NO852165L - ANTISTATIC, SYNTHETIC, ORGANIC DETERGENTS AND PROCEDURES IN THE PREPARATION OF THIS. - Google Patents

Description

The invention relates to detergents and more particularly detergents which comprise an anionic, synthetic, organic

surfactant or a mixture of such surfactants, polyacetal carboxylate builder for such a surfactant or surfactants and a cationically active, antistatic agent. The invention also concerns

a method for producing such an antistatic, built-in detergent. When using the present detergent for washing fiber materials that have been soiled and/or stained, such dirt or stains are removed, and it is prevented that the fiber materials "stick together" due to static electricity.

The need to remove dirt and stains from fiber materials is ancient, and a number of means have been described

to achieve this result. While soap was once the universally used detergent, today almost all detergents for washing clothes at home are based on one or more synthetic, organic surfactants. Among such surfactants, they are anionic

and the non-ionic the most effective, and the anionic surfactants are the most widely used. Ampholytic or amphoteric or cationic surfactants can also be used. Cation-active compounds that have a cleaning effect are often also germicides and act as antistatic agents, and this

is particularly important because these reduce the static bonding of washed items made of synthetic, organic, polymeric plastics, e.g. different qualities of nylon, polyester or acrylic fibres, from sticking to each other. The cationically active compounds also have fabric softening properties.

A disadvantage of the cationic surfactants, however, is their reactivity towards anionic materials, e.g. anionic surfactants, which can cause a serious reduction in the cleaning effect. In recent years, cationic surfactants,

such as quaternary ammonium halides, have been used in detergents so that washed materials or laundry made of synthetic, organic, polymer plastic will have antistatic and softening properties without seriously affecting the cleaning effect of the detergents. Moreover, the polyacetal carboxylate builder has recently been used in detergents as a substitute for polyphosphate builders because the former do not contain phosphate

for and therefore has not been considered to promote freshwater eutrophication. Another plus for such builders is that they can easily break down in normally acidic wastewater.

Although the main components of the present detergents have been used in other such detergents, the present detergents are new, not close and useful and exhibit unpredictably good dirt and stain removal properties. The greatly improved ability of the present detergents, especially non-phosphate-containing detergents, to remove various stains and dirt from synthetic textile materials and cause them to acquire antistatic and softening properties during normal washing in washing machines is of particular importance, as the antistatic properties prevents the washed materials from sticking to each other after automatic drying of the laundry.

The invention thus relates to an antistatic detergent which comprises a cleaning amount of a synthetic, organic surfactant or a mixture of such surfactants, a washing power-building amount of a polyacetal carboxylate builder for such a surfactant or surfactants or a building amount of a mixture of such a polyacetal carboxylate builder and zeolite builder, and an antistatic amount of an antistatic cationic component.

The present detergents preferably comprise 5-30% sodium linear-higher-alkylbenzenesulfonate in which the higher alkyl group has 12-14 carbon atoms, 5-40% sodium polyacetal carboxylate builder with a calculated weight average molecular weight of 3500-10000 or a mixture of such a builder and Zeolite A- builder, 2-10% distearyldimethylammonium chloride, 2-20% moisture and the remainder filler or fillers and/or another builder or builders and/or another auxiliary additive or agents. When the present detergents are used to remove mixed dirt and stains from fiber materials, especially cellulose acetate, the soiled and stained fiber materials are washed in washing water containing a cleaning amount of a synthetic, organic surfactant or a mixture of such surfactants, a cleaning power-building amount of a polyacetal carboxylate builder for such a surfactant or surfactants and an antistatic amount of a cationically active, antistatic agent, the detergent being used in a concentration in the washing water of 0.05-0.5%.

The anionic, synthetic, organic surfactant used in the detergents according to the invention will normally consist of a sulfated and/or sulfonated lipophilic material or materials with an alkyl chain of 8-20, preferably 10-18, more preferably 12- 16, carbon atoms. Although various water-soluble salt-forming cations can be used to form the desired soluble sulfated and sulfonated surfactants, including ammonium and lower alkanolamine (such as triethanolamine) and magnesium, an alkali metal, sodium or potassium, is typically used, and it is strongly preferred that the cation is sodium. Among the various anionic surfactants that can be used in the present detergents, the linear higher alkylbenzene sulfonates with 10-18, preferably 12-16, and more preferably 12-14, carbon atoms in the alkyl chain are considered the most suitable. Also suitable are among others the monoglyceride sulfates, the higher fatty alcohol sulfates, the sulfated polyethoxylated higher alkanols, in which the alkanols can be synthetic or natural, containing 3-20 or 30 ethoxy groups per molecule, paraffin sulphonates and olefin sulphonates, and in all these compounds the alkyl group present has 10-18 carbon atoms. Some of these alkyl groups may be slightly branched, but they will still have a carbon chain length within the described range.

The cationic, antistatic agents that can be used, as a rule in limited quantities, e.g. not more than 20% and preferably only up to 15%, are preferably the higher-alkyl-lower-alkylammonium halides, in which the higher alkyl groups have 10-18, preferably 16-18, carbon atoms,

the lower alkyl groups have 1-3, preferably 1, carbon atoms, and the halogens are chlorine or bromine. Among such materials can be mentioned distearyldimethylammonium chloride, di-tallow-dimethylammonium chloride (in which the alkyl group is written from animal fats) or dihydrogenated-tallow-dimethyl-ammonium bromide. However, various other such may

cationic active materials, including N-cetylethylmorpholine ethosulfate, which also often have deodorizing and germicidal properties, are used. Descriptions of the various suitable anionic and cationic surfactants can be found in various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example in the publication published in 1969. Moreover, such cationic surfactants form a well-known group and are extensively described in the literature (in the same way as the anionic surfactants), and these therefore do not need to be described in detail here. In addition, nonionic or amphoteric surfactants, which are also described in the above-mentioned present publications, may be present together with the anionic surfactant and the cationic antistatic agent, as a rule in smaller amounts than the amount of the anionic surfactant and as a rule also in smaller amounts than the amount of cationic antistatic agent present.

The polyacetal carboxylate can be considered to be what is described in US patent 4144226, and it can be produced using the method mentioned there. A typical such product will have the formula

wherein M is selected from the group consisting of alkali metal, ammonium, alkyl groups of 1-4 carbon atoms, tetraalkylammonium groups, and alkanolammonium groups, both having 1-4 carbon atoms in the alkyl groups, n is on average at least 4, and and R2 are any chemically stable groups which stabilizes the polymer against rapid depolymerisation in alkaline solution. The polyacetal carboxylate will preferably be a polyacetal carboxylate in which M is an alkali metal, e.g. sodium, n is 20-200, R1 is or a mixture thereof, R

and n is on average 20-100, more preferably 30-80. The calculated weight average molecular weights for the polymers will normally lie within the range 2000-20000, preferably 3500-10000, and more preferably 5000-9000, e.g. about. 8000.

Although the preferred polyacetal carboxylates have been described above, it will be understood that they may be substituted in whole or in part with other such polyacetal carboxylates or related organic builder salts which are described in a number of patents to Monsanto on such compounds, processes for their preparation and compositions in which they are used. Moreover, the chain-terminating groups described in the aforementioned patents of Monsanto, in particular US patent 4144226, can be used, provided that they have the desired stabilizing properties which cause the aforementioned builders to be depolymerized in acidic media and facilitate the biochemical "degradation" thereof in wastewater streams, but preserve their stability in alkaline media, such as in washing solutions.

The zeolite component will usually have the formula (Na20)x.(Al203).(Si02).w H20, where x is 1, y is 0.8-1.2, preferably approx. 1, z is 1.5-3.5, preferably 2-3 or approx. 2, and w is 0-9, preferably 2.5-6. Such zeolites are cation exchange and have an exchange capacity for calcium ions of 200-400 or more milligram-equivalent calcium-carbonate hardness per gram. They will preferably be hydrated to a degree of 5-30, preferably 10-25, e.g. about. 20, humidity thereof. Zeolite A is preferred (X and Y are also applicable) and of this zeolite type 4A is most preferred. The particle sizes of the zeolites will generally be 149-37 µm, preferably 105 or 74-44 µm, but their smallest sizes will be below 1 µm. The various zeolites are extensively described in the textbook Zeolite Molecular Sieves, by Donald W. Breck, published by John Wiley & Sons, especially

on pages 747-749.

In the present detergents, builders other than the polyacetal carboxylate can also be present, although this is not necessary. It will often be desirable to avoid the presence of phosphorus in the detergents, and for this reason the polyphosphates, which have been the preferred builders in detergent technology for a number of years (especially pentasodium tripolyphosphate), will preferably be omitted from the available detergents. They may still be present in some cases, provided that they are present in relatively small amounts, e.g. up to 5 or 10%. Among builders other than polyphosphates, such as sodium tripolyphosphate or tetrasodium pyrophosphate, include those which it may be desirable to incorporate into the present detergents to supplement the polyacetal carboxylate's builder action, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, zeolites, e.g. Zeolite A, NTA, sodium citrate, sodium gluconate, borax, other borates or other builders known in the detergent art. Fillers may be present, such as sodium sulphate or sodium chloride, to give the product increased volume if this is desired. Among the builders, it is considered that the zeolites are particularly effective in the present detergents, as indicated earlier, and among the fillers, sodium sulphate will usually be the preferred one.

Among the various auxiliaries that

can be used are coloring agents, such as dyes or pigments, perfumes, enzymes, stabilizers, activators, fluorescent whitening agents, buffers, fungicides, germicides and fluidity promoting agents. Moreover, various additional components or impurities present together with other constituents are also included among auxiliaries, builders and fillers, unless these fall under other groups mentioned.

It is known, for example, that sodium carbonate and water often

is present together with polyacetal carboxylate in "BuilderU"

which is the product that is the source of polyacetal carboxylate in the present detergents.

Moisture will usually be present in the available detergents, either as free moisture or in one or more hydrates. Although moisture is not an essential component of the present detergents, it will normally be present due to the use of water in the manufacture, and it can help to dissolve components in the detergent and bind them to each other.

The amounts of components in the present detergents given below apply to particulate products which generally have particle sizes in the range of 2.38 mm or 2.0 mm to 149 µm or 105 µm. However, such quantities also apply to other solid forms, such as pieces or cakes, more finely divided or coarser powders, granular detergents and agglomerates. They can also apply to liquid detergents. Due to their relatively low stability (due to reactions between anion-active and cation-active components), however, aqueous liquid detergents should be used relatively soon after they have been prepared. While, moreover, the ratios between pairs of components, apart from water, may be approximately the same in liquid or pasty detergents as in solid detergents,

the liquid products are often far more diluted, so that the amount of water or another solvent or mixture of solvents present can be far greater. According to certain aspects of the present invention, the components can be added directly to the wash water, and in this case the wash water containing the various active and other components can be considered the detergent.

In the particulate, solid and other solid detergents according to the invention, the total amount of surfactant present will normally be 5-40, preferably 5-30,

more preferably 10-25, and most preferably 13-23, e.g.

about. 19.%. Such a surfactant will normally be an anionic surfactant, and among these the higher alkylbenzene sulphonates are preferred, e.g. sodium linear tridecylbenzene sulfonate. However, these may be present together with other anionic surfactants or they may be completely or partially replaced by one or more of such other anionic surfactants.

The amount of polyacetal carboxylate builder will usually lie within the range 5-50, preferably 5-40, more preferably 15-30, and most preferably 17-23, e.g. about. 19.% if it is the only builder present, or reaches up to 50%

of a builder or builders other than zeolite is also present. When zeolite is present, the sum of the polyacetal carboxylate and the zeolite will be an amount that has previously been stated for the polyacetal carboxylate alone, and if zeolite is present, the polyacetal carboxylate will make up at least 5% of the detergent. Moreover, the ratio between polyacetal carboxylate and zeolite will lie within the range 1:3-3:1, preferably 2:3-2:1, and more preferably 3:4-7:4, e.g. 1:1-3:2. The cationic active compound which acts as an antistatic compound (and also has fabric softening properties), will be present in an antistatic amount in the present detergents, at least with regard to certain materials. The available detergents have been shown to

be particularly effective when it comes to reducing electrical charges (and thus static cling) on acetate materials, but they are also effective against other types of synthetic textiles, such as acrylic-polyester textiles. The amount of cationic, antistatic agent will usually lie within the range 2-10, preferably 3-8, and more preferably 4-6, e.g. about. 4 or 5, %. The moisture percentage will normally be 2-20, preferably 3-15, and more preferably 5-12, e.g. about. 6 or 8.%. These percentages include moisture in hydrate form which is released during heating for two hours at 105°C (the standard analysis method for moisture). The amounts of other components, such as fillers, will normally be limited to no more than 50%, and they will often lie within the range of 5-35%. Similarly, the content of non-phosphate builders other than the polyacetal carboxylate will be limited, and it is generally below 40%, such as 3-30 or 5-25%, but such supplementary builders are not necessary. However, the presence of other builders and fillers is often desirable. Thus, sodium carbonate is a preferred non-phosphate builder in the same way as sodium silicate. Preferred silicates are the sodium salts in which the ratio Na20:SiC>2 lies within the range 1:1.6-1:3.0, preferably

1:2.0-1:2.6, e.g. 1:2,4. Any amounts of the carbonate and silicate present can be respectively 3-25, preferably 8-18, and more preferably 10-15.% and 2-15, preferably 5-10, and more preferably 6-9.%. Any amount of filler present will usually be 5-35, preferably 20-35, and more preferably 22-30, %.

The overall content of auxiliary additives will not normally exceed 10% or 20% and will normally be below 5%, as the content of the individual common auxiliary additives will not generally exceed 3% or 5% and is often preferably below 1% or 2 %. For example, an optionally used amount of sodium carboxymethyl cellulose, which is a favorable antigen deposition agent, will as a rule amount to 0.3-3, preferably 0.5-2, e.g. 1.% of the detergent.

According to preferred embodiments of the invention where the detergents are particulate, solid detergents with such particle sizes as those that have been described above, it is often preferred to spray dry so

as much as possible of the recipe amount to obtain substantially uniformly shaped, globular particles. Because it

-cationic antistatic agents can react with anionic materials, e.g. the anionic surfactant, the first-mentioned will normally be subsequently added to the rest of the mixture. In order to prevent separation during shipping and storage of the final product, it is desirable that any subsequently added components, such as the cation-active compound, polyacetal carboxylate and enzyme, have a similar shape, <p>particle sizes and spatial density as the rest of the mixture. However, when this is not the case or when the subsequently added materials are present in finely divided form, e.g. with particle sizes

within the range of 95 µm to 44 µm, and has higher room-

density, they can be subsequently added to spray-dried beads or other particles of the detergent base which have a larger particle size, and they will often adhere to such particles so that a desired product is obtained with particle sizes within the range from 2.0 mm to 149 µm. The polyacetal carboxylate can occasionally be spray-dried together with

the detergent provided that care is taken to prevent the polyacetal carboxylate from being decomposed by heat. According to an alternative manufacturing method, the various components, in finely divided form, can simply be mixed with each other. When, moreover, the original particle sizes for the various components or for some of these are smaller than desired, e.g. within the range of 105 µm to 44 µm, particles thereof can be agglomerated to achieve the desired size, sometimes with the aid of agglomerating agents, such as a dilute aqueous solution of sodium silicate, and at other times with just water to facilitate agglomeration.

The anionic surfactant or the mixture of such surfactants which is the primary surfactant or the primary surfactants in the present detergents can be spray-dried together with fillers, such as sodium sulfate, builders, such as sodium carbonate, sodium bicarbonate, borax or sodium silicate, and auxiliary additives, such as fluorescent whiteners, pigments or dyes, in the normal manner using a conventional counter-current or co-current spray drying tower with drying air entering with a

-temperature of 200-600°C (preferably 150-300 or 350°C when polyacetal carboxylate is present). Thereafter, the polyacetal carboxylates and the antistatic agent may be mixed in any order or simultaneously or the antistatic agent and the polyacetal carboxylate may be premixed and then mixed with the spray dried beads. When a relatively small amount of non-ionic surfactant is to be present together with the anionic surfactant, the former can be spray-dried together with such an anionic surfactant and filler etc, and other stable materials to be present can also be incorporated into the kneader slurry and then spray-dried together with the anionic surfactant. However, when more than approx. 4 or 5% (occasionally over 2%) non-ionic surfactant is present according to the recipe, any additional amount will usually be added afterwards, e.g. by spraying on particles of surfactant beads held in turn-

loin movement. The polyacetal carboxylate and the antistatic agent can then be added afterwards. In some cases, the polyacetal carboxylate can be dispersed and/or dissolved in the non-ionic surfactant which is heated so that it is in a liquid state (or it can be dissolved in a solvent), and the combination of non-ionic surfactant and polyacetal carboxylate can be sprayed onto the surfactant beads or the base beads, followed by the addition of the cationic antistatic agent. The manufactured particulate material should preferably have particle sizes within the range from 2.38 mm to 125 µm or from 2.0 mm to 149 µm, and the manufacturing process will be adapted to this. However

sieving can be used to remove under- and over-sized particles, and these particles can be reprocessed, ground, agglomerated or otherwise processed to the desired sizes (sometimes from 2.38 mm to 177^ around).

For the production of the present products in the form of pieces, cakes or briquettes, the detergents can be extruded or pressed or shaped in a known manner so that they obtain the desired shape. To convert these into liquid detergents, the components can be dissolved and/or dispersed in liquid media, such as water and/or a suitable solvent or solvents, such as ethanol, glycerol or isopropanol.

One of the detergents described can be added to a washing water or the various components can be added to a washing water to remove dirt and stains from objects without them sticking to each other and so that they become clean (and also soft). Normally, the concentration of the detergents used will lie within the range from 0.05 or 0.1 to 0.4 or 0.5%, preferably 0.1-0.35%, and more preferably 0.15-0.25 or 0.35%. Higher concentrations, e.g. from 0.25% to 0.45% or more (and less washing water), is often used in machine washing in accordance with European practice where normal washing water with a higher temperature is used. According to American practice, lower concentrations are used, e.g. 0.05-0.25%, and often preferably 0.1-0.2% of the detergents. As a rule, washing temperatures in America will be in the range of 10-55, preferably 35-55, °C compared to 60-99, often 70-90 or 95, C in Europe. However, it is considered that the detergents according to the invention are useful for removing dirt and stains from clothes of different textile types and materials, so that such clothes are free of static electricity and soft regardless of which washing method is used.

When using the detergents according to the invention, a sufficient amount of the detergents is added to washing water in a normal washing machine for washing through clothes (commercial machines can also be used) in the desired amount within the specified areas, e.g. 0.2% (130 g per

65 liters of washing water), and the washing water has a normal washing temperature, e.g. 49°C, and normal hardness (50-250 or 300 ppm, calculated as calcium carbonate). The laundry is then added/and the normal weight of the laundry to be washed is 2.7-4.5, e.g. 3.6, kg. Washing the laundry is carried out during a normal washing cycle of from 2 minutes to 30 minutes, e.g. 5-20 minutes, as needed and usually depending on how dirty the laundry is. It is surprising that the available detergents show approximately the same dirt and stain removal properties in relatively soft and medium hard water with a hardness of 50-150 ppm, but that

they noticeably better at higher hardnesses (250 ppm) than control detergents in which the polyacetal carboxylate is replaced with an equal (even larger) amount of sodium tripolyphosphate. Furthermore, terry towels washed with a detergent according to the invention or with a control detergent (the detergent according to the invention contains polyacetal carboxylate and zeolite, and in the control detergent these are replaced with an equilibrium of sodium tripolyphosphate) appear to have approximately the same softness and overall electrostatic charge. Such detergents according to the invention are, however, noticeably superior compared to the control detergent in terms of reducing the electrostatic charge (and thus that the pieces of cloth stick to each other) for textiles made of acetate fibres.

The following examples serve to describe the invention in more detail. Unless otherwise stated, all parts are based on weight and all temperatures in °C in these examples,

in the rest of the description and in the patent claims.

Example 1

A particulate detergent in the form of spray-dried beads is prepared from all of the above-mentioned components, except for the cation-active compound, by preparing an aqueous mixture (solids concentration 55%) of the specified components in an electric kettle at a temperature of approx. 55°C, after which this mixture is spray-dried. The atomization tower used is a counter-flow tower that is operated under mild conditions with drying air which at the inlet has a temperature of approx. 300°C and with other devices to prevent charring of the beads and splitting of the sodium polyacetal carboxylate (by preventing accumulations on the tower walls using cooling air and regulated spraying to prevent contact between the shower and the tower walls). The product obtained has particle sizes in the range from 2.00 mm to 149 µm, a space density of approx. 0.3 g/ml and a moisture content of approx. 8%. One part of the described product "Arosurf TA-100" is mixed with 20 parts of the detergent thus produced. This product should preferably have particle sizes similar to the particle sizes of the detergent base, but even if it is a more finely divided powder with particle sizes within the range of 149 µm to 44 µm, the antistatic compound is well distributed throughout the detergent and adheres to the detergent particles, so that a product is obtained which still has particle sizes within the range from 2.00 mm to 149 µm and which still has a space density of approx. 0.3 g/ml. The manufactured product is tested to determine its ability to remove dirt and stains using a laboratory test washing machine of the Tergotometer type, in which standard cloths of various materials that have been soiled and stained in the standard manner are washed in wash water with a concentration of 0 .21% of the detergent at a washing temperature of 49°C and during a washing period of 10 minutes, while the agitator has a rotation speed of 100 revolutions per minute. minute. The hardness of the water used is calcium and magnesium hardness in the Ca:Mg ratio 3:2 at hardnesses of 50, 150 and 250 ppm. The reflection of the washed and dried cloths is read, and numbers indicating the weighted sums of the reflections are calculated, as these numbers, based on experience, have been shown to indicate the ability of the investigated detergent to remove dirt and stains (the higher the number, the better is the washing power). At hardnesses of 50, 150 and 250 ppm, the previously described test product according to this example gives figures of 256, 242 and - 234 respectively. _ When the same detergent is produced, but so that sodium tripolyphosphate replaces "Builder U" according to the recipe ( which results in a product with a higher active builder content than according to the experimental recipe), the numbers are respectively 254, 240 and 22. It thus appears that the cleaning and stain removal efficiency in hard water (hardness 250 ppm) for the present detergent is superior compared with a control detergent containing pentasodium tripolyphosphate which is the most successful commercial builder known in the detergent art, and even when more polyphosphate is used in the control detergent.

Example 2

When, according to the recipe according to example 1, half of "Builder U" is replaced with Zeolite 4A (20% hydrate) which is added to the kneader in the form of a finely divided powder with a particle size within the range 149-44 µm, and when the quaternary ammonium halide is mixed with the spray-dried beads in the manner described in Example 1, the resulting antistatic detergent has essentially the same cleaning properties (as measured by the same stain and soil removal number) as a control detergent based on sodium tripolyphosphate builder instead of "Builder U" and zeolite. Furthermore, when examined to determine the electrostatic charge which suggests the "attachment" of washed materials to each other, essentially the same improvement is obtained for the product of the invention containing "Builder U" and zeolite as for the "control" detergent, compared with detergents containing the cationic active compound. It is noted that with a detergent prepared according to the experimental recipe, a superior reduction of the electrostatic charge is obtained for acetate textiles compared to a control detergent containing sodium tripolyphosphate builder and the aforementioned cation active compound (no "Builder U" and zeolite). After washing with the detergents being compared and after drying in an automatic clothes dryer, the acetate cloths thus have an "electrostatic charge of 5.5 kV after washing with the control detergent and 1.6 kV after washing with the test product according to the invention and after such drying. When an investigation is carried out to determine the softening properties, the aforementioned control detergent and the aforementioned experimental detergent are given approximately the same number of points in a test where six panelists ranked sets of terry towels from softest to hardest after washing with one or the other detergent. The test conditions are the same as the previously described test conditions to determine the cleaning ability, except that light washing charges are used (approx. 0.5 kg charge per 65 liters of washing water) and except that the detergent concentration is reduced to 0.15% (100 g in 65 1 washing water).

According to a further variation of this example, the ratio of "Builder U" to zeolite is changed to 3:2.

The soil and stain removal figures obtained are essentially the same as for the control detergent in which the poly-phosphate builder is present instead.

It appears from the above tests that the experimental detergents according to these examples are equal or superior in terms of dirt and stain removal, reduction of electrostatic charge and softening properties compared to a control detergent in which sodium tripolyphosphate is used instead of "Builder U" or instead of a mixture of " Builder U" and zeolite.

Such results are also considered to be achievable when changes are made to the test recipe and/or when changes are made to the manufacturing process and/or the washing process. The aforementioned antistatic compound can thus be replaced with other such materials, e.g. dihydrogenated-tallow-dimethylammonium chloride, the corresponding quaternary ammonium bromides or other known antistatic agents. Likewise, when the sodium tridec<y>lbenzenesulfonate is replaced by other water-soluble higher alkylbenzenesulfonates, e.g. sodium dodecylbenzenesulfonate or mixtures of sodium linear tridecylbenzenesulfonate and sodium lauryl sulfate (in equal parts), or with other anionic surfactants, as previously described, satisfactory products according to the invention can also be obtained. The particular sodium polyacetal carboxylate can be replaced by other such compounds of different molecular weights, e.g. that having a molecular weight of 5250 (Monsanto "Lot No. 2547321") or with other such compounds within the given molecular weight ranges and with described end groups, and useful antistatic detergents will be obtained. Likewise, the builders, fillers and auxiliary additives can be changed, as previously described. For example, Zeolite 4A can be replaced with other Zeolite A qualities or with Zeolite X and/or Y. Moreover, the amounts of the various components can also be changed, usually by -10 or -25%, without the advantages of the present invention being lost , provided that the quantities are kept within the previously described ranges.

In the case of changes to the manufacturing process, the described detergents are made by subsequently adding "Builder U" powder with particle sizes that correspond to the size of spray-dried beads or which are more finely divided (149-44 µm), to the spray-dried beads before, after or together with antistatic particles of similar size or finely divided powder. The polyacetal carboxylate can be pre-mixed with the antistatic agent for later mixing with the spray-dried material. According to certain embodiments of the invention, the individual components can be mixed with each other without prior spray-drying of the main amount of them. In some cases, the various components can be added individually to the wash water. According to a preferred method, the polyacetal carboxylate will be post-added rather than spray-dried along with various other components for the final product, thereby better maintaining its full cleaning power-building and electrostatic charge-reducing effectiveness (by avoiding exposing the builder to possibly too much heat that would could cause it to break down).

When such a change is made for the described manufacturing process, the manufactured product has similar or superior properties compared to the properties mentioned above. By the methods described, the manufactured products have a bulk density of 0.25-0.5 g/ml, in the same way as the spray-dried beads, and both have particle sizes in the range from 2.00 mm to 149 µm, while the polyacetal carboxylate builder and the antistatic distearyldimethylammonium chloride usually has a higher bulk density (0.6-0.9 g/ml) and smaller<p>particle sizes (from 149^um

to 44 µm). Nevertheless, the smaller particles are satisfactorily held onto the larger particles in the final detergent so that the desired product is obtained.

The washing method according to this example can also be changed, e.g. by using water with different mixed calcium/magnesium hardness in the range of 50-250 ppm and even higher;, occasionally up to 300 ppm or more, and the washing can be carried out within the temperature range of 10-55°C and at detergent concentrations within the range 0.05-0.5%, and satisfactory antistatic effects will be obtained without too great a loss of cleaning power, and the products produced will be equal or superior compared to "control" products containing sodium tripolyphosphate instead of the polyacetal carboxylate builder or instead of a combination of a this is how zeolite builds.

Example 3

15 parts sodium linear dodecylbenzene sulfonate and

25 parts of sodium tripolyphosphate are mixed with 4.5 parts of "Arosurf TA-100" (90% active distearyldimethylammonium chloride), all components being present as finely divided powder with particle sizes within the range from 149 µm to 74 µm. Such a material, i.e. the control detergent, is used to wash terry towels using essentially the same method as described in Examples 1 and 2. The towels are then rated by a trained person and given a<p>score of 9 for softness according to a standard scale of 1 to 10, with 10 being the highest softness. In the case of another control attempt is used three parts "Arosurf TA-100" together with the 15 and 25 parts of the other ingredients, and a similar softness test is carried out. The washed towels are given a score of 3 according to this softness scale. -When instead of the 25 parts of sodium tripolyphosphate 25 parts of "Builder U", ("Lot 2538422") are used in such a detergent and the test is repeated, the obtained softness score is 10, and this softness score is also achieved when the content of "Arosurf TA-100" is reduced into 3 parts according to the aforementioned recipe.

The described detergents according to the invention are all satisfactory detergents and exhibit good antistatic and fabric softening properties.

Instead of dry mixing the various components, other detergents according to this example can be produced by spray drying and by other methods that are

described in example 1 and in the preceding description.

The aforementioned detergents can also be used to wash soiled and stained clothes and to soften them and to reduce the static adhesion which is normally the result after washing such clothes, from drying them in an automatic clothes dryer. Instead of using sodium linear dodecylbenzenesulfonate, sodium linear tridecylbenzenesulfonate, sodium laurylsulfonate, or higher fatty alcohol polyalkoxysulfates can be used, and Zeolite A or Zeolite X can be used to replace half of Builder U. Moreover, other of the mentioned antistatic agents can be used instead of "Arosurf TA-100", and the different amounts can be varied as described earlier, and the results will be satisfactory detergents with good softening and antistatic properties.

Claims (11)

1. Antistatic, built-up, particulate detergent, characterized in that it comprises a cleaning amount of a synthetic, anionic, organic surfactant, a building amount of a polyacetal carboxylate builder for such a surfactant or a building amount of a mixture of such a polyacetal carboxylate builder and zeolite builder, and an antistatic amount of an antistatic cationic compound. 2. Detergent according to claim 1, characterized in that the antistatic, cationically active compound is a quaternary ammonium compound. 3. Detergent according to claim 2, characterized in that it is essentially free of phosphate and that the synthetic, anionic, organic surfactant is a sulfated or sulfonated surfactant, the polyacetal carboxylate builder has a calculated weight average molecular weight of 3,500-10,000, the zeolite builder is a hydrated zeolite of type A, type X or type Y, and the quaternary -ammonium salt is a di-higher-alkyl-di-lower-alkylammonium halide in which the higher alkyl group has 10-18 carbon atoms and the lower alkyl group 1-3 carbon atoms. 4. Detergent according to claim 3, characterized in that the synthetic, anion-active, organic surfactant is a higher alkylbenzene sulphonate in which the alkyl group has 10-18 carbon atoms, the polyacetal carboxylate is a polyacetal carboxylate in which the carboxylate is sodium carboxylate, the zeolite is a zeolite of type A with the formula wherein x is 1, y is 0.8-1.2, preferably approx. 1, z is 1.5-3.5, preferably 2-3 or approx. 2, and w is 0 to 9, preferably 2.5-6, and the quaternary ammonium salt is a di-higher-alkyl- dimethylammonium halide in which the higher alkyl group has 10-18 carbon atoms. 5. Detergent according to claim 4, characterized in that it comprises 5-30% sodium linear-higher-alkylbenzenesulfonate in which the higher alkyl group has 12-14 carbon atoms, 5-40% polyacetal carboxylate builder or a mixture of such a builder and zeolite builder, 2-10% distearyldimethylammonium chloride, 2-20 % moisture, and as any remainder consists of filler or fillers and/or another builder or builders and/or an auxiliary additive or agents. 6. Detergent according to claim 5, characterized in that it comprises 10-25% sodium linear tridecylbenzenesulfonate, 15-30% polyacetal carboxylate builder with a calculated weight average molecular weight of 5000-9000 or a mixture of such a builder and zeolite builder, with at least 5% of the detergent being made up of polyacetal carboxylate builder, 3 -8% distearyldimethylammonium chloride, 3-15% moisture, 8-18% sodium carbonate, 5-10% sodium silicate with a ratio of Na2 0:SiO2 within the range 1:1.6-1:3.0 .and 20-35% sodium sulfate. 7. Detergent according to claim 6, characterized in that it comprises 13-23% sodium linear tridecylbenzene sulphonate, 17-23% sodium polyacetal carboxylate builder with a calculated weight average molecular weight of approx. 8000, 4-6% distearyldimethylammonium chloride, 5-12% moisture, 10-15% sodium carbonate, 6-9% sodium silicate with a Na2 0:SiO2 ratio of 1:2.0-1:2.6 and 22-30% sodium sulfate. 8. Detergent according to claim 6, characterized in that it comprises 13-23% sodium linear tridecylbenzene sulphonate, 17-23% of a mixture of sodium polyacetal carboxylate builder with a calculated weight average molecular weight of approx. 8000 and zeolite of type A, in which x is 1, y is 1, z is 2-3 and w is 2.5-6, the ratio between polyacetal carboxylate builder and zeolite builder in this mixture being within the range 2:3-2:1, 4-6% distearyldimethylammonium chloride, 5-12% moisture, 10-15% sodium carbonate, 6-9% sodium silicate with a ratio of Na2 0:SiO2 within the range 1:2.0-1:2.6 and 22-30% sodium sulfate. 9.Process for the production of an antistatic, built, particulate detergent which includes a cleaning amount of synthetic, anionic, organic surfactant, a building amount of a polyacetal carboxylate builder for such a surfactant or a building amount of a mixture of such a polyacetal carboxylate builder and zeolite builder . range from 2.00 mm to 149 µm, and that polyacetal carboxylate builder and an antistatic amount of antistatic quaternary ammonium salt are mixed with the prepared spray-dried beads. 10. Method according to claim 9, characterized in that the synthetic, anion-active, organic surfactant uses sodium linear-higher alkylbenzene sulfonate in which the higher alkyl group has 12-14 carbon atoms, that the polyacetal carboxylate builder uses a sodium polyacetal carboxylate with a calculated weight average molecular weight of 5000-9000, that in the kneading apparatus mixture uses a builder that includes a hydrated Zeolite A, that sodium silicate is used with a ratio Na2 0:SiO2 of 1:2.0-1:2.6 and also sodium carbonate and sodium sulfate, the polyacetal carboxylate builder and the antistatic, quaternary ammonium halide are pre-mixed with each other and mixed with the spray-dried beads, so that a detergent comprising 13-23% sodium linear tridecylbenzenesulfonate, 17-23% total builder consisting of polyacetal carboxylate builder with a calculated weight average molecular weight of approx. 8000 and Zeolite A builder, the ratio of flour to polyacetal carboxylate and zeolite being in the range 2:3-2:1, 4-6% distearyldimethylammonium chloride, 5-12% moisture, 10-15 sodium carbonate, 6-9% sodium silicate with a ratio Na2 0:SiO2 of 1:2.0-1:2.6 and 22-30% sodium sulfate. 11. Method according to claim 10, characterized in that spray-dried beads are produced with a bulk density of 0.25-0.5 g/ml and a mixture of sodium polyacetal carboxylate builder and antistatic distearyldimethylammonium chloride with a bulk density that is higher than the bulk density of the spray-dried beads , and that such a mixture is produced with particle sizes in the range from 149 µm to 44 µm.