CH673468A5 - - Google Patents

Description

DESCRIPTION

The present invention relates to a liquid, fabric softening and antistatic product for addition to detergent compositions or for washing water.

The liquid, fabric softening and antistatic product to be added to detergent compositions or to the washing water in order to impart laundry softening and antistatic properties to washed laundry is characterized in that it contains a fabric softening amount of bentonite and an antistatic amount of isostearamide which is aliphatically substituted on the nitrogen as an antistatic agent in one contains liquid medium.

The invention relates to a liquid product 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 one can consider it to be somewhat representative of

Soiling of common dirty laundry. With the replacement of soap with 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, especially in the absence of certain inorganic builder salts, was often rough and stiff or boardy becomes and feels uncomfortable. It has been known for years that the addition of bentonite to detergent compositions based on anionic surfactants can help to soften the laundry and can be used to 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 15 are sometimes thickened, particularly when they contain suspending 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.

20 With the advent of synthetic polymeric fibers, clothing and other laundry items made from these fibers and from mixtures thereof with natural fibers such as from cotton / polyester mixtures and with the increasing use of automatic laundry dryers, which are mostly of the tumble dryer type 25 (tumbler), it was found that dried laundry often accumulated electrostatic charges, causing them to stick together in an uncomfortable manner, which disrupted normal handling and folding of the laundry for storage.

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), that is to say to reduce the static charges on textiles and thus avoid electrostatic sticking or sticking. To soften laundry, such halo-35 genides 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 common surfactants used in detergents. This reaction, which would presumably be stronger in liquid detergents than with particulate products, would reduce the cleaning effect of the detergent composition and could form undesirable reaction products that settle on the laundry to be washed and result in dirty or greasy stains. In recent years 45, 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 appreciably with the anionic surfactants during storage, but to a certain extent react with them in the washing water. It has been shown that although these compositions have an antistatic effect and reduce the static sticking of washed laundry,

however, that the cleaning power of the detergents containing them is less than that of the base compositions without the anti-55 static.

1h 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 do not react appreciably with anionic surfactants in the compositions or in the wash water. It is also reported that the isostearamides described can be combined with bentonite and used with particulate detergent compositions and thereby obtain a wash water which has both 65 fabric softening and antistatic properties, so that laundry washed with it is soft and free from impermissible static sticking. The present invention describes in detail liquid detergent compositions that both

3rd

673 468

Bentonite and nitrogen-substituted isostearamide as an antistatic, the desired effects achieved hereby, which includes that the washed laundry is sufficiently soft (especially towels made of woven fabrics or other processed vegetable fibers such as cotton and terry cloth), no or only low static sticking, better cleaning and no "quat stains". What is 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, whereas foam formation is used when using quaternary ammonium salts as anti-statics is reduced, apparently due to the reaction of the quaternary salt with the anionic surfactant. Furthermore, yellowing or similar discoloration of the laundry due to an antistatic agent and the re-precipitation of dirt are reduced in comparison with the results obtained.

when using a quaternary ammonium halide in other builder-containing detergent compositions because of its possible 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 qaternary ammonium salt) and the detergent is a builder-containing composition that contains a builder such as sodium tripolyphophate, 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 of the 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 fatty) 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.

5 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, and mixtures of these surfactants io 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 20 having antistatic properties are contemplated, the desired results reported herein can also be achieved with compositions containing other types of surfactants, often with the anionic surfactants, such as nonionic and amphoteric surfactants. The non-ionic and am-photic substances mentioned are normally only present in small proportions, if at all, generally at most half as much as that of the anionic surfactants is present. Preferred nonionic surfactants are the ethylene oxide condensation products of higher fatty alcohols, e.g. B. the condensation products of 30 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 surfactant builder 35, 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 = 40 1.6 to 3.0, preferably 1: 2.4), NTA, sodium citrate, sodium glu -conate, 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 45 bentonite, thereby producing undesirably thick or coagulated products or precipitates.

If zeolite builders are used, they generally correspond to the formula (Na20) x • (Al203) y ■ w H20, where x is 1, y is 0.8 to 1.2, preferably about 1, z 1.5 to 3 , 5, 50 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 60 particle sizes are in the submicron range. The various zeolites are described in detail by Donald W. Breck in "Zeolite Molecular Sieves", published in 1974 by John Wiley & Sons, particularly on pages 747 to 749.

As polyacetal carboxylates, those according to US Pat. No. 4,659,144,226 can be used and prepared by the process described there. A typical such product has the formula

673 468

4th

R1 ~ (ÇH0) n "R2 COOM

wherein M is from the group consisting of alkali metal, ammonium, alkyl groups with 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 polymer against rapid depolymerization in alkaline solution. The polyacetal carboxylate is preferably one in which M alkali metal, e.g. B. is sodium, n is 20 to 200, R] is mooc /

or H ^ C-CO-

MOOC

or a mixture thereof, R2 for och2ch3

I.

-CH

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 by 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 it is used can be. 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-alkyl isostearamides 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 cocoamines by the following condensation reaction:

O O

«Y. "

rcoh + r'nh? - rcnhr '+ h-0

10th

Isostearic acid, 0

II

rc-oh

/

15

is a saturated fatty acid of the formula C17H35COOH, 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 similar purposes to stearic or oleic acid, it is far superior to these materials for the production of effective antistatic substances suitable for incorporation into detergents. Cocoamine is an aliphatic amine, the aliphatic group of which is derived from coconut oil. Other primary aliphatic 25 amines, preferably higher alkyl amines having up to 7 to 18 carbon atoms in the alkyl such as R'NH2, where R 'is such a higher alkyl, can also be used. However, cocoamine produces an N-alkyl isostearamide with the best properties for incorporation in detergents. His name is CISA.

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 derived from primary amines having up to 20 carbon atoms, preferably 7 to 18 carbon atoms, their aliphatic-35 shear Part can optionally be hydrogenated, provided that the amides show sufficient antistatic activity for the stated purpose. Some examples of these are the N-alkyl isostearamides having 7 to 18 carbon atoms, such as those derived from N-decylamine, N-octylamine and N-tallow amine. However, CISA is considered to be the best N-alkyl isostearamide in terms of its antistatic activity, which is why when other isostearamides are used, they are preferably used with CISA and the amount of the other isostearamide is preferably less than that of CISA. In some cases, the hydrogen can 45 atom of the amide nitrogen may be replaced by appropriate radicals such as lower alkyl, e.g., methyl, provided that a desired antistatic effect is still achieved, but 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 THDCO-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 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 levels of about 8% and specific weights of about 2.6. 85% of the powder quality passes through a 200-mesh sieve (US sieve series). This bentonite is equivalent to the Bentonite clay AEG 325 sold by American Colloid Co., which is essentially a screen size of number 325

CH3CH2?

hco-

I.

h3c

5

673 468

owns.

Enriched Wyoming bentonite is preferred as a component of the detergents. However, other bentonites can also be used, especially if they make up only a small proportion of the bentonite used. It has been found that at least about 2%, preferably at least 4%, and particularly preferably 5% or more to about 8% of 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 becomes. It has been found that overdrying to the point where the bentonite loses its "internal" moisture can affect 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 may be present in the liquid detergents 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 agents and flow promoting substances. Also included in the adjuvants, builders and fillers, unless mentioned in other classes, are various additional components or contaminants that are sometimes present in the components of the compositions. 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 portion and 1 to 15 moles of ethylene oxide per mole, preferably 1 to 5% sodium (higher , primary) alcohol polyethoxy ether sulfate with 12 to 15 carbon atoms in the alcohol and 2 to 4 or 6 moles of ethylene oxide per mole, for. B. about 2%. The liquid detergent builder, which may 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, e.g. about 11% and 4%, respectively. The bentonite component is usually 3 to 20% of the liquid detergent composition, preferably 5 to 20% and particularly preferably about 5 to 15%, for example about 12%, the antistatic isostearamide is usually 1 to 10% of the liquid detergent composition, preferably 1 to 7% and particularly preferably about 3 to 7%, e.g. B. about 5%. The content of water or aqueous medium 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 composition, the various constituents of the end product are usually only mixed with one another or mixed and stirred or otherwise sufficiently agitated 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 a 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, mostly 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 25 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 to accelerate the direct dissolution (if they are soluble) or dispersion in the aqueous medium. In general, the powdered materials are of smaller particle size than the numbers 140 or 200 of the US sieve series, mostly these particle sizes are in the range of numbers 140 to 400, often preferably 200 to 400, e.g. B. at about number 325 of the US sieve series. Easily soluble components such as sodium carbonate, sodium tripolyphosphate and the synthetic organic surfactants can have particle sizes which are in the larger sizes of the given ranges, or even larger ones, in the insoluble or slowly soluble materials such as the zeolites and clays the smaller parts are 40 sizes 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 45, does not stick statically in an inadmissible manner, even if substantial amounts 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 hardness levels 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 main part coming from calcium. The hardness of the water is preferably not greater than 250 ppm. Usually, 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 room temperature-60. According to European practice, the detergents can be washed in washing water at temperatures close to the boiling point, e.g. B. 70 to 90 ° C, are used, whereas according to customary American practice, low temperatures are used. According to American practice 65, 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., for. B. at about 40 ° C. The concentration of the liquid detergent in the wash water can vary depending on the circumstances.

673 468

6

be, but is usually in the range of 0.1 to 0.5, preferably 0.1 to 0.4, and particularly preferably 0.15 to 0.25, z. 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 normal 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 practical limits.

Standard household washing machines and the usual washing programs for these machines or commercial washing machines can be used. The laundry is washed in a normal washing cycle for 2 to 30 minutes, e.g. 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 making a liquid detergent that has all the cleaning, builder effects; contains fabric softening and antistatic components of the composition, a liquid composition can be produced in a variation, which contains fabric softening and antistatic components. Such a composition can be used together with a suitable liquid detergent, such as those in large numbers on the market, 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 fabric softening and antistatic supplement composition, one is able to use the present invention with any liquid detergent formulations and to adapt to 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,

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 isostear amid antistatic which is aliphatically substituted on the nitrogen (primary) does not react appreciably with bentonite nor with the anionic surfactants, which is why compositions are relatively stable during storage and their desired cleaning, softening and antistatic activities during storage or before or during use are not significant to lose. 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 reaction products of these cationic materials with anionic surfactants on the laundry to be washed, so that such a wash during the dirt build-up not so subject to washing when working as specified. The detergent compositions result in whiter laundry and also less redeposition of dirt, whereas laundry that will be seen 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 above-mentioned detergents than when using the above-mentioned detergents than when using those in which a quaternary ammonium salt replaces isostearamide. 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 25 reactions of these “quats” with fluorescent brighteners and the resulting reduced lighting of the laundry when using the antistatic agents according to the invention are avoided.

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 35 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.

40 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 free-flowing from a bottle with a relatively narrow discharge opening 45. It has been found that liquids with viscosities in the range from 1 to 5 Pa.s (1000 to 5000 eps) 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 50 is 3 to 5 Pa.s (3000 to 5000 eps), e.g. B. at about 4 Pa.s

(4000 eps) 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 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 60 components that 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 Celsius.

7

673 468

example 1

component

percent

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

N-cocoalkyl isostearamide

5.0

Optical brightener (Tiponal LMS X [Ciba Geigy])

0.3

Sodium carboxymethyl cellulose

0.2

Titanium dioxide

0.5

Coloring pigment (ultramarine blue)

0.2

Dye (polar brilliant blue, 1% aqueous solution)

0.6

Perfume

0.5

Demineralized water

54.7

100.0

* 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% of the water, 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 the rest of the water admitted The product obtained has a viscosity of about 3000 eps at 25 ° 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 gastric esium ion hardness, 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% RH) 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 (the laundry sticks considerably). When evaluating the softness (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.

5 towels washed in the same manner with the comparative detergent were rated 1.

In other tests, the degree of reprecipitation of dirt on the washed laundry was approximately the same with the product according to the invention as with a second comparative 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 dimethyldisteaiylammonium chloride. 15 The test textiles washed with the product according to the invention do not show any “quat stains” that can sometimes be found on laundry that has been washed with similar formulations which contain dimethyldisteaiylammonium chloride or other quaternary compounds instead of the N-isostearamidanü-20 static. 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 25. 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. 30 When, in the stated formulation of the product of the invention, the 5% N-cocoalkyl isostearamide was replaced by 1%, 3% and 7% of this isostearamide, the softness of the products obtained was 8, 8 and 9 and the static indices were 27.19 and 10. Softness indices of 8 or more are considered sufficient 35, as are static indices of less than 30, whereby softness indices as low as 7 and static indices as high as 35 are sometimes acceptable. If the CISA approach was omitted as in the second comparison product, the washed laundry was rated with a softness of 8 and the index of the 40 electrostatic charge was 36 kilovolts.

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

that the comparative product does not make laundry sufficiently soft and results in higher electrostatic charges such as considerable sticking 45. If bentonite is omitted from the approach according to the invention, as in the fourth comparative product, detergent compositions are obtained which are unsatisfactory both in terms of their plasticizing ability 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% bentonite. It can thus be seen that the combination of bentonite and N (higher) alkylisostearamide is important for the success of the detergent composition according to the invention, since

1. This combination leads to a greater antistatic effect than could have been predicted;

2. the bentonite softens the laundry and

3. Critical consumers today demand both textile-softening and anti-static (anti-sticking) properties.

Instead of the preferred N-cocoalkyl isostearamide, 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-dadecylnostearyl, can be used -isostearamide and N (primary hydrogenated) tallow isostearamide.

673 468

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.

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 10%.

The bentonite used can be replaced by any of the other bentonites mentioned above. Sometimes other swelling 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 with 10 to 15 or 18 carbon atoms or other anionic surfactants such as sodium lauryl sulfate, sodium cetyl sulfate, sodium paraffin sulfonate with about 16 carbon atoms Paraffin residue and / or sodium cocomonoglyceride sulfate or any various mixtures thereof can be replaced. The ether sulfate can be replaced by other similar surfactants such as sodium dodecylpenta-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 simply mixing 14.1 parts bentonite (American Colloid Company AEG 325 bentonite) and 5.9 parts N-cocoalkylisostearamide with 80 parts demineralized water (although tap water is sufficient if you do not have demineralized water) . The ratios of bentonite to 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 approach and can be filled, shipped, stored, sold and used in bottles. However, a cosolvent such as ethanol or hexylene glycol can be incorporated to accelerate the dissolution of N-isostearamide (and to serve 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 as hydrotrope in the formulation, with or without 0.1 to

2% sodium polyacrylate to disperse and / or suspend the bentonite in the aqueous system. Coloring substances, antioxidants, buffers, gums, agents to prevent reprecipitation (sodium carboxymethyl-5 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 textile-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 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 25 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. According to the invention, the liquid softening antistatic can also be used as an agent for imparting softening and antistatic properties to laundry which has been washed 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.

Example 3

40 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 Electric Toplader). Alternatively, a washing amount (120 g) of liquid detergent composition (similar to 45 the first comparative product, without bentonite and (CISA)) was added to the washing water, followed by separate additions of the formal amounts of 17.6 g bentonite and 7.4 g N-cocoalkyl 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 run with 651 tap water of a hardness of about 100 ppm, as calcium carbonate, mixed magnesium and calcium hardness, the calcium hardness being above 55. The wash water had a temperature of 40 ° C., the load of dirty laundry added to the wash water was about 3.6 kg made of cotton, cotton-polyester blend, acetate and polyamide (nylon) and was contaminated with normal dirt nt. 60 was washing 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 judged by an expert panel. The evaluation showed that the laundry was sufficiently clean, soft to the touch and free of inadmissible electrostatic sticking. With a similar (but sole) application of the comparative composition, the formulation of which none

9

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Bentonite and no N-substituted isostearamide had, the cleaning power was satisfactory for washing similar laundry, but the laundry felt much harder and showed electrostatic sticking, particularly strongly in laundry items 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. 0.2%. According to a typical example of this embodiment of the invention, the laundry is washed in the manner described in Example 1 with a detergent composition similar to that of the example, with the exception that bentonite and CISA have been replaced by water (optionally with a small amount of rubber added) or other thickener 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 the laundry, which was a normal, mixed fill of cotton and synthetic laundry, the softening antistatic composition of Example 2 demineralized 14.1 parts bentonite and 5.9 parts CISA in 80 parts Water contained, added to the rinse water in a concentration of 0.2% 15 (130 g each 651 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.

20th

Claims (6)

673 468 2nd PATENT CLAIMS 1. Liquid, fabric softening and antistatic product to be added to detergent compositions or to the washing water in order to impart washed fabric softening and antistatic properties, characterized in that it contains a fabric softening amount of bentonite and an antistatic amount of isostearamide which is more aliphatically substituted on the nitrogen as an antistatic in contains a liquid medium. 2. Product according to claim 1, characterized in that the bentonite is a swelling bentonite, that the antistatic is N (higher) alkyl isostearamide, that the liquid medium is an aqueous medium and that the ratio of isostearamide to bentonite is in the range of 1: 1.5 to 1: 5. 3. Product according to claim 2, characterized in that the bentonite is a Western or Wyoming bentonite, that the isostearamide is cocoamine-N-alkyl-isostearamide, abbreviated CISA, and that the total amount of isostearamide and bentonite is in the range from 10 to 30% lies. 4. A process for the commercial treatment of laundry to soften and reduce its capacity to generate and / or maintain electrical charge, characterized in that the laundry is treated with a composition that a fabric softening amount of bentonite and an antistatic amount of nitrogen higher contains aliphatically substituted isostearamide. 5. The method according to claim 4, characterized in that the treatment is carried out in a rinsing process after washing the laundry and that the bentonite and the isostearamide which is more aliphatically substituted on the nitrogen are present in a liquid composition. 6. The method according to claim 5, characterized in that the liquid composition contains about 1 to 10% of isostearamide which is more aliphatically substituted on the nitrogen, about 3 to 20% bentonite and about 30 to 80% of water, that the isostearamide which is more aliphatically substituted on the nitrogen contains cocoamine -N-alkyl-isostearamide, abbreviated to CISA, and that the amount of the liquid composition in the rinse water is 0.05 to 0.5%.