FI58937B - LAOGLOEDDRANDE TVAETTMEDELSKOMPOSITIONER - Google Patents

Description

rBl m advertisement cqq7 „4Ειλ lBJ (11) utlAcgninqsskkift 5 8937 C Patent granted 11 05 1981 '' Patent rr ^ uol ^ t ^" (51) Kv.ik.3 / int.a3 o 11 D 3/18 FINLAND —FINLAND (21) P * t * «ttlh * k * mu · —hK * nt * n« 6lu »tof 750059 (22) HafctmlipMvt —AnaBkninf ^ ag 10.01.75 (FI) (23) ΑΜαφΙΜ — G (Mgh« c * dag 10.01.75 (41) Tullut (ulklMkat - BlWIt off «Kl (| 12.07.75

National Board of Patents and Registration (44) Date of issue. -

Patent · och registerstyrelsen AmWcan uthgd och utUkrtftM publicund 30.01.8l

(32) (33) (31) hnrd ^ ty »TuoHten — priority ll.0i.7U

21.05.7V, 11.11.71 * England-England (GB) 1370/7 ^, 22552 / 7U, kB69k / 7h (71) The Procter & Gamble Company, 301 East Sixth Street, Cincinnati,

Ohio 1 + 5202, USA (72) John Robert Tate, Whitley Bay, Northumberland, Allan Campbell McRitchie, Blyth, Northumberland, England-England (GB) (71+) Oy Kolster Ab (5I +) Low Foam Detergent Compositions - L & glöddrande tvättmedelskomposi -tioner

The invention relates to a granular, builder-containing, low-low detergent composition comprising a) 10-30 wt. an organic detergent selected from one or more nonionic detergents or a mixture thereof and a zwitterionic and / or synthetic anionic detergent, and b) from 10 to 90% by weight. one or more inorganic or organic detergent builders, and which forms no or little permanent foams in the rinsing water.

In general, detergent compositions for washing clothes, especially in pulsator washing machines and hand washes, are expected to generate a lot of foam during the washing phase, although there has been a recent interest in preventing excessive foaming at this stage as well. In automatic drum washing machines, the drum of the washing machine rotates about an approximately horizontal axis. Products intended for use in these machines are required to have a relatively low level of foam during the washing phase. When using the products for both uses, it is important that there is no significant amount of foam in the wash water, especially during the second or subsequent rinses, as these foams make it difficult to properly remove the rinsing water from the wash bowl or machine and may give the impression of an incomplete rinse. Soap products have generally been good in this regard because, with the exception of very soft waters, the hardness of the rinsing water effectively removes any foam. Anionic synthetic detergent products tend to form a lot of foam in the wash, sometimes too much, and form too much foam in the rinse. In these products, the latter disadvantage is avoided by using known additives in the compositions, such as long-chain soaps or fatty acids or silicone compounds. Usually, they also lower the foam during the washing step, but this is often an advantage, or at least acceptable.

To date, most anionic detergent compositions have included significant amounts of phosphate-containing detergent builders.

Detergent compositions based on nonionic or zwitterionic detergents or mixtures thereof with each other or with anionic detergents can achieve a better cleaning effect than anionic detergents alone, especially if less conventional phosphate builder is used. These compositions can generally provide a suitable amount of foam for washing, but can cause considerable difficulty in rinsing due to permanent foam. Defoamers suitable for use with conventional anionic detergents have been found to be unsuitable for overcoming this disadvantage.

This is due to a number of reasons, for example, they may be effective in rinsing only at concentrations that they also. Disadvantageously reduce the amount of foam in the wash or adversely affect the cleaning performance or some other properties of the product or may reduce the foam advantageously in the wash but cannot reduce it sufficiently. In drum washing machines, excessive foaming during the washing and pumping out steps can cause a larger amount of surfactant to be transferred to the rinsing solutions, making it even more difficult to prevent foaming therein.

It has now been found that it is possible to eliminate or significantly reduce the foaming caused by the rinsing of nonionic, zwitterionic and anionic synthetic detergents without much reduction in foaming in the washing step. This is particularly valuable for detergent compositions based primarily on non-ionic or non-ionic / zwitterionic mixed detergents, for which other methods are not suitable, as discussed above. In addition, detergent compositions can be prepared so that the degree of foam reduction in washing can be increased if desired, for example in products specifically intended for use in drum washing machines. These detergent compositions can also be formulated to provide relatively strong foaming at low temperatures and reduced foaming at higher temperatures.

The detergent composition according to the invention is characterized in that the organic detergent contains less than 50% by weight of anionic detergent and that the composition 3,58937 further comprises: c) 0.02-8% by weight of a substantially water-insoluble microcrystalline wax or mixture of waxes, which wax may be microcrystalline petroleum wax , optionally oxidized mountain oil, optionally oxidized Fischer-Tropsch waxes, montan waxes, earth waxes, beeswax, carnauba wax and candelilla wax, wherein the wax or mixture has a melting point above 50 ° C and a saponification number of less than βθ, preferably less than 10, and wax thoroughly mixed with any or all of the organic detergents.

If the invention is applied to a detergent composition which causes a reduction in the foam mainly in the rinsing, but the reduction is only slight in the washing, 0.02-5% by weight /? substantially water-insoluble microcrystalline wax or mixture of waxes.

The manner in which the wax component in these detergent compositions acts is not fully understood, but the following explanation will prove to be appropriate to the facts observed and will help the reader to understand the invention. It turns out that the wax does not significantly affect the foaming of the composition, provided that it is almost completely dissolved by the surfactant. Suitable waxes appear to be those which are insoluble in water, but which, if desired, can be made soluble by the surfactant used and which then remain dissolved at the concentrations and temperatures used in the washing liquid. Thorough mixing with the surfactant during preparation of the composition indicates that it promotes this dissolution.

During washing, there appears to be some interaction between the wax and / or surfactant and the fabric, as well as during the rinsing steps, as the reduction in foam in the rinse is greater if fabrics are present than if a corresponding dilution of the washing solution is performed without the fabrics.

Waxes which are mainly suitable for reducing the foam present in the rinsing have a microcrystalline structure as solids and are preferably relatively high melting waxes. They must be essentially insoluble in water, but must be able to be dispersed in micellar solutions of organic surfactants and / or in pure liquid organic surfactants, for example as colloidal dispersions or micellar solutions or as actual solutions or emulsions. Their melting points are in the above range, preferably at most 115 ° C and most preferably 65-100 ° C. In general, their molecular weights range from about UOO to 100,000. It is advantageous if they are not too hard and brittle, i.e. they have a penetration value of at least 6 measured at 25 ° C according to ASTM-D1321. Preferably, the wax structure has a large number of hydrocarbon chains, i. they have a saponification number of less than 100, preferably less than 60.

58937

Suitable waxes include microcrystalline rock oil waxes derived from rock oil, oxidized microcrystalline rock oil waxes and the rock oil itself (petroleum jelly); synthetic waxes such as Fischer-Tropsch waxes and oxidized Fischer-Tropsch waxes; earth and peat waxes such as ozokerite, ceresin and montan wax; and natural waxes such as beeswax, candelilla wax and carnauba wax.

Japanese waxes, waxes such as polyglycol distearate and polyethylene glycols (trade name Carbovax) have been found to be unsuitable. Paraffin wax, which is macrocrystalline, has only a minor effect similar to that of microcrystalline waxes and is not particularly suitable for the types of compositions under consideration.

The terms "microcrystalline wax" and "rock oil wax" are well known in the art and include slightly varying groups of substances. They are described in "The Chemistry and Technology of Waxes", A.H. Warth, Second Edition, i960, Reinhold Publishing Corporation, pages 391-393 and pages 1 * 21 et seq. As the name suggests, the individual crystals of microcrystalline wax are much smaller than paraffin wax. As such, microcrystalline waxes are tough rather than hard; some of them are flexible even at low temperatures. Although microcrystalline wax is highly paraffinic in chemical nature, the compounds from which it is formed are not the same as those from which paraffin wax is formed. The compounds that make up the microcrystalline wax have substantially higher molecular weights and have a higher amount of branched chain hydrocarbons than paraffin waxes. Microcrystalline wax is derived from heavier oils than paraffin waxes, i. oils from the final stages of distillation. The structure of rock oil and rock oil jelly is also microcrystalline, as are natural waxes, beeswax, carnauba wax, and ozokerite (Warth, ibid., Pp. 391-393). Fiseher-Tropsch waxes are obtained by a method known by this name and are also microcrystalline in nature.

Particularly recommended are microcrystalline rock oil waxes known as "Be Square 175" »sold by Bareco division, Petsolite Corporation, Tulsa, Oklahoma," Mobilwax 2305 ", sold by Mobil Oil Company Limited, Wallasey Bridge Road, Birkenhead, Cheshire, England and Shell Microwax 185/190 ".

In general, relatively low wax contents are sufficient, for example 0.1-3 w / w, especially 0.2-1.5 wt. Concentrations greater than 5% t may be effective, but as the amount of wax increases, the anti-foaming effect in the wash becomes greater.

When the invention is used to prepare compositions which have a significant antifoaming effect in washing, it has been found that the waxes are in part the same as those suitable mainly for rinsing in the preparation of compositions with reduced foaming properties and are particularly effective powders in washing detergents. , 5,58937 based on non-ionic or non-ionic / zwitterionic detergent active ingredients. To date, it has been surprisingly difficult to reduce the foam produced by these compositions sufficiently satisfactorily in front-loading automatic washing machines.

In general, antifoaming agents such as high molecular weight fatty acids and soaps are ineffective in these compositions. In addition, they can greatly degrade the washing performance of the detergent composition. In some cases, silicone-based defoamers are effective when it is desired to reduce foam in a wash. However, they may have adverse side effects in some compositions and, in addition, to be fully effective, they must be isolated from most surfactants, as disclosed in GB Patent 1 b07997. On the other hand, the waxes used in the invention need not be and in fact must not be isolated; they can then be added much more easily to detergent compositions.

The waxes of this invention should be hydrocarbon waxes, or at least for the most part, i.e. they have saponification numbers of less than 60, preferably less than 10. In addition, their melting points should be higher than 50 ° C, preferably higher than 65 ° C and especially higher than 85 ° C. Without wishing to be bound by theory, it has proved necessary that when the wax is useful as a defoamer in washing, it has a melting point approximately equal to or higher than the temperature at which the product is used in washing. Although some washes are performed at ifQ ° C or even lower, most products are also used at at least 60 ° C, so the above. temperatures are suitable. Products designed for use at the highest temperatures of conventional washing machines (about 95 ° C) have the best waxes, melting at least 90-95 ° C.

For strong foam reduction in washing, waxes such as carnauba wax, candelilla wax and beeswax are not suitable as such. Microcrystalline linseed oil waxes and Fischer-Tropsch waxes (provided that, when oxidized, their saponification numbers are as indicated) are suitable, with microcrystalline waxes being preferred.

In washing, the amount of wax in the foam-reducing detergent compositions is preferably slightly higher than in the detergent compositions, which are intended to achieve a mainly reduction in foam during rinsing; Preferred amounts are 0 → 5-6 wt.%, preferably 1-3 wt.

During washing as well as rinsing, there is some interaction between the wax and the fabric. It has also been found that the foam-reducing effect of the wax used in the detergent composition when used in the prewash stage of a modern automatic washing machine passes to the main washing stage more strongly than would be expected from the amount of detergent used in the prewash. For example, if a different detergent product, which may not contain a wax defoamer, is used as the detergent in the main wash step, its foaming may be reduced by the effect of the defoamer wax in the prewash composition.

In the low-foam detergent compositions according to the invention, which are intended to reduce foaming in washing, anionic detergents can even be used as the main organic detergent component, provided that the wax is thoroughly mixed, e.g. preferably dissolved or melted with a non-ionic detergent. A nonionic detergent recommended for this purpose is one having a relatively long carbon chain, e.g. tallow fatty alcohols condensed with 8 to 13 (especially about 11) moles of ethylene oxide, but other nonionic detergents may be used. If the wax is simply mixed as such with these, mainly anion-based compositions, even, for example, as a liquid in a mixer (slurry) for spray drying, it is less effective as a defoamer in washing. The cleaning ability of these compositions generally corresponds to the cleaning ability of typical anionic detergent compositions.

For purity only, anionic detergents are not used at all in compositions based mainly on non-ionic and / or zwitterionic detergents, as they tend to impair the special cleaning properties of these active detergents. However, especially in cases where it is desired to avoid spray-dried mixtures containing non-ionic detergents, the use of a small amount of anionic detergent, e.g. up to 2/5 of the weight of the composition, preferably about 1%, is advantageous in preparing spray-dried granules which can serve as carriers. or for a low melting nonionic detergent. A process for preparing these carrier granules is disclosed in GB 1 b63 198. The addition of small amounts of anionic detergents in this way does not impair the effectiveness of the compositions of this invention even when wax is added without special measures.

It is to be understood that some experimentation with waxes, surfactants, and their proportions may be required in selecting within the scope of the invention combinations that perform optimally for the desired application. Thus, in order to reduce foam solely or mainly in rinsing, in light of the experimental explanation of the mechanism of action of waxes described above, it may be necessary to select a particular combination of waxes and surfactants or mixtures thereof so that the wax dissolves completely (or, if desired, incompletely) in the surfactant. at the temperature and concentration used in the wash, but is affected by the dilution in the rinse in the presence of the fabrics so that its foam-reducing effect occurs. In general, in order to reduce foam, high melting microcrystalline waxes are the strongest defoaming agents and are especially recommended with highly foaming surfactants, for example non-ionic detergents which contain significant C1g or lower alkyl groups, e.g. Tergitol 15 — S — 9 (trade name), based on secondary alcohols or coconut alcohols containing 9 elio groups or non-ionic / zwitterionic detergent mixtures. Of course, larger amounts of wax may be required with substantially more foaming detergents. Another factor to consider when selecting a wax is that it should preferably be soluble or finely dispersible at reasonable temperatures, e.g. up to 90 ° C, in non-ionic detergents for the processing reasons set out below.

The following microcrystalline waxes are very effective:

Shell Microwax 160/165, sold by Shell Chemicals,

Shell Microwax 185/190, sells Shell Chemicals (especially recommended), BP Microwax 160 / 25Y »sells BP Chemicals microcrystalline wax 0K239» sells Astor Chemicals Limited,

Mobilwax Cerese, sold by Mobil Oil Company Limited,

Mobilvax 2305, sold by Mobil Oil Company Limited and Mobilwax 2360, sold by Mobil Oil Company Limited.

Fischer-Tropsch waxes sold by Veba Chemie AG are also suitable.

Suitable anionic synthetic surfactants for all compositions of the invention include those known in the art, such as those disclosed in GB Patent 1,400,898. It is preferred that no soap be present, but may be used up to about 3% by weight of the composition in the compositions required. mainly a reduction in foam during rinsing. Suitable nonionic surfactants include all alkoxylated surfactants known in the art. Preferred nonionic surfactants are detersive surfactants of the general formula R-O- (C H0) - (C H0 O) -C H0 OH 'y 2y az 2z bw 2w, wherein R is a primary, secondary or a branched alkyl or alkenyl hydrocarbyl radical, a primary, secondary or branched alkyl or alkenyl-substituted phenol hydrocarbyl radical, when the hydrocarbyl chain of the hydrocarbyl radical has a hydrocarbyl chain length of 8 to 20, preferably 10 to 18, carbon atoms; z and y are both 2 or one of them is two and the other 3 (i.e. excluding propylene oxide (PO) surfactants only); v is 2 or 3, preferably 2; and a and b (which need not be the same) are both 0 or integers 1-13, with the sum a + b being 3-25, preferably 4-10. The above formula includes ethylene oxide as well as mixed β 58937 ethylene oxide-propylene oxy (EO-PO) alkoxylates, all of which are useful. PO surfactants alone do not provide cleaning benefits in detergent compositions and their use is not discussed in this context.

Preferred nonionic surfactants for use herein include:

Straight-chain primary alcohol alkoxylates of n-decanol, n-dodecanol, n-tridecanol, n-tetradecanol and n-octadecanol hexa, hepta, octa, nona, deca, undeca, dodeca, tetradeca and hexane -decaalkoxylates are useful surfactants in the context of this invention; the corresponding ethylene oxide condensates are the most preferred alkoxylates. Examples of alkoxylated primary alcohols include: n-C 1 QEO (3); n C1QE0 (9); n-C12EO (9); n ClltE0 (7); n CllfEO (LO); n-C10EO (LO); n C1QE0 (6); n-C ^ E0 (9); n-C ^ EOI)?; n-C ^ EOilU); and η-0 ^ Ε0 (6) Ρ0 (3). Ethoxylates of natural or synthetic alcohol blends having a carbon chain length similar to that of coconut oil are also useful. Some examples of these are coconut alkyl-E0 (6) and coconut alkyl-EO (9) ·

Straight-chain secondary alcohol alkoxylates of 2-decanol, 2-tetradecanol, 3-hexadecanol, 2-octadecanol, i * -ecosanol and 5-eicosanol hexa-, hepta-, octa-, nona-, deca-, undeca-, dodeca, tetradeca and hexadeca alkoxylates are useful surfactants in the context of this invention; the corresponding ethylene oxide condensates are the most preferred alkoxylates. Examples of alkoxylated secondary alcohols include: 2-C1QEO (9); 2-C12E0 (9); 2-C ^ EOOo); 2-C ^ EOOl); U-C2QE0 (11); 2-C ^ EOOM; and 2-C ^ E0 (6) P0 (3). The most preferred straight-chain secondary alcohol alkoxylates are those sold under the tradenames Tergitol 15-S-9, Tergitol 15-S-7 and Tergitol 15-S-5, which consist of a mixture of secondary alcohols with an average hydrocarbyl chain length of 13 with an average number of 9 carbon atoms condensed. »With 7 and 5 moles of ethylene oxide per mole equivalent of alcohol, respectively.

alky phenol alkoxylates

As with alcohol alkoxylates, alkoxylates of alkylated phenols ranging from hexaalkoxylate to hexadeca alkoxylate, especially monovalent alkylphenols, are useful as a surfactant in the composition of the invention. The corresponding ethylene oxide condensates are the most preferred alkoxylates. alkoxylates of p-hexenophenol, m-octylphenol, p-octylphenol, p-nonylphenol from hexa-alkoxylate to hexadeca-alkoxylate, and the like are useful herein; the most preferred are the ethoxy compounds of p-octylphenol and p-nonylphenol, as these substances are readily available. Examples of alkoxylated alkylphenols include: p-octylphenol-E0 (9); p-nonylphenol-E0 (9), p-Decylphenol-E0 (9), o-dodecylphenol-E0 (10), and p-octylphenol-E0 (9) P0 (2) · The most preferred alkylphenol alkoxylates are p-octylphenol ( nonaoxyethylene) and p-nonylphenol (nonaoxyethylene).

Olefinic alkoxylates

Both primary and secondary alkenyl alcohols and alkenylphenols corresponding to the above can be alkoxylated and used as surfactants in the compositions of the invention. Typical alkenyl alkoxylates include 2-n-dodecanol-E0 (9), 3-n-tetradecanol-EO (9), p- (2-noneyl) phenol-E0 (9) PO (2) and 2-tetradecane -14-olE0 (9).

Branched alkoxylates

Branched chain primary and secondary alcohols obtained by the well-known "0X0M method" can be alkoxylated and used as a surfactant. Examples of branched chain alkoxylates are 2-methyl-1-dodecanol-E0 (9), 3- ethyl 2-tetradecanol-EO (9)> 2-grain-1-hexadecanol-E0 (9) P0 (2) Dobanol (trade name-Shell) and Synprol (trade name ICl) are particularly recommended. series of ethoxylated alcohols, for example Dobanol U5-i * or 1 * 5-7.

The above alkoxylated nonionic surfactants may be used in the compositions of the invention individually or in combination, and the term "nonionic surfactant" includes mixed combinations of nonionic surfactants containing multiple alkoxylated nonionic surfactants. active substances.

Amine oxide surfactants, in particular detergents of the general formula 11½¾¾-> 0, in which R1 is an alkyl group having 10 to 28 carbon atoms, 0 to 2 hydroxy groups and 0 to 5 ether bonds and in which R1 contains at least one moiety, are also to be regarded as non-ionic detergents. which is 10 to 18 carbon atoms and does not contain any alkyl-2 3-containing ether bonds. .

the group and R and R are both selected from the group consisting of alkyl radicals having 1 to 3 carbon atoms and hydroxyalkyl radicals.

Typical examples include amiinioksidipesuaineista: dimetyylidode, amine oxides, dimetyylitetradekyyliamiinioksidi, etyylimetyylitetradekyyli-amine oxide, setyylidimetyyliamiinioksidi, setyylietyylipropyyliamiinioksidi, dimethylstearylamine, dietyylidodekyyliamiinioksidi, dietyylitetrade, amine oxides, dipropyylidodekyyliamiinioksidi, bis (2-hydroxyethyl) amine oxides dodeca-bis (2-hydroxyethyl) -3-dodecoxy -1-hydroxypropylamine oxy-10,589,37 di, (2-hydroxypropyl) methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide and the corresponding decyl, hexadecyl and octadecyl homologues of the above compounds. The corresponding phosphine oxides and sulfoxides are also suitable.

Suitable zwitterionic surfactants are disclosed in GB Patent No. 1,900,898, and in particular alkyl dimethylammoniohydroxypropanesulfonates, wherein the alkyl group is linear and the quaternary nitrogen is attached to the terminal carbon atom of the alkyl chain, should be mentioned. The presence of relatively large amounts of some zwitterionic detergents inherently provides highly foaming compositions that require relatively large amounts of wax to obtain very low levels of foam.

Suitable detergent builders are disclosed in GB 1 UOO 898. These include well known polyphosphate builders, including recently invented non-phosphate builders, both inorganic and organic. Structural salts are therefore generally selected from the group consisting of alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, silicates, sulfates, water-soluble aminopolyacetates and polyphosphates. Preferred building blocks are sodium tripolyphosphate, sodium nitrilotriacetate, sodium metal acetate, sodium citrate and sodium carbonate. Water-insoluble builders disclosed in Belgian Patent 813,581 can also be used.

The composition of the invention contains from 10 to 30% by weight of organic surfactant. The content of the building material is 10 to 90% by weight, preferably 20 to 70% by weight, most preferably 20 to 50%.

The compositions may also contain other conventional ingredients used in laundry detergent compositions. These include bleaching agents such as inorganic perhydrates, e.g. sodium perborate, dirt suspending agents such as sodium carboxymethylcellulose, other inorganic salts such as sodium chloride, other foaming agents such as those disclosed in GB Patent 1,492,939, enzymes, enzymes, stabilizers for bleaching agents or enzymes, stain retardants, optical brighteners, germicides, fabric softeners, agents which facilitate the preparation of spray-dried compositions based on non-ionic detergents (as disclosed in GB 1 U60 6b6), and colorants.

In the preparation of compositions which reduce the foam mainly by rinsing, careful incorporation of the wax into the surfactant is important and this proves to be possible only by mixing the wax with a liquid or pasty surfactant at some stage of product preparation 11 58937 under liquid conditions. This can be done in different ways. In general, it is preferred to mix the molten wax and the organic detergent before adding them to the other major ingredients of the composition. In this case, the wax can be dissolved or dispersed in a liquid detergent or a liquid aqueous dispersion or "paste" consisting of a zwitterionic or anionic detergent. Usually the latter may be in the form of a "paste" in which detergents are suitably prepared, for example as a paste containing from about 10 to 50% by weight, more usually from 20 to 10% by weight, of a surfactant. The wax and detergent mixture may be added to the slurry of other ingredients (rod mixer) for spray drying or may be sprayed or otherwise mixed with one or more granular or powdered ingredients of the final composition, for example spray dried ingredients or some other suitable carrier material. Of course, suitable minor ingredients, such as perfumes, enzymes or antioxidants, may be added to the wax-detergent compositions if desired.

Alternatively, said other ingredients may be prepared into granules, e.g. by spraying with a dowel by the method disclosed in GB Patent 1 1 * 63 198, and a liquid wax-detergent mixture may be sprayed thereon, whereby it is absorbed into these granules. This latter method avoids spray-drying of mixtures containing non-ionic detergents and the associated quality control and smoke difficulties in spray-drying equipment.

The wax may also be added as a liquid to the slurry formed by the other ingredients, including the organic detergent or detergents, provided that the slurry is so hot that the wax is well dispersed.

For compositions for which foam reduction in washing is desired, except those containing higher amounts of anionic detergents, as described above, these methods are suitable, however, a very careful mixing of the wax and organic detergent is not critical and the latter method can generally be used advantageously. because it is practical.

The invention is illustrated by the following examples. The abbreviations and trade names used in the examples are given below:

Tergitol 15 — S — 9 · trade name for 9 moles of ethylene oxide condensate per mole of mixed straight-chain secondary alcohols containing 11 to 15 carbon atoms, sold by Union Carbide,

Dobanol 1 * 5 ~ E7; trade name and means an average of 7 moles of ethylene oxide condensate per mole of mixed 12 58937 alcohols with 1U to 15 carbon atoms, sold by Shell Chemicals Company,

Dobanol 23 ~ E6.5; trade name and means an average of 6.5 moles of ethylene oxide condensate per mole of alcohols containing 12 to 13 carbon atoms, sold by Shell Chemicals Company,

Dobanol U5-E &; trade name, and means an average of 1 * ethylene oxydimol condensate per mole of alcohols having 1 U to 15 carbon atoms, sold by Shell Chemical Company, C with coscohol, LAS is sodium linear dodecylbenzene sulphonate, soap is 80/20 tallow / coconut sodium soap, CMC is carboxymethylcellulose, STPP is sodium tripolyphosphate

Hyfac is a trade name and means a fatty acid derived from hardened fish oil containing 18 to 22 carbon atoms, sold by Humbo Corporation.

Microcrystalline hydrocarbon waxes derived from rock oil Mobilvax 2360 (m.p. 66 ° C), sold by Mobil Oil Mobilvax 2305 (m.p. 77 ° C), sold by Mobil Oil Mobilvax Cerese (m.p. 82 ° C), sold by Mobil Oil BP Microvax 160 / 25Y (m.p. 77 ° C), sold by BP Chemicals Shell Microvax 185/190 (m.p. 93 ° C), sold by Shell Chemicals Microcrystalline synthetic hydrocarbon waxes SH 105 (prepared by the Fischer-Tropsch method (m.p. 99 ° C), sold by Veba Chemie.

Microcrystalline waxes derived from plants or insects m.p. (° C) saponification number

Carnauba wax 82-85 80-85 85% fatty esters

Beeswax 63-66 70-75 70% "

Japanese wax i + 9-52 200-230 95% fatty acid glycerides

Macrocrystalline hydrocarbon waxes derived from rock oil White paraffin wax (m.p. 52 ° C)

Synthetic non-hydrocarbon wax Polyethylene glycol (PEG) 100

58937

Example 1

The following compositions were prepared:

Composition of. 123 ^ 5

Tergitol 15 — S — 9 6 gHAPS 6 6

Pobanol t5-3-7 - 6 12 CNAEg 12 LAS <- - - - 1J4

Sodium toluene sulphonate - - ~ ~ 1 »5

Soap - - - 2 ~

Thalimonoethanolamide _ _ - U 1

Sodium tripolyphosphate (STPP) 36 28 36 36 3T

Sodium silicate 7 7 7 7 6

Sodium sulphate 5 13 5 5 5

Sodium perborate tetrahydrate

Sodium CMC 0.5 0.5 0.5 1 1

Mobilvax 2305 0.5 0.5 0.5 0.5 0.5

Moisture and minor ingredients 1U 1U 11+ 7 »5 1 ^

In the table above, the figures in the table are percentages by weight of the total composition.

In each case, a control sample without wax was prepared and numbered 1a, 2a, etc. in the results. Compositions with wax were prepared as follows: 1 58837

Nos. 1, 2 and 4 - The molten wax was dissolved in a liquid nonionic detergent or a mixture of nonionic detergents heated to a temperature above the melting point of the wax. Spray-dried granules were made from ingredients other than perborate and perfume. The mixture of nonionic detergent and wax was sprayed onto the spray-dried granules, which were perfumed and then mixed dry with perborate.

Well. 3 - The molten wax was dissolved in Dobanol as above and the mixture was added to a rod mixer containing the other ingredients of the composition except perborate and perfume. This was then spray dried and the perborate and perfume were mixed with the spray dried granules.

Well. 3- The wax was melted and added to the hot LAS paste in a rod mixer. After mixing these, ingredients other than perborate and perfume were added together and spray dried. Perfume and perborate were added to the spray-dried granules.

The foaming of these compositions was compared as follows: Equipment and conditions

Bowls - 4 perspex bowls 30 cm in diameter 2 hand towels, approximately 120 g each water - softened clock - second timing temperature - wash 45 ° C, rinse cold

Product concentration - general hand wash content - or as directed *

Procedure 4.5 liters of water at 45 ° C were added to the first wash bowl and 4.5 liters of cold water to each of the other three (rinse) bowls. The towels were placed in the first bowl.

The product was added to the wash bowl and stirred for 30 seconds and allowed to settle for 2 minutes. The height of the foam was measured in centimeters.

Each towel was lifted in turn and squeezed for 60 seconds. Each towel was squeezed 16 times. The towels were removed and most of the washing solution was removed by gently squeezing the towel lengthwise. Finally, each towel was folded Fourfold and as much washing solution as possible was removed by twisting. The height of the foam was measured in centimeters.

'5 58937

The towels were transferred to the first rinsing bowl and each towel was lifted and squeezed Four times for 15 seconds. The rinse water was removed as above. The height of the foam was measured and the percentage of water covered by the foam was determined visually.

Foam height x coverage = rinsing index.

The rinsing procedure was repeated for the second and third rinses.

The foams measured were as follows:

Composition Washing foam height, Rinse 1 Rinse 2 Rinse 3 ___ ^ _ Rinse index_ Sat 2. 4 60 60 20 1 5.1 40 18 8 2a 2.54 60 20 10 2 2.0 20 8 5 3a 3.8 60 30 20 3 1.0 8 3 1/2 4a 3.8 60 40 20 4 3.3 40 16 Remaining.

5a 7.6 60 50 20 5 7.6 50 40 10

Compositions Nos. 1, 2 and 4 show little or no reduction in foam in the wash and a strong reduction in foam in the rinse; composition 3 also shows a reduction in foam in the wash. Composition 5 exhibits a slightly smaller but still valuable wax addition effect in the anlon-based composition.

Example 2 (a) Comparison of the efficacy of different waxes as defoamers.

The effect of different waxes on the foam profile of Dobanol 45-E7 in the rinse was determined using the hand wash / rinse procedure described in Example 1. Test results were prepared by injecting 1 fo solutions of various waxes onto 12 Dobanol 45-E7 carrier granules formed from the rest of the composition.

The experiments were performed with a concentration of 0.3% product in soft water (30 ppm CaCO 3).

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The test products:

ABCDEFGHIJK

Dobanol 1 + 5-E7 12 12 12 12 12 12 12 12 12 12 12 LAS 11111111111 STPP 36 36 36 36 36 36 36 36 36 36 36

Silicate 77777777777

Sulphate 55555555555

Perborate 25 25 25 25 25 25 25 25 25 25 25 25

NaCMC 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Mobilvax 2360 0.1 BP Microwax 160 / 25Y 0.1

Mobilvax 2305 0.1

Shell Microwax 185/190 0.1 SH 105 0.1

Carnauba wax 0.1

Beeswax 0.1

Japanese wax 0.1

Paraffin wax 0.1 PEG UOO 0.1 17 58937

Product Flushing index

Washing Flushing 1 Flushing 2 Flushing 3 Flushing 4 A 150 90 40 15 5 B 140 30 10 0 o C 140 35 15 0 0 D 130 10 0 0 0 E 140 10 5 0 0 F 130 40 5 0 0 G 150 30 10 0 0 H 140 15 5 0 0 1 150 60 25 10 0 J 150 50 20 10 0 K 160 100 80 30 10

The most effective aids in rinsing are microcrystalline carbon-hydrogen waxes. Natural waxes with a soap count of less than 100 are also effective. Unsuitable at this level are macro-paraffin waxes which have only a minor effect and polyethylene glycol wax, which in fact increases the foam somewhat.

(h) Comparison of the effectiveness of different amounts of wax to adjust the foam in the rinse

Variable amounts of Shell Microwax 185/190 were added to a 12-night Dobanol 45-E7 matrix (injected) and hand wash / rinse profiles were determined as described in Example 1.

Product content = 0.5%

The hardness of the water corresponded to 30 ppm CaCO 3.

Test products A JB jC D

Dobanol 45-E7 12 12 12 12 LAS 1111 STPP 36 36 36 36

Silicate 7777

Sulphate 5555

Perborate 25 25 25 25

NaCMC 0.5 0.5 0.5 0.5

Shell Microwax 185/190 O 0.1 1.0 3.0

Miscellaneous substances until 100% 18 58937

Washing Rinsing 1 Rinsing 2 Rinsing 3 Rinsing 4 A 150 90 40 15 0 B 140 10 5 15 0 C 100 0 0 0 0 D 50 0 0 0 0

Example 3 (a) Effect of wax on foaming of a nonionic / anionic active system on rinsing

The hand wash / rinse profile of the nonionic / anionic product containing Shell Microwax 185/190 was determined using the test procedure set forth in Example 1.

Test products ABC.

LAS 999

Dobanol 45-E7 333 STPP 30 30 30

Silicate 777

NaCMC 0.5 0.5 0.5

Sulphate

Shell Microwax 185/190 0 0.5 3.0

Perborate 25 25 25

Miscellaneous until 100% A little was dissolved in Dobanol-E7 and the other ingredients were mixed into these.

Huuhteluindeksi

Washing Rinsing 1 Rinsing 2 Rinsing 3 Rinsing 4 A 300 40 10 0 0 B 300 10 0 0 0 C 200 10 0 0 0 (b) The foaming of the following compositions was compared by washing naturally soiled laundry in a Hoover 3286H home washing machine in soft water (30 ppm CaCO 2). hardness) in a "soup-wash" cycle using 70 g of product.

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The compositions mainly contained:

Composition D

LAS 8 8

Taiialkoholi-Ej! 3 2

Hyfac 3

Shell Microwax 185/190 - 2 STPP 30 30

Sodium silicate 7 7

Sodium carboxymethylcellulose

Sodium sulphate 10 12

Sodium perborate 25 25

Humidity 10 10

Miscellaneous substances

Notes (1) "Hyfac" is the trade name for a material containing mainly saturated Cjg_2o “fat * iaPP0> ia · (2) The wax was melted with tallow alcohol-E11 before mixing in a fork mixer for rolling drying.

The foam heights in the machine window when heated were average

D E

After 10 minutes 1.5 cm 2.5 cm After 15 minutes 6.9 cm 2.5 cm After 20 minutes 13 cm 2.5 cm After 25 minutes 13 cm 2.5 cm

When using Composition D, although no over-foaming occurred, foam was observed in 25% of cases with a full window, while a full window was never obtained with Composition E. Example k

Granular detergent compositions were prepared according to the following formulas:

Composition from 6789

Oobanol 45-E7 12 12 12 12

Sodium tripolyphosphate

Sodium silicate 7 7 77

Sodium sulphate

Sodium carbonate 5.5 5.5 5.5 5.5

Sodium perborate (tetrahydrate)

Water 10 10 10 10

Various minor ingredients 3 3 3 3

Mobile wax 2305 0 1 3 -

Hyfac _ _ _ 2 20 58937 These compositions were used to dispose of soiled laundry at home in either a Hoover 3236H or Indesit LS LGB automatic washing machine. The laundry was washed in amounts of 5> 5 kg using a white wash cycle of the washing machines in water with a hardness of 12 ° (172 ppm CaCO 3). The content of the product was 0.5 * & ·

In the Hoover machine, the foam level in the wash was determined as the height of the foam in centiroethers as seen from the machine window. An Indesit machine, whose mode of operation tends to cause large amounts of foam in the rinse, was used to determine foaming in the rinse solutions. In both machines, a washing step was performed followed by several cold rinses, with five rinses performed in the Indesit machine. Foam in the rinse was determined in two ways, by measuring the foam in the window (percentage coverage) after the wash or rinse solution was pumped out and collecting the pumped solution in the tank and estimating the area covered by the foam solution (in percent) immediately after rinsing the solution.

Composition 6 provided excess foam to the machine and was unsuitable for use.

Compositions 7 and 8 gave foam levels of 7.5 cm and 5 cm at the Friday stage.

The amounts of foam coverage in the window (as a percentage) after pumping out each solution were as follows:

Composition Washing Rinsing 1 2_3 4_ £ 7 100 50 25 0 0 0 8 100 50 25 0 0 0 9 100 75 25 10 0 0

The foam-covered portions of the tank surface after each solution was pumped into it were as follows:

Composition Washing Rinsing 1 2_3_4_ 7 100 100 100 25 0 0 8 100 100 50 10 0 0 9 100 100 100 90 75 50

Example 5 Experimental conditions:

The clean laundry was washed in a Hoovermatlc vertical washing machine at 54 ° C for 6 minutes, the foam heights were determined and the percentage of the surface area of the foam-covered washing solution was evaluated. The laundry was then blown dry and machine washed in cold water. The height of the foam was measured again and the surface coverage was evaluated. In the same way, 58937 two more rinses were performed. The results shown below are average values from five washes. Product content = $ 0.05>.

Water hardness = 30 ppm CaCO 3

The test products:

A B

CNAE6 12 12

Soap 2 2

Thalimonoethanolamide k k STPP 36 36

Silicate 7 7

Sulphate 5 5.5

Perborate 25 25

NaCMC 1 1

Mobilwax 2305 0.5 0

Miscellaneous until 100%.

Score:

Flushing index A B

Wash 17 ^ 1 180

Flushing 1 60 160

Flushing 2 20 125

Rinsing 3 5 50

Example 6 Products were used to wash soiled household laundry in a Hoover 3236H (Matchbox) automatic washing machine with the "white laundry" setting (maximum temperature 85 ° C). The product content was 0.5% and the water hardness corresponded to 30 ppm CaCO3. Foam in the machine inlet was observed during pumping out, following washing and rinsing steps. The effluent was pumped into a large glass cylinder, the height of the foam formed was measured, and the percentage of the surface covered by the foam was estimated.

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Test results r

A B

Dobanol 45-E7 6 6 g-dimethylammonium hydroxypropanesulfonate 6 6 STPP 36 36

Silicate 7 7

Sulphate 5 5

Perborate 25 25

NaCMC 0.5 0.5

Mobilwax 2305 (2) 0.5 0

Silica / silicone foam reducer (1) 0.2 0.2

Miscellaneous substances until 100% is reached.

Notes: (1) Present as chips. Sllika and yesterday are each 4% of the chip weight. The remainder of the chip consists of STPP (^ 66%) and TAEg ^ (/ W6%).

(2) The wax was dissolved in Dobanol 45-E7 before the latter was sprayed onto granules containing the zwitterionic active ingredient and other conventional ingredients.

Percentage of covered surface of the inlet at pumping out

A B

Washing 100 100

Rinsing 1 50 90

Rinsing 2 10 75

Rinsing 3 0 15

Flushing 4 0 10

Rinsing 5 00

Foam height in cylinder (") x surface coverage

A B

Washing 300 300

Flushing 1 75 150

Rinsing 2 10 100

Flushing 3 0 75

Flushing 4 0 25

Flushing 5 0 25 58937 23

Example 7 (a) Effect of wax as a defoamer in highly active conditions 1. Effect as a defoamer for washing foam Test method:

The effect of the wax on the foam / temperature profile of the following products was determined using a Minidrum washing machine (compact drum washing machine). The products were used (at 0.5% concentrations) to wash a normally soiled laundry consisting of two cotton towels and one cotton tea towel. In this case, the garment / washing solution ratio was the same as that found in an automatic drum machine (about 1/10). The hardness of the water corresponded to 260 ppm CaCO 2. The wash water was heated with stirring to 90 ° C in about 45 minutes and the foam height was measured every 20 ° C.

Test result t: A B

Dobanol 45-E7 18 18 LAS 1 1 STPP 36 36

Silicate 7 7

Sulphate 5 5

Perborate 25 25

NaCMC 0.5 0.5

Shell Microwax 185/190 3

The wax was dissolved in Dobanol 45-E7 and the solution was sprayed onto carrier granules formed from the other ingredients of the composition.

Temperature ° C 30 50 70 90

Foam height (cm) A 2.5 5 * 0 5 * 0 10.0 B 23 28 30.0 * 30 i 30 en = over-foaming 2. Effect as a foam-reducing agent in rinsing Test method:

The hand wash / rinse profiles of the following products were determined in the usual manner. Product content = 0.5%.

The hardness of the water corresponded to 30 ppm CaCO 3.

\ 24 58937

The test products:

A B

Dobanol 23E6.5 25 25 LAS 1 1 STPP 30 30

Silicate 7 77

Sulphate 6 6

Perborate 20 20

NaCMC 0.5 0.5

Mobilwax 2305 0.5

Miscellaneous substances until 100%

Dissolved in a non-ionic detergent and sprayed on a carrier. Results: Foam height x coverage

Washing Rinse 1 Rinse 2 Rinse 3 Rinse 4 A 400 I50 50 0 0 B 400 300 I50 50 0 (b) Effect of wax as a foam reducer in rinsing under low activity conditions and low builder concentrations.

Test method: Hand wash / rinse test as in Example 1.

The test products:

C D E F

Dobanol 23-E6.5 5 5 5 25 LAS 111 1

STPP 30 30 0 O

Silicate 777 7

Sulphate 26 26 36 36

Perborate 20 20 20 20

NaCMC 0.5 0.5 0.5 0.5

Mobilwax 2305 * 0.1 - 0.5

Miscellaneous until 100% x Sprayed non ** ionic detergent.

Results Washing Rinsing 1 Rinsing 2 Rinsing 3 Rinsing 4 C 250 50 0 0 0 D 300 150 50 50 0 E 400 150 50 O 0 F 400 400 25Ο 100 50 25 58937

Example 8 Test products:

A B_ C

Dobanol 45-E7 12 12 12 LAS 1 1 1 STPP 36 36 36

Silicate 777

Perborate 35 25 25

Sulphate 5 55

NaCMC 0.5 0.5 0.5

Shell Microwax 185/290 sprayed 1 - mixed dry 1 Miscellaneous substances up to 100%

Test method: Hand wash / rinse test as in Example 1.

Product concentration = 0.5%, 30 ppm CaCO2.

Results: Foam height x coverage

Washing Rinse 1 Rinse 2 Rinse 3 Rinse 4 A 140 10 5 0 0

B 150 75 30 5 O

C 150 90 40 15 5

The results show that the wax is less effective when mixed dry, i. the mixing is not thorough with the organic surfactant.

Example 9

Products with the following composition were prepared:

Product: A 13 C_ JL iL

Dobanol 45-E7 (1) 12 12 12 12 12 LAS (2) - - - 1

Sodium tripolyphosphate 30 30 30 30 30 Fate

Sodium silicate 7 7 777

NaCMC 1 1 111

Sodium sulphate 5 5 555

Sodium perborate

Mobilvax 2305 - l * 3) 3 ^ 3 ^ - 1 ^)

Silicone defoamer (5) - - 3

Miscellaneous substances until 100%.

2S 5 8 9 3 7

Notes: (l) trade name, Shell Chemicals Company (2) sodium linear alkyl benzene sulfonate.

(3) the wax dissolved in a non-ionic oesuant and poured into a fork mixer.

(¾) wax dissolved in a non-ionic detergent and sprayed onto carrier granules.

(5) The chips contained 4% by weight of a mixture of silica and silicone.

The products were used to wash soiled household laundry in a Hoover 3236H automatic washing machine at 85 ° C (boiling). The product content was 0.5%, the water hardness was 2 ° H (i.e. 29 ppm (CaCO 3)). The foam heights visible in the machine feed opening were observed during the washing step. The values given below are averages of 10 washes.

The heights of the foam were as follows in centimeters:

Product A C D E

Time 5 9.4 0 0 1.5 0 10 12.7 1.5 O 2.0 0 15 14.2 3.3 0 4.0 1.0 20 14.6 7.8 2.3 4.0 4.5 25 18.8 8.6 4.8 4.0 6.6 These results show that the compositions are effective in a full-size washing machine and that spraying a wax solution on a non-ionic detergent is slightly more effective than adding it to a fork mixer *

Example 10 This example shows the effect of wax in controlling foam in various non-ionic active systems.

In these compositions, the waxes were pre-dissolved in a non-ionic detergent and the solution was sprayed onto carrier granules consisting of roll-dried granules of the test composition except perborate, which was added with final mixing.

27,58937

Product _F G H J k L

Tergitol 15-S-9 12 12 - - CNAE6 - 12 12 -

Dobanol 45-E-4 - - - - 12 12 LAS 1 1 1 lii

Sodium tripolyphosphate

NaCMC 11 1111

Sodium silicate 77 7 777

Sodium sulphate 55 5 555

Sodium perborate 25 25 25 25 25 25 25

Shell iiicrowax 185/190 3 3 0.5

Miscellaneous substances until 100%.

The products were used to wash normally soiled laundry (2 towels / l tea using approximately the same laundry / wash-solution ratio as in the drum machine of Example 1) in a Minidrum washing machine. The system was heated - with stirring - to boiling point over about 45 minutes. The garment / wash solution ratio was about 1:10 by weight.

The height of the foam in centimeters was as follows:

Product F_ G_ H _J_ JK JL

temperature

30 ° C 10 1.25 12 2.5 1.25 O

50 ° C 23 2.5 20 1.25 2.5 0 70 ° C 30 * 7.5 30 * 2.5 10 1.25

90 ° C 23 2.5 25 2.5 5.0 O

xFoam filled the drum.

These results, in a compact drum washing machine, show the effect of wax with various nonionic detergents, requiring more wax with more self-foaming nonionic detergents. .

Example 11

The following products were tested as in Example 10 (wax in a non-ionic / anionic system). The wax in product N was dissolved in LAS paste (about 30% + a by weight of active content) 3a was then added to the fork mixer. In product P, the wax was dissolved in a non-ionic detergent and the solution was added to a fork mixer. In Product K, the wax was dissolved in a non-ionic detergent and sprayed onto the parent granules formed from the rest of the composition except perborate.

28 58937

Product; M N 0 JP £ R

LAS 12 12 6 6 1 1

Dobanol 45-E-7 - - 6 6 12 12

Sodium tripolyphosphate

Sodium silicate 666666

Sodium sulphate 555555

Sodium perborate 20 20 20 20 20 20

Sodium CMC 111111

Shell Microwax 135/190 - 5 - 3 - 1

Miscellaneous substances until 100 #.

Product R1 was the same as product R except that the wax itself was spray cooled to a fine solid powder and this was dry blended with the test product.

The heights of the foams in centimeters were as follows:

Product MN 0 PQR R1 30 ° C 30 30 20 12.5 1.25 1.25 1.25 50 ° C 30 30 30 22.5 5 1.25 5 70 ° C 30 30 30 30 22.5 1.25 19.5 90 ° C 15 17.5 10 2.5 30 3.75 15 These results show the absence of foam reduction in products containing exclusively anionic detergents, a slight reduction in foam in the 50/50 anionic / non-ionic product and a satisfactory foam reduction in the preferred formulations according to the invention. products. The wax, if not effectively mixed with the organic detergent, was considerably less effective.

Example 12

The following products were tested as in Example 10 to demonstrate the effectiveness of different types of wax. In all cases, the wax was dissolved in a nonionic detergent and sprayed onto the carrier granules.

29 58937

Product S. X JJ V Ά A 1 Z

Dobanol A5-E-7 12 12 12 12 12 12 12 12 LAS llllllll

Sodium tripolyphosphate 36 36 36 36 36 36 36 36

Sodium silicate 77777777

Sodium sulphate 55555555

Sodium perborate

Sodium CMC 0.5 0.5 0.5 0.5 0.50, 50.5 0.5

Paraffin wax (m.p. 52 ° C) -1 ------

Mobilwax 2360 (m.p. 66 ° C) - - 1 - - _

Mobilwax 2305 (m.p. 77 ° C) --- 1 ----

Mobilwax Cerese (m.p. 82 ° C)

Fischer Tropsch wax SH105 (m.p. 99 ° C) 1

Carnauba wax (m.p. 82 ° C) ------ 1 ^

Beeswax (m.p. 66 ° C) ------- l

Miscellaneous substances until 100%>.

The heights of the foams were as follows in centimeters Product S T U V W X II

Temperature 30 ° C 1.25 1.25 1.25 1.25 1.25 1.25 10 10 50 ° C 5 5 1.25 1.25 1.25 2.5 15 15 70 ° C 22.5 22 .5 3.8 1.25 1.25 10 22.5 25 90 ° C 30 30 22.5 15 12.5 12.5 30 30

The results show that low melting paraffin wax (52 ° C) is ineffective as well as high melting ester waxes as defoaming agents. The improving effect of microcrystalline waxes (MOBIL) as the melting point increases also occurs. Fischer Tropsch wax is effective, although weaker than microcrystalline rock oil-based wax. Example 13 (a) The following products were prepared (wax in a zwitterionic / non-ionic detergent) with the wax dissolved in the non-ionic detergent and added to the fork mixer. They were assembled as in Example 10.

30 58937

Products A B_

Dobanol 45-E-7 6 6 g-alkyl dimethyl ammonium hydroxypropanesulfonate 6 6

Sodium tripolyphosphate 28 28

NaCMC 0.5 0.5

Sodium silicate 7 7

Sodium sulphate 13 18

Sodium perborate 25 25

Shell Microvax 185/190 _ 5 moisture content 10 10

Miscellaneous substances until 100%.

The heights of the foams in centimeters were as follows:

Product A B

Temperature 30 ° C 10 1.25 50 ° C 14 5 70 ° C 22.5 7.5 90 ° C 30 15 (b) The following compositions were used to wash conventionally soiled laundry in a Mlele 421 washing machine with a wash water hardness of 18 ° H ( 258 ppm CaCO 2), in a "cooking-wash" step using 70 g of product in the prewash and 140 g in the main wash.

Composition C. D

Dobanol 45-E-7 8 8 ^ 14 8 -alkyl'l * <1 * ,, ie * 'yy ** a ,, ul, on * jmkyclrt) * C8 * “propanesulfonate 4 4

Shell Microwax 185/190 - 2

Sodium sulphate 13 11

The remainder as in Compositions A and B in Example 13 (a) · During the heating cycle, the foam heights in the Window were:

D

30 minutes 6 cm 35 "10 cm 40" 12 cm 50 "15 cm 55" 17 cm

Composition C caused over-foaming.

Example 14

Washing experiments were performed using real soiled household laundry in a Miele 416 washing machine using prewash and main wash 31 5 89 37 ("soup wash") - step east # the following compositions were used:

Composition A g. £ D

LAS - - 8 8.5

Dobanol 45-E7 15 15

Or alcohol - - 2 1.5

Fatty acid - - 3,5 2

Wax 2 - - -

Sodium tripolyphosphate 45 45 32 66

Sodium silicate 5 5 6 -

Sodium sulphate 19 21 89

Sodium perboate - 25

Carboxymethylcellulose 1.5 1.5 1 1.5

Moisture content 10 10 12 9

Other minor ingredients 2.5 2.5 2.5 2.5 When using the compositions in the prewash and the main wash, the foams formed in the main wash were measured during the heating phase as well as during the wash.

Prewash composition (weight) A- (100 g) B- (100 g) D- (100 g) Main wash composition C- (125 g) C- (125 g) C- (125 g)

Foam height in the machine window at 70 ° C 0 - - 80 ° C - 3 cm - 85 ° C 3.5 cm 2 cm 6.2 cm at 90 ° C 9.9 cm 22 cm 11.5 cm

Excess foam was observed in repeated washes, as shown below, with figures showing the percentage of washes in which the above foaming was observed.

Window just foam filled zero 8 # 18%

Product dispenser foam filled zero 33% il%

Over foaming zero 25% 11%

Example 15

The cleaning properties of the following compositions A and B were compared.

s? 5 8 9 3 7

A B

Dobanol 45-E-7 6 6 C,. g-alkyldimethylammonium urea-hydroxypropanesulfonate 6 6

Shell Microwax 185/190 2 O

Sodium sulphate 4 6

Sodium tripolyphosphate 36 36

Sodium silicate 7 7

Sodium 25 25

Sodium CMC 0.5 0.5 Moisture content 10 10

Miscellaneous substances

The naturally soiled laundry (3.5 kg family bundle) was divided into two 1.75 kg bundles, which were as evenly soiled as possible. These were washed in water with a hardness of 18 ° H (258 ppm CaCO 2), the pallets of the washing machine "white laundry" using the cycle in conjunction with artificially soiled pieces of fabric (facial dirt, eyeshadows, lipstick, ballpoint pen ink, dirty engine power, cosmetics, tea dirt, blood on polyester / cotton and cotton fabrics). 70 g of product were used in the pre-wash and 140 g in the main wash. the experiments were performed five times (with different laundry bundles). The fabric pieces cleaned by Product A were compared with the specimens cleaned with Product B by examining either visually by comparison in pairs or by reflection measurements adjusted according to the soiling. No significant difference could be observed in the cleaning performance of the two products, either as a whole or in any given dirt / fabric combination.

Example 16

Naturally soiled household laundry bundles were washed in a Miele 416s washing machine using the "white laundry" step in 18 ° H water (258 ppm CaCO 3). In the prewash step, 100 g of detergent composition was used, and 125 g in the main wash.

The compositions tested were:

A B

Dobanol 45-ET 10 10

Sodium tripolyphosphate

Sodium silicate 3 3

Sodium sulphate 13 14.4

Sodium perborate 32 32

Shell Microwax 185/190 1.4 0

Moisture content and minor ingredients up to 100 100 33 58937

The foam heights in the machine window with composition A were: 30-85 ° C 0 90 ° C k, k cm

Composition B gave a foam of at least 20 cm at 90 ° C with a high risk of over-foaming.

Claims (7)

3b 58937 f A granular, builder-containing, low-foaming detergent composition comprising a) 10-30% by weight of an organic detergent selected from one or more nonionic detergents or a mixture thereof and a zwitterionic and / or synthetic anionic detergent, and h) 10-90% by weight of one or more inorganic or organic detergent builders, characterized in that the organic detergent contains less than 50% by weight of anionic detergent and in that the composition further comprises: c) 0.02-8% by weight of a substantially water-insoluble microcrystalline wax. or a mixture of waxes, which may be microcrystalline petroleum wax, oxidized linseed oil if desired, oxidized Fischer-Tropsch waxes if desired, montan waxes, earth waxes, beeswax, carnauba wax and candelilla wax, wherein the wax or mixture has a melting point greater than 50 ° C and a soap 60, preferably less than 10, and the wax or mixture is thoroughly mixed with one or all of the organic detergents machines. Composition according to Claim 1, characterized in that the wax has a melting point of at most 115 ° C. Composition according to Claim 2, characterized in that the wax has a melting point of 65 to 100 ° C. Composition according to Claim 2 or 3, characterized in that the wax has a molecular weight of 0000 to 1000. Composition according to one of Claims 2 to k, which is low-foaming on rinsing, characterized in that it contains 0.02 to 5% by weight of wax. Composition according to Claim 5, characterized in that it contains 0.2 to 1.5% by weight of said wax. Composition according to Claim 5 or 6, characterized in that it contains at most 2% by weight of anionic detergent, based on the total weight of the composition.