each of sodium bicarbonate, sodium carbonate and sodium silicate of Na20:SiO2 ratio of about 1:2.4 (Example 1 C). Similarly, such second formula may be varied by utilizing a mixture of equal parts of the alkylbenzene sulphonate and sodium lauryl sulphate (totalling 16%) or by omitting the alkylbenzene sulphonate and replacing it with post-sprayed nonionic detergent (Neodol 25-7 or Neodol 23-6.5), after which the sodium perborate and Builder U are admixed with the base beads containing nonionic detergent (Example 1 D).In such instances the improved stain removing property, attributable to the combination of polyacetal carboxylate and perborate in the present formulations, will also be obtained. Instead of the mentioned non ionic detergents other such detergents may be substituted, including the condensation products of ethylene oxide and nonylphenol, as previously described, Pluronics, e.g. F-68, and Neodol 45-11, and mixtures thereof containing two to four components. The word NEODOL and PLURONICS are trade marks.

Other variations in this example may be made, as by utilizing other builders and fillers than those employed, including small proportions, e.g. 1 to 10 or 2 to 5% of amphoteric and/or cationic detergents (the cationic detergents may be employed as antistatic agents) in the formulations, and/or by varying the proportions of the indicated constitutents :::: 1 0 and + 25%, while maintaining them within their respective ranges. Also, the conditions of manufacturing may be varied, as by spray drying essentially all the components (usually except perborate, perfume and enzymes) together, using mild conditions (to prevent degradation of the Builder U).

EXAMPLES 2A to 20 The formulations of the products of Examples 1A, 1 C and 1 D are modified by use of a Builder U of calculated weight average molecular weight of about 5,250, which is 83% of sodium polyacetal carboxylate polymer (Examples 2A, 2B and 2C). Such formulations, when made by the methods described in Example 1 A, 1 C and 1 D are of improved stain removing properties, compared to controls containing sodium tripolyphosphate instead of the Builder U polymer, and the products of these Examples exhibit stain removing capabilities like those of the formulations of Examples 1 A, 1 C and 1 D. Such is also the case when an equivalent proportion of perborate monohydrate is employed instead of the tetrahydrate, with the difference being made up by inert builder (Na2SO4) (Example 2D).The described products are also producible in paste, liquid and bar or cake forms by conventional means, as mentioned previously.

EXAMPLE 3 In the formulation of Example 1A the sodium linear tridecylbenzene sulphonate is replaced by sodium dodecylbenzene sulphonate, sodium paraffin sulphonate, sodium olefin sulphonate (averaging about 16 carbon atoms), sodium lauryl sulphate and sodium monoglyceride sulphate, respectively. When tested by the method described in Example 1 A such products are also significantly superior for the removal of stains from laundry, compared to various controls, utilizing other builders instead of the sodium polyacetal carboxylate, among which builders is included pentasodium tripolyphosphate.

In variations of such formuias the composition is modified to include an activating proportion, e.g. about 1 %, of TAED (with the sodium sulphate content being correspondingly diminished), with such activator being post-added to the composition. Upon testing in the manner described in Example 1A for use at 60"C, but lowering the temperature of the wash water to 30"C, in accordance with American practice, and using a G.E. top-loading washing machine, improved stain removing results are obtained, compared to a control containing sodium tripolyphosphate instead of Builder U. Such is the case with polyacetal carboxylate active polymers of molecular weights of about 5,000* and about 8,000**.However, it is considered that best stain removals are obtained by the method of Example 1A, which may be modified to have present other polyacetal carboxylates of calculated weight average molecular weights in the given ranges.

* Monsanto Lot No. 2547312 (M.W. = 5,250) ** Monsanto Lot No. 2538422 (M.W. = 8,034) In a modification of this example (Examples 1 and 2 may also be so modified) a liquid product or slurry is made by replacing the sodium sulphate or other fillers and/or builders (except polyacetal carboxylate) in the various formulas with water. Such products, when made at the same active ingredient concentrations as those of these examples, are also effective stain removers. In still another variation of the invention, the various components of the composition may be separately added to the wash water to obtain the desired results.Of course, for final commerical products adjuvants will also be present, for example, 0.5% of perfume, 1% of proteolytic enzyme, 2% of fluorescent brightener composition, 0.2% of colourant, such as Polar Brilliant Blue dye and/or Ultramarine Blue pigment for making a blue product, and 3% of flow improving agent, such as magnesium silicate hydrate, if thought to be desirable. It is not considered that employment of any such adjuvants will significantly adversely affect the desirable properties of the invented compositions, or the operations of the invented processes.

From the foregoing description and the examples of compositions and processes within the present invention it is apparent that the combination of polyacetal carboxylate and perborate in the present compositions leads to surprisingly improved stain removing products and methods, especially with respect to hard to remove combination sebum and particulate stains on polyesters, even when the washing medium is a hard water. It is especially surprising that such results should be obtained, considering that sodium tripolyphosphate has been the most effective detergent builder employed in the past, and also considering that the proportion of active polyacetal carboxylate polymer employed is less than the proportion of polyphosphate in the control compositions. Thus, it is thought that a significant advance in the stain removing and cleaning arts has been made by the present invention.

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 substituents without departing from the invention.

Claims

1. A bleaching detergent composition comprising a detersive proportion of a synthetic organic detergent or of a mixture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) and a bleaching proportion of a perborate.

2. A composition according to Claim 1, which is particulate.

3. A composition as claimed in Claim 1 or 2, which is substantially free of phosphate.

4. A composition according to Claim 1, 2 or 3, wherein the synthetic organic detergent is selected from anionic, nonionic and mixed anionic and nonionic detergents.

5. A composition as claimed in Claim 1, 2 or 3, wherein the detergent is a mixture of anionic detergent and nonionic detergent.

6. A composition as claimed in Claim 5, containing from 3 to 30% of anionic detergent and from 2 to 25% of nonionic detergent.

7. A composition as claimed in Claim 5, containing from 4 to 20% of anionic detergent and from 2 to 10% of nonionic detergent.

8. A composition as claimed in Claim 5, containing from 4 to 10% of anionic detergent and from 2 to 6% of nonionic detergent.

9. A composition as claimed in Claim 5, containing about 8% of anionic detergent and about 4% of non ionic detergent.

10. A composition as claimed in any one of Claims 4 to 9, wherein the anionic detergent is a sulphated or sulphonated detergent having a lipophilic moiety having from 8 to 20 carbon atoms.

11. A composition as claimed in any one of Claims 4 to 9, wherein the anionic detergent is a higher alkyl benzene sulphonate, wherein the higher alkyl moiety is of 10 to 1 8 carbon atoms.

1 2. A composition as claimed in any one of Claims 4 to 9, wherein the anionic detergent is sodium linear tridecylbenzene sulphonate.

13. A composition as claimed in any one of Claims 4 to 9, wherein the nonionic detergent is a condensation product of ethylene oxide and a lipophilic group donating compound capable of forming the non ionic detergent with the ethylene oxide.

14. A composition as claimed in any one of Claims 4 to 9, wherein the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol has from 10 to 1 8 carbon atoms, and the nonionic detergent contains from 3 to 20 moles of ethylene oxide per mole.

1 5. A composition as claimed in any one of Claims 4 to 9, wherein the nonionic detergent is a higher fatty alcohol polyethoxy ethanol, wherein from 5 to 9 moles of ethylene oxide are condensed per mnole of higher fatty alcohol having an average of 1 2 to 1 5 carbon atoms.

16. A composition as claimed in any one of Claims 4 to 9, wherein the nonionic detergent is a higher fatty alcohol polyethoxy ethanol, wherein about 7 moles of ethylene oxide are condensed per mole of higher fatty alcohol having an average of from 1 2 to 1 5 carbon atoms.

1 7. A composition as claimed in any one of Claims 1 to 16, including from 4 to 50% of polyacetal carboxylate builder.

18. A composition as claimed in any one of Claims 1 to 16, including from 10 to 30% of polyacetal carboxylate builder.

1 9. A composition as claimed in any one of Claims 1 to 16, including from 10 to 25% of polyacetal carboxylate builder.

20. A composition as claimed in any one of Claims 1 to 1 6, including about 18% of polyacetal carboxylate builder.

21. A composition as claimed in any one of Claims 1 to 20, wherein the polyacetal carboxylate builder has a calculated weight average molecular weight in the range of from 3,500 to 10,000.

22. A composition as claimed in any one of Claims 1 to 20, wherein the polyacetal carboxylate builder has a calculated weight average molecular weight in the range of from 5,000 to 9,000.

23. A composition as claimed in any one of Claims 1 to 20, wherein the polyacetal carboxylate builder has a calculated weight average molecular weight in the range of from 7,000 to 9,000.

24. A composition as claimed in any one of Claims 1 to 20, wherein the polyacetal carboxylate builder has a calculated weight average molecular weight of about 8,000.

25. A composition as claimed in any one of Claims 1 to 24, wherein the perborate is an alkali metal perborate.

26. A composition as claimed in Claim 25, wherein the alkali metal perborate is anhydrous sodium perborate and/or sodium perborate hydrate having up to four moles of water of hydration per mole.

27. A composition as claimed in Claim 25, wherein the alkali metal perborate is hydrated sodium perborate.

28. A composition as claimed in Claim 25, wherein the alkali metal perborate is sodium perborate tetrahydrate.

29. A composition as claimed in any one of Claims 1 to 28 including from 10 to 50% of perborate.

30. A composition as claimed in any one of Claims 1 to 28 including from 10 to 40% of perborate.

31. A composition as claimed in any one of Claims 1 to 28 including from 15 to 30% of perborate.

32. A composition as claimed in any one of Claims 1 to 28 including about 22% of sodium perborate.

33. A composition as claimed in any one of Claims 1 to 32 including from 3 to 20% of moisture, including any hydrate moisture, which is removable at 105"C.

34. A composition as claimed in any one of Claims 1 to 32 including from 5 to 15% of moisture.

35. A composition as claimed in any one of Claims 1 to 32 including about 10% of moisture.

36. A composition as claimed in any one of Claims 1 to 35 including an antiredeposition agent.

37. A composition as claimed in Claim 36, wherein the antiredeposition agent is sodium carboxymethyl cellulose.

38. A composition as claimed in Claim 36 or 37 including from 0.3 to 3% of the antiredeposition agent.

39. A composition as claimed in Claim 36 or 37 including about 1 % of the antiredeposition agent.

40. A composition as claimed in any one of Claims 1 to 39 including from 2 to 6% of soap.

41. A composition as claimed in any one of Claims 1 to 39 including about 4% of soap.

42. A composition as claimed in Claim 40 or 41 wherein the soap is a sodium higher fatty acid soap, wherein the higher fatty acid has from 10 to 18 carbon atoms.

43. A composition as claimed in Claim 40 or 41, wherein the soap is sodium tallow soap.

44. A composition according to Claim 1, which is particulate and substantially free of phosphate and wherein the synthetic organic detergent is selected from anionic, non ionic and mixed anionic and nonionic detergents, the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of about 3,500 to 10,000, and the perborate is an alkali metal perborate selected from anhydrous sodium perborate and sodium perborate hydrate having a content of water of hydration up to four moles per mole.

45. A detergent composition according to Claim 44, which is phosphate-free and wherein the detergent is a mixture of anionic detergent and nonionic detergent, the polyacetal carboxylate is of a calculated weight average molecular weight in the range of 5,000 to 9,000 and the alkali metal perborate is a sodium perborate.

46. A detergent composition according to Claim 45, which comprises from 3 to 30% of sulphated or sulphonated anionic detergent having a lipophilic moiety that includes an alkyl chain or from 8 to 20 carbon atoms, and from 2 to 25% of nonionic detergent which is a condensation product of ethylene oxide and a lipophilic group donating compound capable of forming the nonionic detergent with the ethylene oxide, from 4 to 50% of polyacetal carboxylate builder and from 10 to 50% of a hydrated sodium perborate.

47. A detergent composition according to Claim 46 which comprises from 4 to 20% of higher alkylbenzene sulphonate wherein the higher alkyl moiety has from 10 to 1 8 carbon atoms, from 2 to 10% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alchol, wherein the higher fatty alcohol has from 10 to 1 8 carbon atoms and the non ionic detergent contains from 3 to 20 moles of ethylene oxide per mole, from 10 to 30% of polyacetal carboxylate builder wherein the carboxylate is sodium carboxylate, from 10 to 40% of sodium perborate tetrahydrate, from 3 to 20% of moisture, including hydrate moisture which is removable at tO5 C, and the balance of filler(s) and/or other builder(s) and/or adjuvant(s).

48. A detergent composition according to Claim 47, which comprises from 4 to 10% of sodium linear tridecylbenzene sulphonate, from 2 to 6% of higher fatty alcohol polyethoxy ethanol wherein from 5 to 9 moles of ethylene oxide are condensed per mole of higher fatty alcohol of an average of from 1 2 to 1 5 carbon atoms, from 10 to 25% of polyacetal carboxylate builder of calculated weight average molecular weight in the range of from 7,000 to 9,000, from 1 5 to 30% of sodium perborate tetrahydrate, from 2 to 6% of sodium higher fatty acid soap wherein the higher fatty acid has from 10 to 18 carbon atoms, from 0.3 to 3% of sodium carboxymethyl cellulose, and from 5 to 15% of moisture.

49. A detergent composition according to Claim 48, which comprises about 8% of sodium linear tridecylbenzene sulphonate, about 4% of higher fatty alcohol polyethoxy ethanol wherein about 7 moles of ethylene oxide are condensed per mole of higher fatty alcohol of an average of 1 2 to 1 5 carbon atoms, about 18% of polyacetal carboxylate builder of calculated weight average molecular weight of about 8,000, about 22% of sodium perborate tetrahydrate, about 4% of sodium tallow soap, about 1 % of sodium carboxymethyl cellulose and about 10% of moisture.

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

51. A process for removing stains from fibrous materials, the process comprising washing the fibrous materials in water containing an effective amount of a composition as claimed in any one of Claims 1 to 50.

52. A process for removing mixed particulate and sebum stains from fibrous polyester materials which comprises washing such stained fibrous materials in wash water at a temperature in the range of from 50 to 99"C with a built detergent composition comprising a detersive proportion of a synthetic organic detergent or mixture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) and a bleaching proportion of a perborate, at a concentration of such detergent composition in the wash water in the range of from 0.05 to 1.5%.

53. A process according to Claim 52 wherein the detergent composition is substantially free of phosphate, the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of from 3,500 to 10,000 and the perborate is a sodium perborate having up to 4 moles of water of hydration per mole, and the wash water is of a hardness over 200 ppm, as calcium carbonate.

54. A process according to Claim 53, wherein the detergent composition comprises from 4 to 20% of higher alkylbenzene sulphonate wherein the higher alkyl has from 10 to 18 carbon atoms, from 2 to 10% of a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol has from 10 to 1 8 carbon atoms and the non ionic detergent contains from 3 to 20 moles of ethylene oxide per mole, from 10 to 30% of polyacetal carboxylate builder of molecular weight in the range of from 7,000 to 9,000 wherein the carboxylate is sodium carboxylate, from 3 to 20% of moisture, including hydrate moisture which is removable at 105"C, and the balance of filler(s) and/or other builder(s) and/or adjuvant(s), and the washing is at a temperature in the range of 60 to 90"C in wash water of a hardness in the range of 250 to 350 ppm, as calcium carbonate, and at a concentration of detergent composition in the wash water in the range of 1.0 to 1.5%, and is conducted in an automatic washing machine.

55. A process for removing stains from fibrous materials substantially as herein described with reference to any one of the Examples other than the comparative Examples.