CH673466A5 - - Google Patents

Description

DESCRIPTION

The present invention relates to: a softening and antistatic liquid composition which is suitable for addition to the rinse water in order to make washing soft and antistatic.

The softening and antistatic liquid composition, which is suitable for addition to the rinse water in order to make laundry soft and antistatic, is characterized by a content of 1 to 10 parts of isostearamide which is more aliphatically substituted in nitrogen and 3 to 20 parts of bentonite in an aqueous medium , the ratio of concrete to isostearamide in the range of 1: 1 to 20: 1.

The invention relates to a liquid composition in which one or more antistatic substances are incorporated, as described in US SN 674 194, a CIP of US SN 404 794.

Builders and compositions containing synthetic organic surfactant are now the cleaners of choice for washing dirty laundry. Such compositions have proven to be extremely effective for washing textiles made of synthetic and / or natural fiber materials, both for oily and protein or clay-containing soils, these three types of soiling being the ones which occur most frequently in household laundry and which are considered to be can be seen as somewhat representative for the soiling of usual dirty laundry. With the replacement of soap by synthetic organic surfactants in detergents, the softening effect of soap (mostly as insoluble soap deposited on the textile fibers of the laundry) was lost, so that the laundry often becomes rough and stiff or sticky, especially in the presence of certain inorganic builder salts and feels uncomfortable. It has been known for years that the addition of concrete to detergent compositions based on anionic surfactants can help to soften the laundry and can thereby produce detergents that are accepted by the consumer.

Although liquid detergent compositions have been known for years, heavy-duty detergents in the liquid state have only become popular relatively recently. Such formulations are sometimes thickened, particularly when they contain suspended solids, to prevent these components from settling when stored. Gel-forming bentonite such as western or Wyoming bentonite has thickening properties and is also a textile softening agent.

With the advent of synthetic polymeric fibers, clothing, and other laundry items made from these fibers, as well as from blends thereof with natural fibers such as cotton / polyester blends, and with the growing use of automatic laundry dryers, most of which are tumble dryers, it has been found that dried Laundry frequently accumulates electrostatic charges, which causes them to stick together in an unpleasant manner, which disrupts normal handling and folding the laundry for storage. S It has been known for years that cationic compounds such as quaternary ammonium salts, e.g. B. Di (higher) -alkyldi (lower) -alkylam-monium halides are able to act as antistatic agents (anti-statics), ie to reduce the static charges on textiles and thus to avoid electrostatic sticking or sticking. To soften laundry, such halides would normally be added during a wash program in the rinse water and not in the detergent composition or in the wash water since they react chemically with anionic surfactants, which are the most commonly used surfactants in detergents. This reaction, which would presumably be stronger in liquid detergents than with particulate products, would reduce the detergent effect of the detergent composition and could form undesirable reaction products that settle on the wash to be washed and result in 20 dirty or greasy stains. In recent years, cationic compounds, such as the quaternary ammonium halides, have been incorporated into detergent compositions containing builders, especially particulate detergent compositions, in which they do not react significantly with the anionic surfactants when stored, but react to a certain extent with them in the wash water. It has been shown that, although these compositions have an antistatic effect and reduce the static adhesion of washed laundry, the cleaning power of the detergents 30 containing them is less than that of the base compositions without the antistatic.

US SN 404 794 and the CIP, US SN 674 194, describe the use of nitrogen-substituted primary alkyl isostearamides as antistatic agents in detergent compositions and report that these isostearamides are not significant with anionic surfactants in the compositions or in the wash water react. It is also reported that the described isostearamides can be combined with bentonite and used with particulate detergent compositions 40, thereby obtaining a wash water that has both fabric softening and antistatic properties, so that the laundry washed with it is soft and free from impermissible static sticking is. The present invention describes in detail liquid detergent compositions containing both 45 bentonite and nitrogen-substituted isostearamide as an antistatic, the desired effects achieved thereby, including that the laundry washed is sufficiently soft (especially towels made from woven fabrics or otherwise processed) Vegetable fibers, such as cotton and 50 terry cloth), no or only little static sticking, better cleaning and no "quat stains". Particularly noteworthy is the surprising improvement in the antistatic effect of the isostearamide, which is primarily aliphatic substituted on nitrogen, due to the presence of bentonite in the liquid builder-containing detergent composition (in the presence of anionic surfactant). In addition, it was found that there is neither a reduction in foaming nor a reduction in the effect of fluorescent brighteners when using the detergent compositions according to the invention containing anionic surfactant and bentonite and CISA 60, whereas the use of quaternary ammonium salts as antistatic agents reduces foam formation becomes apparent due to the reaction of the quaternary salt with the anionic surfactant. Furthermore, yellowing or similar discoloration of the laundry 65 by an antistatic agent and the re-precipitation of dirt are reduced in comparison with the results obtained.

if in other builder-containing detergent compositions a quaternary ammonium halide is possible because of its

3rd

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have antistatic effects with an anionic surfactant. The invention is characterized by the features in independent claim 1.

Typically, the active detergent component of the detergent composition described is an anionic surfactant (which would react with a quaternary ammonium salt) and the detergent is a builder-containing composition that contains a builder such as sodium tripolyphosphate, sodium carbonate, NTA or polyacetal carboxylate or other suitable builders or a mixture of these builders contains. In a preferred liquid detergent composition, the isostearamide is dissolved, emulsified or dispersed and the bentonite is present as a fine-particle dispersion, the particles of which are preferably smaller than number 200 US sieve series, for example sizes from numbers 200 to 400, e.g. B. have about number 325. The bentonite and / or the N-isostearamide can, if desired, be added to the wash water before, after or together with the rest of the constituents of the liquid detergent composition described.

The anionic surfactant used in the detergent compositions is normally sulfated and / or sulfonated lipophilic material with an alkyl chain of 8 to 20, preferably 10 to 18 and particularly preferably 12 to 16 carbon atoms, which is preferably a particulate mixture of 2 types of these surfactants. Although various water-soluble salt-forming cations can be used to form the desired sulfated and sulfonated surfactants including ammonium and lower alkanolamine (such as triethanolamine) and magnesium, an alkali metal such as sodium or potassium is normally used, with sodium being the preferred cation. Among the various anionic surfactants that can be used are the linear higher alkylbenzenesulfonates having 10 to 18, preferably 12 to 16 and particularly preferably about 12 to 14 carbon atoms in the alkyl chain, e.g. B. dodecyl and tridecyl most suitable, often with a fatty alcohol sulfate of a polyethoxylated higher fatty alcohol. The alcohol ether sulfate normally comes from a higher, linear (for example fat) alcohol having 10 to 18, preferably 12 to 15, carbon atoms, the degree of ethoxylation usually being 1 to 15 ethoxy groups per mole, preferably 2 to 10, particularly preferably 2 to 5, e.g. B. 3. Are usable a. also the monoglyceride sulfates, higher fatty alcohol sulfates, paraffin sulfonates and olefin sulfonates, the alkyl group present in all of these compounds having 10 to 18 carbon atoms.

Some of these alkyl groups can be slightly branched (not preferred) as long as they have a carbon chain length in the ranges described.

Although the linear higher alkylbenzenesulfonates and the sulfated polyethoxylated higher alcohols than sodium salts are the preferred anionic surfactants, mixtures of these surfactants with other such sulfonates and sulfates which have other cations, as well as mixtures of these surfactants with others, e.g. B. the fatty alcohol sulfates can be used. In some cases, only relatively small proportions or smaller amounts of the linear alkylbenzenesulfonates and polyethoxylatesulfates are present, or the anionic surfactant can be a mixture of other anionic surfactants of the types described. Various other anionic surfactants can also be used, as are well known to the person skilled in the art and are described in various publications, for example in McCutcheon's Detergents and Emulsifiers, 1969.

Although primarily anionic detergent compositions having antistatic properties are contemplated, the desired results reported herein can also be obtained with compositions containing other types of surfactants, often with the anionic surfactants, such as nonionic and amphoteric surfactants. The nonionic and amphoteric substances mentioned are normally only minor

Shares present, if any, are generally at most half as much as the anionic surfactants present. Preferred nonionic surfactants are the ethylene oxide condensation products of higher fatty alcohols, e.g. B. the condensation products of higher fatty alcohols with 12 to 18 carbon atoms and 3 to 20 moles of ethylene oxide, preferably condensation products of higher fatty alcohols with 12 to 15 carbon atoms and 5 to 15 moles of ethylene oxide.

The detergent is preferably built up with a tenside builder, so that it has increased cleaning power and is suitable as a full detergent. Useful builders for the compositions are the polyphosphates such as sodium tripolyphosphate and tetrasodium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate (Na20: SiO2 = 1.6 's to 3.0, preferably 1: 2.4), NTA, sodium citrate, sodium glucose -nat, borax, other borates, zeolites, polyacetal carboxylates and other useful builders known for liquid detergents. Sodium silicates are often omitted because they can react inadmissible in liquid media with carbonate and zeolite builders as well as with 20 bentonite and this leads to undesirably thick or coagulated products or precipitates.

If zeolite builders are used, they generally correspond to the formula (Na20) xx (Al203) yxw H20, where x is 1, y is 0.8 to 1.2, preferably about 1, z 1.5 to 3.5, 25 preferably represents 2 to 3 or about 2 and w is 0 to 9, preferably 2.5 to 6. These zeolites are cation exchangers with a calcium ion exchange capacity of about 200 to 400 or more milligram equivalent calcium carbonate hardness per gram. They are often hydrated to a moisture level of 5 to 30, preferably 10 to 25%, e.g. B. about 20%. Zeolite A is preferred (X and Y are also useful) and Type 4A zeolite is most preferred. The particle sizes of the zeolites are usually 100 to 400 meshes (or sieve numbers), preferably 140 or 200 to 325 meshes, but their outermost particle sizes are in the submicron range. The various zeolites are described in detail by Donald W. Breck in “Zeolithe Molecular Sieves”, published in 1974 by John Wiley & Sons, particularly on pages 747 to 749.

Polyacetal carboxylates which can be used are those according to US Pat. No. 4 ° 4 144 226 and are prepared by the process described therein. A typical such product has the formula

45 - (CHO) n - R2

COOM

such that M is from the group consisting of alkali metal, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium and alkanolamine groups which have 1 to 4 carbon atoms in their alkylene, n is on average at least 4 and R] and R2 are chemically stable groups, which stabilize the 55 polymer against rapid depolymerization in alkaline solution. The polyacetal carboxylate is preferably one in which M alkali metal, e.g. B. is sodium, n stands for 20 to 200, Ri for

MOOC /

H-jC-CO—

J i

MOOC

or a mixture thereof, R2 for ch3ch2o

HCO or

I.

H3C

673 466

4th

OCH2CH3

I.

-CH

i stands and n means on average 20 to 100, preferably 30 to 80. The calculated weight average molecular weights of the polymers are normally in the range from 2000 to 20,000, preferably from 3500 to 10,000 and particularly preferably from 5000 to 9000, e.g. B. at about 8000.

Although the preferred polyacetal carboxylates have been described, they may be wholly or partially replaced with other such polyacetal carboxylates or related organic builder salts as described in various Monsanto patents, including methods of making the same and compositions in which they are used can. The chain end groups specified in the Monsanto patent specifications, in particular US Pat. No. 4,144,226, can also be used, provided that they have the desired stabilizing properties which enable the builders mentioned to be depolymerized in acidic media , which facilitates their biodegradation in wastewater, but preserves their stability in alkaline media such as in washing solutions.

If the presence of phosphorus in the detergents is to be avoided, the polyphosphate builders can be omitted. In these cases, it is preferred to use other phosphate-free builders such as those mentioned here. Combinations of zeolite with polyacetal carboxylate represent a very useful substitute for the polyphosphate builders. Such combinations with N-alkylisostearamides in detergent compositions (but without bentonite) have already been described in US Pat. No. 674,899. The sodium salts of these builders are preferred, but alkali metal and other soluble salts can at least partially be used in their place.

Electrolytes and fillers may be present in the liquid detergent, for example sodium sulfate (preferred) and sodium chloride, to modify the physical properties of the detergent and, if desired, add electrolyte to the product and wash water. They can also serve various other purposes.

The antistatic agent of choice for practicing the invention is N-cocoisostearamide. This antistatic is an amide that can be chemically formed from isostearic acid and cocoamine by the following condensation reaction:

O O

"A"

RCOH + R'NH2 - »- RCNHR1 + H20 _

Isostearic acid, o

II

RC-OH.

>

is a saturated fatty acid of the formula Q7H35COOH, a complex mixture of isomers, especially those with methyl side chains, which are mutually soluble and essentially inseparable. Although this acid is normally used for purposes similar to stearic or oleic acid, it is far superior to these materials for the production of effective antistatic substances which are suitable for incorporation into detergents. Cocoamine is an aliphatic amine, the aliphatic group of which is derived from coconut oil. Other primary aliphatic amines, preferably higher alkyl amines having 7 to 18 carbon atoms in alkyl such as R'NH2, where R 'is such a higher alkyl, can also be used. Cocoamin, however, produces an N-alkyl isostearamide with the best properties for incorporation in detergents. His name is CISA.

5 Although CISA is the most preferred antistatic, other isostearamides which are aliphatically substituted on the nitrogen can also be used according to the invention, such as those which are derived from primary amines having up to 20 carbon atoms, preferably 7 to 18 carbon atoms, their aliphatic-10 shear Part can optionally be hydrogenated, provided that the amides show sufficient antistatic activity for the stated purpose. Some examples of this are the N-alkylisostearamides with 7 to 18 carbon atoms, such as those derived from n-decylamine, N-octylamine and N-tallow amine. However, CISA is regarded as the best N-alkylisostearamide in terms of its antistatic activity, which is why when using other isostearamides these are preferably used with CISA and the amount of the other isostearamide is preferably less than that of CISA. In some cases, the hydrogen atom of the amide nitrogen can be replaced by suitable residues such as, for example, lower alkyl, e.g. B. methyl, provided that you still achieve a desired antistatic effect. However, it has been found that the tertiary isostearamides generally show little antistatic activity. The bentonite used is preferably a Wyoming or Western bentonite with a swelling capacity of 3 to 15, preferably 7 to 15 ml / g. Its viscosity at 6% concentration in water is usually in the range of 3 to 30, preferably 8 to 30 cps. Useful source bentonites of this type are sold under the trade name "Mineral Colloid" as industrial bentonites by the Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials were previously distributed by this company as IHIXO-JEL. These are selectively mined and enriched bentonites. Most useful are those available as mineral colloid 101, etc., which correspond to those previously sold as THIXO-JEL's Nos. 1,2, 3, and 4. These materials have pH values (at a concentration of 6% in water) from 8 to 9.4, maximum free moisture contents of about 8% and specific weights of about 2.6. The powder quality is 85% continuous a 200 mesh sieve (US sieve series) This bentonite is equivalent to the Bentonite clay AEG 325 sold by American Colloid Co., which essentially has a sieve size of the number 325.

45 Enriched Wyoming bentonite is preferred as part of the detergent, but other bentonites can also be used, especially if they only make up a small proportion of the bentonite used. It has been found that at least about 2%, preferably at least 4%, and particularly 50%, preferably 5% or more to about 8% water should be present in the bentonite initially before it is mixed with other bead components and with the liquid medium for the liquid Detergent is mixed. It has been found that overdrying to the point where the bentonite loses its "inner" moisture can impair the ability of the bentonite to effectively hydrate in an aqueous medium and greatly reduce the utility of the fabric softening compositions.

The various auxiliaries that can be present in the liquid washing machine 60 include coloring substances such as dyes and pigments, fragrances, enzymes, stabilizers, thickeners, solvents, dispersants, activators, fluorescent brighteners, bleaches, buffers, fungicides, germicides, foaming agents , Anti-foaming agent and the flowability promoting substances. The auxiliaries, builders and fillers, unless mentioned in other classes, also include various additional components or impurities that are present in the components of the compositions

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are sometimes present. For example, it is known that sodium carbonate and water with polyacetal carboxylate are often present in Builder U, a product that is used according to the invention as a supplier of polyacetal carboxylate.

The amounts of the essential ingredients of the detergent compositions are chosen so that they are effective for the intended purposes. The synthetic organic surfactant or mixture is present in the liquid detergent in a cleaning amount, the bentonite in a fabric softening amount and the antistatic, more aliphatically substituted isostearamide in an antistatic amount. When Builder or a mixture of builders is used, which is most often the case, it is present in an amount possessing a builder effect. The proportions of liquid detergent are normally 3 to 25%, preferably 3 to 15% and particularly preferably 5 to 13% sodium (linear, higher) alkylbenzenesulfonate, e.g. about 9% sodium (linear) alkylbenzenesulfonate with 12 to 14 carbon atoms, 0.5 to 10% sodium (higher) fatty alcohol polyethoxy ether sulfate with 8 to 18 carbon atoms in the alcohol part and 1 to 15 moles of ethylene oxide per mole, preferably 1 to 5% sodium ( higher, primary) alcohol polyethoxy ether sulfate having 12 to 15 carbon atoms in the alcohol and 2 to 4 or 6 moles of ethylene oxide per mole, e.g. B. about 2%. The liquid detergent builder, which can be a builder mixture, normally makes up 5 to 40% of the composition and is often a combination of 5 to 25% sodium tripolyphosphate and

2 to 10% sodium carbonate, preferably often a combination of 8 to 14% sodium tripolyphosphate and 3 to 7% sodium carbonate, for example about 11 or 4%. The bentonite component is usually 3 to 20% of the liquid detergent composition, preferably 5 to 20% and particularly preferably approximately 5 to 15%, for example approximately 12%, the antistatic isostearamide mostly 1 to 10% of the liquid detergent compositions, preferably 1 to 7% and particularly preferably about

3 to 7%, e.g. B. about 5%. The water or aqueous medium content of the liquid detergent is generally in the range from 3 to 80%, preferably 40 to 70%, particularly preferably about 45 to 65%, e.g. B. at about 55%.

In the liquid detergent composition, the ratio of bentonite to antistatic is usually in the range from one part of antistatic per 1 to 20 parts of bentonite, preferably in the range from 1: 1.5 to 4 and particularly preferably from 1: 2 to 3, for example 1: 2.4.

To produce the liquid detergent compositions, the various constituents of the end product are usually only mixed with one another or mixed and stirred or otherwise sufficiently moved in order to produce a uniform liquid product. The order of addition of the components can be chosen so that the best possible mixing is guaranteed. Sufficient liquid medium is usually present at all times to prevent the solids from caking due to a lack of liquid and to avoid the formation of lumps which could later be difficult to disperse. According to “normal” production methods, both the soluble and the insoluble fine-particle components are generally mixed with part of the aqueous medium and the mixture is then diluted with the rest of the aqueous medium. The mixture can be run through a homogenizer to accelerate the dispersion of the components and to prevent them from settling. In some cases, hydrotropic substances such as sodium cumene sulfonate and sodium xylene sulfonate, usually in small amounts such as up to about 1 or 2%, may be present in the formulation to help keep the liquid composition homogeneous. Similarly, solvents such as ethanol and ethylene glycol or other suitable glycols can be used to solubilize components. These solvents also help prevent the product from freezing or freezing in cold weather. The various solid components of the liquid detergent composition are usually in finely divided form in order to accelerate the direct dissolution (if they are soluble) or dispersion in the aqueous medium. In general, the powdery materials are of smaller particle size than the numbers 140 or 200 US sieve series, usually these particle sizes are in the range of numbers 140 to 400, often preferably 200 to 400, e.g. B. at about number 325 US sieve row. Easily soluble components such as sodium carbonate, sodium tripolyphosphate and the synthetic organic surfactants can have particle sizes ■ which are larger in the given range, or even larger, in the case of insoluble or slowly soluble materials such as zeolites and clays the smaller 15 Particle sizes are generally more desirable.

For use, laundry is washed with a liquid detergent in washing water, which is easily done in the usual way with standard equipment and normal washing concentrations and where you get a clean laundry that feels soft, does not stick statically in an inadmissible manner, even if substantial amounts are involved on synthetic fibers such as polyester, e.g. B. Dacron, and polyamides, e.g. B. nylon, are present. The wash water used can be normal tap water. The liquid detergent compositions are also effective at greater hardnesses of about 300 ppm than calcium carbonate, and sometimes even more. Normally, the water hardness is a mixed magnesium and calcium ion hardness, with the majority coming from calcium. The hardness of the water is preferably not greater than 250 ppm. Typically, the tap water used has a hardness of 20 to 150 or 200 ppm, e.g. B. about 50 or 100 ppm. The compositions can be used in wash water at any temperature between 10 and 90 ° C and are even effective with wash water at lower temperatures, such as at about 35 room temperatures. According to European practice, detergents can be used in wash water at temperatures near the boiling point, e.g. 70 to 90 ° C, whereas lower temperatures are used according to common American practice. According to American practice, particularly good results are achieved when the compositions are used in wash water at temperatures in the range from 10 to 50 ° C., preferably 30 to 50 ° C., eg. B. at about 40 ° C. The concentration of the liquid detergent in washing water can be varied depending on the circumstances, but is usually in the range from 45 0.1 to 0.5, preferably 0.1 to 0.4 and particularly preferably 0.15 to 0.25, e.g. . B. at about 0.2%. Thus, in a washing machine containing about 651 water, half a measuring cup or 145 g of the liquid detergent, often a density of about 1.1 to 1.3 g / ml, e.g. B. about 1.2 g / ml can be used to wash a norma-50 len filling, about 2.7 to 4.5 kg, e.g. B. about 3.6 kg of dry laundry. If one wishes to use larger or smaller volumes of liquid detergent per wash load, the concentrations of the constituents in the liquid composition can accordingly be increased or decreased within 55 practical limits.

Standard household washing machines and the usual washing programs for these machines or commercial washing machines can be used. The washing of the laundry takes place in a normal washing cycle for 2 to 30 minutes, 60 z. B. 5 to 20 minutes, e.g. B. about 10 minutes, which generally depends on the degree of soiling of the laundry and the type of fabric. At the end of the wash cycle, the laundry is automatically rinsed and then dried in an automatic tumble dryer by circulating it while drying air flows through it.

Instead of producing a liquid detergent which contains all of the cleaning, builder, fabric softening and antistatic components of the composition, in

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a variation, a liquid composition is prepared which contains fabric softening and antistatic components. Such a composition can be used together with a suitable liquid detergent, such as those on the market in large numbers, in order to impart to the laundry washed with such a detergent textile-softening and antistatic properties. For example, CISA or other suitable isostearamides and bentonite (or another fabric softening clay) substituted on nitrogen with a primary aliphatic group can be emulsified, dispersed, suspended and / or partially in one with a small amount of hydro-trop, emulsifier, suspending agent and / or solvent be dissolved in a suitable liquid medium, which is preferably water, in order to produce a suitable pourable liquid which can be used to supplement the liquid detergent. Such liquid preparations can be added to the liquid detergent beforehand and / or together with the liquid detergent in the washing medium, or they can be added to detergents or to the washing water with these detergents in order to further improve the softening and the antistatic behavior of the washed laundry. With the textile softening and antistatic supplement composition, one is able to use the present invention with any liquid detergent formulations and to adapt them. It is up to the consumer to determine within reasonable limits how much softening and antistatic properties the laundry should receive. It is possible to use more of the supplement composition when using detergents that are particularly effective or "hard" detergents, which requires a stronger softening and stronger antistatic treatment. Typically, the amount of fabric softener and antistatic present in the make-up fluids is 10 to 30%, but can be 10 to 50%, especially if a cosolvent such as ethanol is present. The ratio of antistatic to bentonite is in the same ranges as given above for the liquid detergent compositions containing both antistatic and plasticizer.

Various advantages, most of which have already been pointed out, are highlighted in the following working examples. The isostearamide antistatic which is aliphatically substituted on the nitrogen (primary) does not react appreciably with bentonite or with the anionic surfactants, which is why compositions are relatively stable when stored and their desired cleaning, do not significantly lose softening and antistatic activities during storage or before or during use. Unlike the compositions based on the currently generally used cationic fabric softeners and antistatic agents, such as quaternary ammonium salts, the compositions mentioned do not deposit any reaction products of these cationic materials with anionic surfactants on the laundry to be washed, so that such laundry removes dirt during the Washing is not subject to this when working as specified. As a result, the detergent compositions result in whiter laundry and less redeposition of dirt, whereas laundry washed with compositions containing anionic surfactant and quaternary ammonium salt (in antistatic and fabric softening amounts) tends to yellowing, especially with repeated washing . The cleaning power is measurably better when using the detergents mentioned than when using those in which a quaternary ammonium salt replaces isostearamide. There is also an impairment of the foaming power of the anionic surfactant, which is normally observed in the presence of cationic compounds such as quaternary ammonium salts, and reactions of these "quats" with fluorescent brighteners and the resulting reduced glow in the

Avoid washing when using the antistatic agents according to the invention.

Such undesirable interactions of anionic and cationic materials are particularly severe and unacceptable if both the anionic surfactants and the cationic softening and antistatic substances are in intimate contact over comparatively long periods of time, as is the case when they are in the same aqueous Medium are such. B. in certain textile softening io anionic liquid detergents. The invention thus brings about a significant improvement in detergent technology, it being important nowadays that detergents have textile-softening and antistatic properties in addition to excellent detergency.

15 The liquid detergents and make-up liquids are both preferably sufficiently viscous or thixotropic to keep finely divided components in suspension and to prevent them from settling during storage. Nevertheless, the liquids should be freely flowable from a bottle with a relatively narrow discharge opening 20. It has been found that liquids with viscosities in the range of 1 to 5 Pa.s (1000 to 5000 cps) generally do not settle and have the desired flow properties. The liquids therefore have viscosities in this range in the desired manner. In particular, this range is 3 to 5 Pa.s (3000 to 5000 cps), e.g. B. about 4 Pa.s (4000 qps) at room temperature (25 ° C). Although the viscosities of the compositions are comparatively stable, it can be assumed that relatively small changes in the production processes and in the storage conditions can influence the viscosity of the product, which increases more frequently than decreases during storage. When the viscosity or thickness increases excessively and the bottles packed or packaged are placed in a shaker, the compositions generally become fluid again and disperse the components which may have separated.

The following examples illustrate the invention. In the examples, the description and the claims, unless otherwise stated, all parts are by weight and the temperatures are in degrees C.

40

example 1

component

percent

45 sodium (linear) tridecylbenzenesulfonate

9.0

Sodium (primary, higher) alcohol ether sulfate *

2.0

Bentonite (American Colloid Company AEG 325)

12.0

Sodium tripolyphosphate

11.0

sodium

4.0

5o N-cocoalkyl isostearamide

5.0

Optical brightener (Iinopal LMS X [CIBA

GEIGY]

0.3

Sodium carboxymethyl cellulose

0.2

Titanium dioxide

0.5

55 coloring pigment (ultramarine blue)

0.2

Dye (polar brilliant blue 1% aqueous solution)

0.6

Perfume

0.5

Demineralized water

54.7

100.0

60

* Reaction product of primary alcohol with 12 to 15 carbon atoms and 3 moles of ethylene oxide per mole.

The detergent components were dissolved in 2A of the water, 65 after which the CISA was dispersed and dissolved in the detergent solution thus prepared, the builder salts were dissolved in this aqueous medium, then the finely divided bentonite was dispersed in the composition and finally the various auxiliaries and

7

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added the rest of the water. The product obtained has a viscosity of about 3000 cps at 250 ° C., which was measured using a Brookfield viscometer with a spindle number 3 and a speed of 12 rpm. The detergent composition is stable, its components remain dissolved and dispersed in the aqueous medium and do not separate.

3.6 kg of a laundry filling made of various materials (polyester, nylon, acetate and polyester-cotton blend) were washed in a conventional GE top loader, which contained 651 water with 100 ppm, as calcium carbonate, mixed calcium and magnesium ion hardness, with 145 g of the liquid Detergent composition were used according to the above approach. The washed laundry, including test samples of the various materials mentioned, was rinsed and then dried in a tumbler. The softness of the various textiles was assessed by experts. The level of protection provided by each textile part against the generation of electrical charge (and significant static adhesion) when drying in a tumbler or during other movements was also determined by determining the extent of electrostatic adhesion shown by the individual laundry parts. The washed laundry was sufficiently soft and not sticky.

Quantitative determinations of the electrostatic charge recordings of the various washed and dried textile parts were obtained by rubbing each textile part with wool in a controlled manner at low relative humidity (25 to 30% R.F.) and measuring the charges accumulated by the sample parts. A variety of sample parts were used in this test and an average of each material was calculated from the readings. In order to obtain an antistatic index, which represents an overall assessment of the antistatic ability of a liquid detergent composition, it has proven to be expedient to use the sums of the charges on the materials mentioned. For the liquid detergent according to the invention, this sum is 12 kilovolts, whereas the index for a liquid comparative detergent of the same approach, but with the omission of bentonite and CISA, is 48 kilovolts. In the tests of the invention, readings above 35 kilovolts were generally unacceptable (laundry sticks considerably). When the softness was assessed (terry towels were the washed laundry parts) by a panel of experts, the towels washed with the liquid detergent of this example according to the procedure given above were given the .softness rating or softness rating 9 on a scale of 1 to 10, on which 10 indicates the greatest softness . Towels washed in the same manner with the comparative detergent were rated 1.

In other tests, the degree of dirt re-precipitation on the washed laundry was approximately the same with the product according to the invention as with a second comparison product, which differed from the approach according to the invention by replacing N-alkylisostearamide with water. This reprecipitation was worse with a third reference product in which the isostearamide was replaced by the same percentage of dimethyldistearylammonium chloride.

The test textiles washed with the product according to the invention show no "quat stains" which can sometimes be found on laundry which has been washed with similar formulations which contain dimethyldisteaiylammonium chloride or other quaternary compounds instead of the N-isostearamidantatic. The optical brightening effect is also greater in the product according to the invention containing N-isostearamide than in a similar product in which the isostearamide is replaced by dimethyldisteaiylammonium chloride or other such antistatic quaternary ammonium halide. Another advantage of using CISA instead of the "Quat" or the quaternary compound is an improvement in the appearance of the liquid detergent composition due to the absence of any precipitated product from the reaction of the quaternary compound and anionic surfactant.

When the 5% N-cocoalkyl isostearamide in the stated batch of the product of the invention was replaced by 1%, 3% and 5 7% of this isostearamide, the softness of the products obtained was 8, 8 and 9 and the static indices 27, 19 and 10. Softness indices of 8 or more are considered sufficient, as are static indices of less than 30, softness indices as low as 7 and static indices as high as 10 35 are sometimes acceptable. If one omitted the CISA approach as in the second comparative product, the washed laundry was rated with a softness of 8 and the electrostatic charge index was 36 kilovolts.

When the first comparative product and the products of the invention were compared in practical washing tests,

that the comparative product does not make washing sufficiently soft and results in higher electrostatic charges such as considerable sticking. If bentonite was omitted from the approach according to the invention, as in the fourth comparative product, 20 detergent compositions are obtained which are unsatisfactory in terms of both their plasticizing properties and the avoidance of static sticking, even if a relatively large proportion of the isostearamide is present. If the isostearamide was left out, an inadmissible static sticking of the washed laundry was observed despite the presence of 12% 25 bentonite. It can thus be seen that the combination of bentonite and N (higher) -allfylisostearamide is important for the success of the detergent compositions according to the invention, since 1.) this combination leads to a greater anti-30 static effect than could be predicted; 2.) The bentonite softens the laundry and 3.) Critical consumers today demand both textile softening and antistatic (preventing sticking) properties.

Instead of the preferred N-cocoalkyl isostearamide, 35 other higher aliphatic isostearamides, preferably higher primary aliphatic isostearamides and particularly preferably higher primary N-alkyl isostearamides, such as, for example, Nn-octylisostearamide, Nn-decylisostearamide, Nn-heptylisostearamide, Nn-dodecylnostadamido, can be used -40 sostearamide and N (primary hydrogenated) tallow isostearamide.

If the bentonite content of the formula given above was modified within the range from 3 to 20%, for example to 10%, 15% and 18%, useful softening and antistatic detergent compositions were obtained. 45 Even if the bentonite content was reduced to 5%, remarkable textile softening was achievable. Similarly, the levels of anionic surfactant can vary in the range of 3.5 to 25%, e.g. B. bring to 5%, 15% and 25%. The total content of builder salt can also be varied in the range from 5 to 40%, e.g. B. 10.20 and 30%, wherein effective softening and antistatic detergent compositions are available. In all of these compositions, water is the rest, with the exception of any excipients present, which normally do not make up more than 55%.

The bentonite used can be replaced by any of the other bentonites mentioned above. Sometimes other source clays such as montmorillonite can be used, but mostly western or Wyoming bentonites are preferred. The sodium (linear) tridecylbenzenesulfonate can be either in whole or in part by sodium (linear) dodecylbenzenesulfonate or other linear higher alkylbenzenesulfonates having 10 to 15 or 18 carbon atoms or other anionic surfactants such as sodium lauiyl sulfate, sodium cetyl sulfate, sodium paraffin 65 sulfonate with about 16 carbon atoms in the paraffin residue, and /

or sodium cocomonoglyceride sulfate or any various mixtures thereof. The ether sulfate can be replaced by other similar surfactants as sodium dodecylpenta-

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ethoxysulfate or other of the above-mentioned anionic surfactants. Instead of polyphosphate, other builders such as those mentioned above can be used to produce phosphate-free detergents.

With the various modifications of the preferred approach according to the invention given above, useful, fabric softening and antistatic detergent compositions are obtained which are superior in the properties described above to formulations which do not contain bentonite and isostearamide and those in which quaternary ammonium salts have been used instead of isostearamide.

Example 2

Instead of producing the complete, textile-softening and antistatic liquid detergent composition of the approach of Example 1, in a modification of the invention, a textile-softening and antistatic composition was prepared, which for the sake of simplicity is referred to as "softening antistatic" and which is bentonite in a liquid, aqueous medium and contains nitrogen (primary, higher) aliphatic substituted isostearamide (CISA). This liquid composition was prepared by merely mixing 14.1 parts of bentonite (American Colloid Company AEG 325 bentonite) and 5.9 parts of N-cocoalkylisostearamide with 80 parts of demineralized water (although tap water is sufficient if one does not have demineralized water). The ratios of bentonite: isostearamide according to Example 1 can also be used. Because of the thickening effect of the swelling bentonite, the powdery N-isostearamide is kept suspended in the aqueous medium. The softening antistatic is ready without further modifications to the formulation and can be filled, shipped, stored, sold and used in bottles. However, a cosolvent such as ethanol or hexylene glycol can be included to accelerate the dissolution of N-isostearamide (and to act as an anti-freeze), in which case a sufficient amount of ethanol or hexylene glycol or both is used to accelerate the dissolution and prevent solidification. About 1% sodium xylene sulfonate can also be incorporated into the formulation as a hydrotrope, with or without 0.1 to 2% sodium polyacylate, in order to disperse and / or suspend the bentonite in the aqueous system. Coloring substances, antioxidants, buffers, gums, agents to prevent re-precipitation (sodium carboxymethyl cellulose), optical brighteners and perfumes can also be introduced into the formulation in customary amounts for auxiliaries, mostly below 2% and often below 1%.

The softening antistatic can be added to another liquid detergent either by the manufacturer or by the consumer in order to improve the fabric softening and antistatic properties thereof. The amount of softening antistatic agent added to the liquid detergent is selected so that sufficient textile softening and antistatic effects are ensured when the improved detergent composition is used. Because of the thinning effect of the softening antistatic, it is generally desirable to use a larger amount of the improved detergent composition. Alternatively, the concentrations of the active components in the softening antistatic can be kept as high as reasonably possible in order to achieve optimal softening and antistatic effects. The liquid softening antistatic can also be added to the washing water in the washing machine directly with the liquid detergent. Any of these application methods can be used to improve any commercially available builder-containing detergents based on anionic surfactants with regard to their textile-softening and antistatic effects. The liquid softening antistatic can according to the invention

8th

can also be used as an agent to impart laundry softening and antistatic properties which have been seen with any particulate or liquid detergent based on nonionic or amphoteric and anionic surfactants. In this way, the invention can be successfully used with all known commercial builder-containing detergent products without the improvement achieved at the expense of cleaning power, brightening or other desired properties of these detergents.

10th

Example 3

A washing amount of the composition according to the approach of Example 1 was used to wash a standard laundry load in a conventional household washing machine (General 15 Electric Toplader). Alternatively, a washing amount (120 g) of liquid detergent composition (similar to the first comparative product, without bentonite and CISA) was added to the wash water, followed by separate additions of the formal amounts of 17.6 g bentonite and 7.4 g 20 N-cocoalcyl isostearamide (which may be dispersed in, dissolved in, or mixed with a suitable liquid medium or particulate carrier, and is preferably in 125 g of a softening antistatic as described in Example 2). The machine was filled with 651 tap water with a hardness of about 100 ppm as calcium carbonate, mixed magnesium and calcium hardness, the calcium hardness being predominant. The wash water had a temperature of 40 ° C, the load of dirty laundry added to the wash water was about 3.6 kg. The washed laundry consisted of 30 cotton, cotton-polyester blend, acetate and polyamide (nylon) and was dirty with normal dirt. The washing was carried out for 10 minutes, after which the laundry was automatically rinsed and spun. It was then dried in an automatic washer, in which it was circulated while hot, drying air flowed through it. After drying, the laundry was assessed by an expert panel. The evaluation found that the wash was sufficiently clean, soft to the touch, and free of inadmissible electrostatic sticking. With a similar (but sole) application 40 of the comparative composition, the formulation of which had no bentonite and no N-substituted isostearamide, for washing similar laundry, the cleaning power was satisfactory, but the laundry felt much harder and showed electrostatic sticking, particularly strongly in laundry items 45 containing synthetic polymer fibers.

Example 4

Instead of using the composition of Example 2 to improve a liquid detergent or adding it to the wash water, it can also be used as a softening and antistatic agent to be added to rinse water. In this embodiment of the invention, the liquid softening antistatic can be added to the rinse water after washing the laundry with a conventional detergent composition. Usually the amount of softening antistatic is sufficient to make the washed laundry noticeably antistatic and soft. For example, the amount added to the rinse water is 0.05 to 0.5%, preferably 0.1 to 0.3%, e.g. B. 0.2%. According to a typical example of this embodiment of the invention, the wash is washed in the manner described in Example 1 with a detergent composition similar to that of the example, except that bentonite and CISA have been replaced by water (optionally with the addition of a small amount of gum or 63 other thickeners to the liquid to regulate the viscosity, for example 0.1 to 1% CMC, PVA (polyvinyl alcohol), PVP (polyvinyl pyrrolidone) or another rubber-like substance known for this purpose). After washing

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673 466

The laundry, which was a normal, mixed fill of cotton and synthetic laundry, was given the softening antistatic composition of Example 2, containing 14.1 parts bentonite and 5.9 parts CISA in 80 parts demineralized water Rinse water added in a concentration of 0.2% (130 g each 65 1 of the 100 ppm hard rinse water). The laundry was then dried, sometimes after repeated rinsing. After drying with the machine, it had a low electrostatic charge and was softer than comparative laundry which was not subjected to the rinsing treatment described.

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Claims (3)

673 466 1. Softening and antistatic liquid composition which is suitable for addition to the rinse water in order to make laundry soft and antistatic, characterized by a content of 1 to 10 parts of isostearamide which is more aliphatically substituted on the nitrogen and 3 to 20 parts of bentonite in an aqueous medium , the ratio of bentonite to isostearamide in the range from 1: 1 to 20: 1. 2. Composition according to claim 1, characterized in that the aqueous medium is water and that the isostearamide on nitrogen is substituted with higher primary alkyl isostearamide. 2nd PATENT CLAIMS 3. Composition according to claim 2, characterized in that it contains about 14 parts of bentonite and about 6 parts of cocoamine-N-alkyl-isostearamide, abbreviated CISA, in about 80 parts of water.