CH670652A5 - - Google Patents

Description

DESCRIPTION

The invention relates to detergent compositions as defined in claim 1. The invention also relates to methods for producing these compositions and for washing soiled and / or stained fiber-containing materials in order to clean them and to prevent electrostatic “sticking” of the materials.

The need to remove dirt and stains from fiber materials has existed since time immemorial. Many compositions have been described to achieve this goal. While in the past, soap was used extensively for this purpose, today almost only household detergents based on one or more synthetic organic surfactants are used. Of these surfactants, the most effective are the anionic and the nonionic, the most common being the anionic. Ampholytic, amphoteric, zwitterionic and cationic surfactants have also been used, but with less success. Cationic compounds can act as antistatic substances or antistatic agents to prevent electrostatic adhesion of washed articles made of synthetic organic polymers, e.g. To reduce plastics from nylon, polyesters, acyl compounds and mixtures of such materials with cotton, each other and on other polymer fibers. In US SN 400 794, antistatic agents for detergent compositions based on anionic surfactants on nitrogen with alkyl-substituted isostearamides have been proposed since, unlike the cationic compounds hitherto used for this purpose, they do not significantly impair the cleaning ability of these anionic surfactant compositions. Recently, polyacetal carboxylate builders have been used in detergent compositions in place of polyphosphate builders because they are phosphorus-free and therefore should not contribute to eutrophication of inland waters. Another plus of these builders is their easy degradability in normally acidic wastewater. Zeolites and other builders, both water-soluble and water-insoluble, and organic and inorganic, have served for years to improve the cleaning ability of synthetic organic surfactants. Phosphate-free, builder-containing detergent compositions which do not have an eutrophic effect are also known.

Thus, although the essential components of the detergents according to the invention have already been used in other detergents, the products of the invention are new, not obvious, valuable and have a surprisingly good ability to remove dirt and stains. Of particular importance is the considerably improved capacity of the detergents according to the invention, in particular of the phosphate-free compositions, to remove many common and difficult-to-remove stains and soiling from textiles, and to impart the latter with antistatic properties during washing in the washing machine, which subsequently adhere the washed materials to one another prevent drying in the machine.

The object of the invention is to provide an improved antistatic, builder-containing, particulate washing fluid composition.

To achieve the object, a composition is proposed which contains a cleaning amount of a surfactant, preferably an anionic surfactant or a mixture of such surfactants, an amount of polyacetal carboxylate builder or a mixture of this polyacetal carboxylate builder with zeolite builder, and an antistatic amount of antistatic amide as described in Claim 1 is defined, for example N-Koko-sostearamide (CISA). Preferred compositions of this type contain about 5 to 30% sodium (linear, higher res) alkylbenzenesulfonate having 12 to 14 carbon atoms in the higher alkyl group, about 5 to 40% sodium polyacetal carboxylate builder of a calculated weight average molecular weight in the range of 3500 up to 10,000 or a mixture of this builder with zeolite A builder, about 2 to 20% CISA, about 2 to 20% moisture and the remainder optionally filler (s) and / or other builder and / or other auxiliary or other auxiliary substances . Methods are also proposed for making these compositions and removing dirt and stains from fiber materials by washing these materials in water containing such detergent composition or components thereof.

The preferred anionic surfactant is normally sulfated and / or sulfonated lipophilic material with alkyl chains of 8 to 20, preferably 10 to 18 and particularly preferably 12 to 16 carbon atoms. 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 commonly used, with sodium being particularly preferred as the cation. Among the various anionic surfactants suitable for the invention, 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 are highly suitable. Among others, the monoglyceride sulfates, higher fatty alcohol sulfates, sulfated polyethoxylated higher synthetic or natural alkanols with 3 to 20 or 30 ethoxy groups per mole, paraffin sulfonates and olefin sulfonates are also valuable, the alkyl group present in all these compounds having 10 to 18 carbon atoms. Some of these alkyl groups can be somewhat branched, but are said to have a carbon chain with a length in the range described.

Although the linear higher alkyl sulfonates than sodium salts are the preferred anionic surfactants for practicing the invention, mixtures of these surfactants with other linear higher alkyl benzene sulfonates with other cations can be used, as well as mixtures of these surfactants with others, e.g. the fatty alcohol sulfates and sulfated polyethoxylated higher alkanols. In some cases, only minor amounts of linear alkylbenzenesulfonates are present or the anionic surfactant can be a mixture of the other anionic surfactants described. Other anionic surfactants such as those in various yearbooks, e.g. McCutcheon's Detergents and Emulsifiers, 1969, can also be used.

Although the invention preferably relates to antistatic detergents based on anionic surfactants, the desired results according to the invention can also be achieved with compositions which contain other surfactants with the anionic, such as nonionic and amphoteric surfactants. In some cases, cationic substances like that

Di (higher) alkyldi (lower) alkylammonium halides, ditallow dimethylammonium chloride, other quaternary ammonium halides and other cationic substances may be present, primarily for fabric softening (although it is often preferred, for this purpose, bentonite or other fabric softening clays, sometimes with additional cationic plasticizer). The non-ionic, amp-

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Hotter and cationic substances are usually present, if at all, only in small proportions, mostly only at most half the amount of anionic surfactant. Preferred nonionic surfactants are the ethylene oxide condensation products of higher fatty alcohols such as 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 polyacetal carboxylates used correspond to those described in US Pat. No. 4,144,226 and can be prepared by the process specified there. A typical product has the formula

El - <CHO) n - R2 COOM

wherein M from the group consisting of alkali metal, ammonium, alkyl groups with 1 to 4 carbon atoms, tetraalkylammonium and alkanolamine groups with 1 to 4 carbon atoms in the alkylene, n is on average at least 4 and Ri and R2 are chemically stable groups which are the polymer stabilize against rapid depolymerization in alkaline solution. Preferred is a polyacetal carboxylate in which M alkali metal, e.g. Is sodium, n means 20 to 200, Ri for

CH3CH2O MOOC

HCO- or H ~ C-C0-

I 3 I

H3C MOOC

or a mixture thereof, R2

och2ch3

-CH

represents and n is on average 20 to 100, preferably 30 to 80. the calculated weight average molecular weights of the polymers are normally in the range 2000 to 20,000, preferably 3500 to 10,000 and particularly preferably 5000 to 9000, e.g. about 8000.

Builders other than the polyacetal carboxylate and the zeolite may also be present in the compositions of the invention, although they are not necessary. It is usually desirable to avoid the presence of phosphorus in the detergent, which means that the polyphosphates which have been the builders of choice for years (in particular pentasodium tripolyphosphate) are preferably omitted from the formulations according to the invention. In some cases, however, they can be present in relatively small amounts, e.g. up to 5 or 10%. Builders other than polyphosphates such as sodium tripolyphosphate and tetrasodium pyrophosphate and other than the above-mentioned polyacetal carboxylates and zeolites, the incorporation of which into the detergents of the invention may be desirable to supplement the builder action of the polyacetal carboxylate, are, for example, sodium carbonate, sodium bicarbonate, sodium ses-quicarbonate, sodium silicate, sodium silicate , Sodium citrate, sodium gluconate, borax, other borates and other builders known in the detergent sector. If it appears appropriate to increase the mass or volume of the product, fillers such as sodium sulfate and sodium chloride can be added, also for other purposes. Particularly effective builders along with the

Polyacetal carboxylates of the invention are the zeolites as stated above, mostly sodium sulfate is preferred as filler.

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

O O

M / \ "H

RCOH + R'NH2 - RCNHR1 + HjO

The polyacetal carboxylates described above are preferred, but they can also be used in whole or in part by other such polyacetal carboxylates or related organic builder salts as described in various Monsanto patents including methods of making them and compositions using the same. The chain end groups described in the Monsanto patents, particularly US Pat. No. 4,144,226, can also be used, provided that they have the desired stabilizing properties that allow the builders mentioned to decompose in acidic media to facilitate their biodegradation in wastewater However, maintain stability in alkaline media such as washing solutions.

The zeolite component generally corresponds to the formula (Na20) x- (Al203) y- (SÌO2) • w H2O, where x = 1, y is 0.8 to 1.2, preferably about 1, z 1.5 to 3 , 5, preferably 2 to 3 or about 2 and w is 0 to 9, preferably 2.5 to 6. These zeolites are cation exchangers and have an exchange capacity for calcium ions in the range from about 200 to 400 or more milligram equivalents of calcium carbonate hardness per g. They are often from 5 to 30%, preferably 10 to 25%, e.g. 20% of them hydrated. Zeolite A is preferred (X and Y are also valuable), Type 4 A zeolite is most preferred. The particle sizes of the zeolites are usually 149 to 37 µm (100 to 400 mesh), preferably 105 or 74 to 37 (in (140 or 200 to 325 mesh), with limits in the submicron range. The various zeolites are described in detail in "Zeolite Molecular Sieves" , by Donald W. Breck, published in 1974 by John Wiley & Sons, particularly pages 747 to 749.

Isostearic acid, RCO-OH, is a saturated fatty acid of the formula C17H35COOH, namely a complex mixture of especially the isomers containing methyl groups, which are mutually soluble and factually inseparable. Although this acid is generally used for purposes similar to stearic or oleic acids, it is far superior to these materials in the preparation of effective antistatic substances suitable according to the invention. Cocoamine is an aliphatic amine in which the aliphatic group is derived from coconut oil. Other primary aliphatic amines, preferably higher alkylamines having 7 to 18 carbon atoms in alkyl, such as R'NH; where R 'is such a higher alkyl, can also be used, but cocoamine forms an isostearamide with the best properties for incorporation into those of the invention Compositions.

Although CISA is the most preferred antistatic substance, other isostearamides which are aliphatic substituted on the nitrogen, such as those derived from primary aliphatic amines having 7 to 18 carbon atoms, the aliphatic parts of which are hydrogenated or not hydrogenated, can also be used within the scope of the invention can be, provided the antistatic effect of the amides is sufficient. Some examples are the N-alkylisostearamides derived from N-tallow amine, N-decylamine and N-octylamine. However, since N-alkylisostearamides other than CISA show an inferior antistatic effect compared to CISA, these substances are, if at all, pre-5

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preferably used only in smaller amounts with respect to CISA. In some cases the hydrogen atom on the amide nitrogen can be substituted by suitable radicals such as lower alkyl, e.g. Methyl, provided that a desired antistatic effect is still ensured, but it has been found that the tertiary isostearamides mostly have a low antistatic effect.

Coloring substances such as dyes and pigments, fragrances, enzymes, stabilizers, activators, fluorescent brighteners, bleaching agents, buffers, fungicides, germicides, agents which prevent foam formation and substances which promote flowability can optionally be present as auxiliaries. The auxiliary substances, builders and fillers, if they fall into the specified classes, can also include various additional constituents or impurities of the components of the compositions. For example, it is known that sodium carbonate and water are often present in Builder U with polyacetal carboxylate, which according to the invention serves as a supplier of polyacetal carboxylate.

In general, moisture is present in the compositions of the invention, either as free moisture or in one or more hydrates. Moisture is not an integral part of the solid detergent compositions of the invention, but is usually present due to the use of water in the manufacture and can help to solubilize the components and bind them together.

The proportions given below for the compositions according to the invention relate to particulate products which generally have particle sizes in the 2380 or 2000 to 149 or 105 micrometers (8 or 10 to 100 or 140 mesh) range. These proportions also apply to other solid shapes such as sticks or cakes, fine or coarse powders, granulated compositions and agglomerates. They can also be used for liquid, gel-like and pasty preparations. With the exception of water, the ratios between component pairs in liquid, gel-like and pasty preparations can be approximately the same as in solid. However, since the liquid products are often more dilute, the proportion of water or another solvent or mixture of solvents present is usually much larger. If the components of the product of the invention are added directly to the washing water, the washing water containing the various active and other ingredients can be considered the "detergent composition".

In the particulate and other solid detergent compositions according to the invention the total amount of surfactant is usually 5 to 40, preferably 5 to 30, particularly preferably 10 to 25 and most preferably 13 to 23, e.g. about 18%. This surfactant is usually an anionic surfactant and of these the higher alkylbenzenesulfonates are preferred, e.g. Sodium (linear) tridecylbenzenesulfonate. However, this can be present with other anionic surfactants or can be partially or completely replaced by one or more other anionic surfactants. The proportion of polyacetal carboxylate builder is usually 5 to 50, preferably 5 to 40, particularly preferably 12 to 30, most preferably 13 to 26, e.g. about 17% if it is the only builder or if up to 50% of builders other than zeolite, e.g. 15 to 40% are also present. When using zeolite, the sum of polyacetal carboxylate and zeolite corresponds to the proportion previously given for polyacetal carboxylate alone. If zeolite is present, the polyacetal carboxylate makes up at least 4% of the detergent composition. Furthermore, the ratio of polyacetal carboxylate to zeolite is in the range of 1: 2 to 4: 1, preferably 1: 2 to 3: 1, and more preferably about 2: 3 to 3: 2, e.g. about 1: 1. The CISA antistatic, which also has textile softening properties, is present in the compositions according to the invention in an antistatic amount, so that it significantly reduces static charge, at least in the case of certain synthetic fibers and fabrics. The detergents according to the invention have proven to be particularly effective in reducing electrical charges (and, accordingly, electrostatic adhesion) to polymeric materials, but they reduce these undesirable effects which occur when drying with the machine, even with substances made from natural fibers and from mixtures of natural and syn -io thetic fibers. The proportion of antistatic is usually in the range from 2 to 20, preferably 3 to 15, particularly preferably 4 to 13, e.g. at about 9%.

The percentage of moisture is generally 2 to 20, preferably 3 to 15, particularly preferably 4 to 12, e.g. about 15 5 or 6%. These percentages include the hydrate moisture released at 2 hours while heating to 105 ° C (the standard method for analyzing moisture). The amounts of filler are normally limited to no more than 50% and are often in the range 5 to 40, preferably 20 to 15 to 35, e.g. at about 25%. The content of phosphate-free builders other than polyacetal carboxylate and zeolite builders is limited and is generally less than 40% e.g. 3 to 30 or 5 to 25%. Such complementary builders are not necessary, but their presence, often with filler, is often desirable. Like sodium silicate, it is a preferred phosphate-free builder. Preferred silicates are the sodium salts, the Na20: SiO2 ratio in the range from 1: 1.6 to 1: 3.0, preferably 1: 2.0 to 1: 2.6, e.g. is 1: 2.4. The proportions of optionally present carbonate 30 and silicate can be 3 to 25%, preferably 8 to 20%, particularly preferably 10 to 18% for the carbonate and 2 to 15%, preferably 5 to 10% and particularly preferably 6 to 9% for the Amount of silicate.

The total content of auxiliaries or additives generally does not exceed 10 or 20% and is preferably less than 5%, the content of customary individual auxiliaries generally not exceeding 3 or 5% and frequently preferably below 1 or 2%. For example, the amount of sodium carboxymethylcellulose, if any, which is a desirable anti-redeposition agent, generally increases 0.3 to 3%, preferably 0.5 to 2%. 1% of the composition.

In the preferred embodiments of the invention, the particulate solid compositions of the particle sizes listed above, it is often preferred to spray dry as much of the formulation as possible to obtain substantially uniformly shaped spherical particles. The antistatic can be added to the rest of the composition subsequently, for example by spray coating it in liquid form on 50 circulating spray-dried detergent base grains. In order to prevent separation of the end product during shipping and storage, it is advantageous that components added later, such as enzyme, bleach, bento-nit (if not spray-dried) and polyacetal carboxylate (if 53 not spray-dried), in terms of shape, particle sizes and bulk density of the remaining composition correspond. However, even if this is not the case, and if the substances subsequently added are in finely divided form, for example in particle sizes in the range from 94 to 44 micrometers (160 60 to 325 mesh) and with a higher bulk density, they can subsequently be spray-dried beads or others Particles of the larger detergent base detergent composition are added and often adhere to them, creating a desired product in the 2000 to 149 micro-65 meter (10 to 100 mesh) range. The polyacetal carboxylate can be spray dried with the detergent composition if it is prevented from being decomposed by the heat. Alternatively, the various components in

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finely divided form can be mixed together. Even if the initial particle sizes of the various components or some of them are smaller than desired, for example in the 94 to 44 micron (160 to 325 mesh) range, these particles can be agglomerated to the desired size, sometimes with the aid of agglomerating agents such as a diluted one aqueous sodium silicate solution or only with water. Such agglomeration can only take place with the undersized particles, or one agglomerates these particles with the larger spray-dried beads or with larger particles of the constituents of the composition or mixtures of these constituents.

The anionic surfactant or mixture of these surfactants, which are the main surfactants of the desired compositions, can be mixed with fillers such as sodium sulfate, builders such as sodium carbonate, sodium bicarbonate, borax and sodium silicate and auxiliaries such as fluorescent brighteners, pigments and dyes in a manner known per se using a countercurrent. or direct current spray drying tower, the drying air entering at temperatures of about 200 to 600 ° C (preferably 150 to 300 or 350 ° C in the presence of polyacetal carboxylate). Then the polyacetal carboxylate and antistatic can be admixed, either sequentially or together, or the antistatic and polyacetal carboxylate can be premixed and then sprayed or dripped or mixed with spray-dried granules, or the antistatic alone can be sprayed or mixed with the beads when the polyacetal carboxylate is in the spray-dried base grains. In certain cases, the polyacetal carboxylate and / or the antistatic can be spray dried with other components that are sufficiently stable to withstand the spray drying conditions used, which are preferably mild. However, often the operations in the crutcher and spray drying reduce the antistatic activity of the isostearamide, which is why it is preferred that polyacetal carboxylate and / or the CISA be added subsequently, often by layering on the particulate components of the composition or on the spray-dried base beads . When CISA is layered on a component of the product such as borax beads, agglomerated zeolite, microcel C (a synthetic calcium silicate) or betonite to mix or agglomerate, the flowable product obtained is readily miscible with the spray dried beads to form the finished product.

If a relatively small amount of nonionic surfactant is to be present with the anionic surfactant, it can be spray dried with this anionic surfactant, fillers and other stable materials. However, if more than about 4 or 5% (sometimes more than 2%) of nonionic surfactant is to be present in the final formulation, any additional amount is added subsequently, for example by spraying on circulating detergent granules with or without CISA and / or polyacetal carboxylate and any other suitable ones Liquids like perfume, although perfume is usually applied last. In some cases, the polyacetal carboxylate can be dispersed and / or dissolved in the nonionic surfactant to be subsequently sprayed onto the base beads, the nonionic surfactant being heated or dissolved in a solvent so that it is in a liquid state. The combination of nonionic surfactant and polyacetal carboxylate can be sprayed onto detergent granules or base granules, after which the antistatic agent is added, preferably by spray coating the spray-dried detergent beads. It is desirable that the particulate material have particle sizes in the 2380 to 125 or 2000 to 149 micron (8 to 120 or 10 to 100 mesh) range, the manufacturing process is controlled accordingly. However, one can sieve to remove undersize and oversize particles and these particles can be reworked, ground, agglomerated, or otherwise processed to the desired sizes (sometimes 2380 to 177 microns corresponding to 8 to 80 mesh). The bulk densities of the spray dried granules and finished beads are usually in the range of about 0.2 to 0.6 g / ml, preferably 0.25 to 0.5 g / ml, e.g. about 0.3 or 0.4 g / ml.

To produce the products according to the invention in the form of bars, cakes or briquettes, the compositions can be extruded or pressed or shaped in a manner known per se. In order to convert them into liquid, gel-like or pasty preparations, the constituents can be dissolved and / or dispersed in liquid media such as water and / or suitable solvents such as ethanol, glycerol and / or isopropanol, wherein a gelling agent can be used. Occasionally, it is necessary to avoid dissolving CISA or similar isostearamide in alcohol or a similar solvent, as these sometimes reduce the antistatic effect of the same.

20 In order to remove dirt and stains, and to keep the washed textiles non-sticky, clean and with improved softness, one of the compositions described or the various constituents can be added to washing water. The concentrations of the compositions used are usually in the range of 0.05 or 0.1 to 0.4 or 0.5, preferably 0.1 to 0.35, and particularly preferably 0.1 to 0.2% of the wash water . Higher concentrations such as 0.25 to 0.45% or more (and less wash water) are often used in washing machines of European construction and 3o mode of operation, the wash water temperature being generally higher. In America, lower levels of detergent compositions are typically used, such as 0.05 to 0.25, preferably about 0.1 to 0.2%. Usually the washing temperature in America is 10 to 55 ° C. 35 While the higher temperatures in this range, such as 35 to 55 ° C, are best for cleaning, the lower temperatures, such as 10 to 35 and 15 to 25 ° C, are more sensitive to washing Best fabrics and some dyed fabrics as well as for energy saving reasons. Good cleaning at these 40 lower temperatures is therefore important. The compositions of the invention are valuable for removing dirt and stains from laundry of various types of fabric, giving charge-free laundry with improved softness, even when washing at low temperature.

45 For washing in a normal household or commercial washing machine, detergent is used in the desired amount according to the specified areas, e.g. 0.15% (100 g per 65 liters of wash water) added to the wash water, the normal wash temperature, e.g. 21 ° C and normal hardness (about 50 to 250 ppm, 50 as calcium carbonate, e.g. 150 ppm). Then the laundry is weighed in the usual amount, e.g. 2.7 to 4.5 kg, e.g. 3.6 kg added. Washing the laundry in a normal program requires 2 minutes to 30 minutes, e.g. 5 to 20 minutes, e.g. about 10 minutes, depending on the soiling 55 of the laundry. Surprisingly, the compositions of the invention at 41 ° C are about the same as a comparative composition (from which CISA has been omitted) in terms of washing power in medium hard water (about 150 ppm), but considerably better at lower temperatures, e.g. 15 to 25 ° C 60 this comparative composition. In these comparative compositions, polyacetal carboxylate or zeolite plus polyacetal carboxylate is replaced by an equal amount of sodium tripolyphosphate. Also, terry towels washed with the detergent of the invention (which contains polyacetal carboxylate, zeolite and CISA-85) appear to be softer than those washed with a comparative product without CISA (in which polyacetal carboxylate and zeolite are replaced by an equal weight of sodium polyphosphate). This shows that the together

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composition of the invention is clearly superior with regard to the properties of non-sticking, in particular with acyl substances.

The advantages of the invention are significant. The use of CISA permits the production of antistatic, phosphate-free or essentially phosphate-free detergents with a cleaning action which is essentially as good as that of the detergents containing phosphate. Unlike the detergents now on the market that contain polyphosphate builders and quaternary ammonium halide as an antistatic (and plasticizer), in which the quaternary ammonium halide reacts with the anionic surfactant and thereby reduces its cleaning power, CISA does not impair the anionic surfactant (or the phosphate) . Thus, by using CISA in detergent compositions containing polyacetal carboxylate builders or a mixture of polyacetal carboxylate and zeolite builders, generally as the main builder, an antistatic phosphate-free detergent composition can be prepared, the cleaning power of which is the same as that of a product without a CISA in which the main builder consists a similar amount of pentasodium tripolyphosphate or another sodium polyphosphate (equal to the total amount of polyacetal carboxylate present and water softening or cation exchange zeolite). The antistatic activity of the compositions according to the invention is comparable to that of plasticizers which are added in the rinse cycle. In addition, the compositions according to the invention make the laundry washed with them noticeably soft. With various washing tests, i.a. The following important results were found:

1. In a test in a washing machine, in which an anionic detergent composition based on polyacetal carboxylate and zeolite builders with 9% CISA was used, the cleaning effect was as good as with a comparative detergent without CISA, in which sodium tripolyphosphate the builder mixture of polyacetal carboxylate and Zeolite replaced. It also cleaned significantly better than such a comparative detergent containing phosphate builder containing 5% disteaiyldimethylammonium chloride, with the assumption that the use of 9% disteaiyldimethylammonium chloride would worsen the detergency of such a comparative detergent even more.

2. In Tergotometer tests, the compositions according to the invention were the same or better than comparison compositions with polyphosphate as a builder, which were used for washing in cold water of medium hardness (normal washing conditions).

3. The compositions of the invention are far superior to comparative compositions in controlling electrostatic behavior, especially for double-faced polyester fabrics and those made from polyester-cotton blends. The compositions according to the invention also regulate the static behavior when washing goods made from polyester-cotton blends better than comparative compositions containing 5% quaternary ammonium halide. The non-phosphate-containing compositions of the invention containing CISA are significantly better than similar compositions in which polyphosphate builders take the place of the polyacetal-carboxylate-zeolite mixture in terms of limiting static charges to acyl materials.

4. The phosphate-free compositions of the invention make washed cotton / polyester blend towels considerably softer than a builder-containing detergent composition without CISA.

The following examples are intended to illustrate the invention. Unless otherwise stated, all parts in the examples, the description and the claims are weight-related and all temperatures are measured in ° C.

example 1

Part of percent

Sodium (linear) tridecyl

benzenesulfonate 18.2 Builder U (79.7% sodium polyacetal carboxylate, from Monsanto Co. Lot No. 2538422, calculated weight average

MW of about 8030) 10.9

Zeolite 4A (20% hydrated) 10.9

Sodium carbonate (anhydrous) 12.7

Sodium silicate (Na20: SiO2 = 1: 2.4) 7.3

Sodium sulfate (anhydrous) 25.4

CISA (N-cocosisostearamide) 9.1

Humidity 5.5

100.0

To produce particulate spray-dried detergent pellets, an aqueous crutch mixture (solids concentration 55%) was prepared from all of the above ingredients except for CISA at a temperature of about 50% and spray dried under mild conditions, being careful not to cause the polyacetal carboxylate to separate decomposed and the walls of the spray drying tower were kept as clean as possible during the spray drying. A countercurrent tower operating under mild conditions was used as the spray drying tower, in which the drying air had an inlet temperature of about 220 ° C. and further precautions were taken to avoid scorching of the beads and decomposition of the polyacetal carboxylate (by preventing "build-up" ( buildup) on the tower walls, application of cooling air and / or controlled spraying so that the spray does not come into contact with the tower walls).

The product obtained had particle sizes in the range of 2000 to 149 microns (# 10 to 100 US sieve series), a bulk density of about 0.3 g / ml and a moisture content of about 6%. 10 parts of the detergent composition thus prepared were sprayed with 1 part of CISA in liquid form so that the CISA enveloped the particles. The temperature at which CISA was applied was typically about 5 ° C above its melting point or 5 ° C above the highest part of a solid to liquid transition region. This temperature was used so that CISA solidifies quickly when it comes into contact with the cooler detergent particles, usually at about room temperature (but they can also be at higher temperatures), without the spray-dried beads agglomerating into undesirably large aggregates. Alternatively, the CISA present in the desired particle sizes in the range of 2000 to 149 microns (numbers 10 to 100 U.S. sieves) can be mixed with the spray dried particles. Even though it is in a finer powder form, such as in particle sizes in the range of 149 to 44 micrometers (100 to 325 mesh), the antistatic can be well distributed "through" or into the detergent composition and normally adheres sufficiently to the particles thereof, taking one Obtains product that is in the desired sizes and bulk density, generally in the range of 0.3 to 0.4 g / ml as well as the coated product.

The manufactured coated product was tested for its ability to remove dirt and hedges using a tergotometer washing machine (laboratory type), in which standard samples of various materials, which were soiled and stained in a standardized manner, were used in water of 150 ppm hardness for 10 minutes Calcium carbonate, using a detergent concentration of 0.15%

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on the wash water, washed at a temperature of 21 ° C. The water hardness was a mixed calcium and magnesium hardness in a 3: 2 Ca: Mg ratio. The reflectance or reflectivity of various washed and dried material samples with different stains on them were measured according to a standard test for the hedge distance index (SRI) and the indices or “indicative indices” of the weighted sums of the reflectivity were calculated. These experience-based indexes are a measure of a tested detergent composition's ability to remove dirt and stains, the higher the index, the better the detergency. Similar compositions were made which maintained the total amount of 21.8% polyacetal carboxylate and zeolite, but the weight ratio of polyacetal carboxylate to zeolite was changed to 3: 2 and 2: 1, respectively. The soil removal indices (SRI) obtained were +6, +12 and + 9, respectively, compared to a comparison detergent composition of the same formulation as the basic detergent (without CISA), in which polyacetal carboxylate and zeolite were replaced by sodium tripolyphosphate. When the same tests were repeated, with the only change being the wash water temperature, 41 ° C., indices of 0.4 and 3 were found, respectively. It was found that the observed index differences when washing at 21 ° C. were significant and show that the compositions according to the invention are superior to the comparison composition in terms of dirt and hedge removal at such lower temperatures.

In other experiments described below, detergent systems were used to wash two 36 cm x 36 cm sample pieces of the following compositions: 5 polyester-cotton blend; Acetate; Aciyl; and double-faced polyester. The detergent systems used were a) 100 g anionic surfactant containing 24% polyphosphate builder without CISA (base beads [BB]; b) 100 g polyphosphate BB plus 10 g CISA (CISA layered on BB); c) BB containing 100 g 12% polyacetal-lo carboxylate plus 12% zeolite (instead of 24% polyphosphate) plus 10 g CISA (CISA layered on spray-dried product); d) 100 g polyphosphate BB plus rinse cycle softener (with Downy fabric softener); and e) 100 g polyphosphate BB plus 5 g dimethyldisteaiylammonium chloride. 15 The specified amounts of detergent were used to wash test substances in 60 liters of water with a hardness of 150 ppm in a General Elektric Company washing machine at 43 ° C. for 10 minutes. The electrostatic measurements were carried out by measuring the electrostatic charge which was generated by the long, controlled rubbing of the respective test substances against a woolly test pattern for 5 seconds. The measurements of the electrostatic charge were carried out with an electrostatic voltmeter under controlled environmental conditions (constant temperature and low humidity). The following 25 table shows the measured electrical charges after drying with the machine.

Table 1

Read electrostatic charge (kilovolts)

Detergent system

Polyester tree acetate wool

mixture

Acrylic double total area

Polyester a) 12.0 5.0

b) 0.6 4.0

c) 0.8 4.0

d) 4.7 4.0

e) 8.5 0.8

The table above shows that the compositions of the invention c) provide results that are comparable in electrostatic to a rinse cycle softener. In this respect, the composition c) according to the invention is also significantly better than the composition b), the difference in the electrostatic charge being greatest in the case of acyl substances. Furthermore, the electrostatic charge on polyester / cotton fabrics after washing with the compositions according to the invention is much lower than after washing with a detergent containing polyphosphate plus quaternary ammonium halide. When interpreting the above data, larger charge differences than 4 kilovolts are considered significant.

The cleaning power was also tested with the wash liquors in which the above detergent compositions were applied and / or carried out. A set of SRI standard samples was placed in each wash, the reflectance of which was read after washing. In each set of samples, there were 4 samples of nylon, cotton, Piscataway (NJ) clay on cotton, Piscataway clay on a cotton / dacrone blend, and EMPA 101. The highest reading was achieved with the composition of the invention containing polyacetal carboxylate, zeolite and CISA, all the other treatments were essentially the same except for treatment e), which was significantly worse.

Terry towels in the same washing water as that

18.0 10.2 45.2

15.0 1.8 21.4

9.8 1.5 16.2

4.5 0.7 13.9

2.1 0.9 12.3

Test samples were washed were softer when washing with the composition c) according to the invention than when washing 45 with a comparison composition a) without CISA, in which sodium tripolyphosphate was the builder.

This example shows that the heavy-duty detergents of the invention containing CISA, polyacetal carboxylate and zeolite A, which have no phosphate but have anionic surfactant with carbonate and silica-50 cat as a builder, have a cleaning power similar to that of phosphate-containing detergents, but a far superior antistatic effect a comparison detergent containing phosphate. Textiles washed with the composition according to the invention are softer than if they were washed with the comparison substance, the best cleaning compared to the comparison substance being carried out in cold water. Furthermore, the cleaning power in the product of the invention is significantly better if, instead of a quaternary Ammonium halide CISA is installed.

Example 2

The data given in Example 1 relate to detergents containing CISA with polyacetal: zeolite carboxylate ratios of 1: 1 to 2: 1. Similar results are obtained when the polyacetal carboxylate completely replaces the zeolite, with the CISA imparting antistatic activity and the polyacetal carboxylate serving as an effective builder. These compositions also improve the softness of washed towels more

60

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670 652

as a comparative product with sodium tripolyphosphate as a builder and without CISA.

Example 3

If the compositions of the invention according to Examples 1 and 2 were modified by using Builder U-material of batch No. 2538422 instead of the Builder U-material of batch No. 2547312, the results were essentially the same. The replacement builder U contains about 38% polyacetal carboxylate, which has a weight average molecular weight of 5200. In these experiments, in which the lower molecular weight polyacetal carboxylate was used, and in experiments according to Examples 1 and 2, in which isostearamides substituted on nitrogen with higher alkyl, such as, for example, those derived from N-tallow amine or N-octyl amine or mixtures thereof, with each of the two Builder U types useful antistatic effects, plasticization and cleaning were obtained without reducing the cleaning power due to the presence of the amine. Overall, however, the results are not as good when using amides other than CISA. Comparable desired results were also obtained when a

Part of the anionic surfactant of Examples 1 and 2 has been replaced by nonionic surfactant such as Neodol 23-6.5, Neodol 25-7 or Neodol 34-11, all of which are condensation products of ethylene oxide with higher fatty alcohols. In these experiments, the proportion of sodium (linear) tridecylbenzenesulfonate can be reduced in proportion to the addition of 2.4 and 6% nonionic surfactant. These results are also obtained when CISA or similar amide is mixed with the rest of the composition and not coated on the particle surfaces thereof.

10th

Example 4

Useful products with the desired cleaning and antistatic properties were also obtained by modifying the various proportions of the components of the components of the compositions according to the invention from Examples 1 to 3 by ± 10% and ± 30% of the stated amounts, these proportions being given in the amounts given according to the invention Areas. Similarly, the manufacture and application can be modified, and the spray drying, spray-20 coating, and washing procedures can be changed to obtain useful, satisfactory products.

G

Claims (16)

670 652 2nd PATENT CLAIMS 1. Antistatic, particulate, builder-containing detergent composition, characterized by a content of a cleaning amount of a surfactant, an amount of a polyacetal carboxylate builder or a mixture of polyacetal carboxylate with zeolite builder, and an antistatic amount of isostearamide which is more aliphatically substituted on the nitrogen: 2. Composition according to claim 1, characterized in that it is essentially phosphate-free, that the amide is an isostearamide substituted on nitrogen with higher alkyl, the alkyl having 7 to 18 carbon atoms, that the surfactant is an anionic sulfate or sulfonate surfactant, that the polyacetal carboxylate builder has a calculated weight average molecular weight in the range of 3,500 to 10,000 and that the zeolite builder is a hydrated A, X or Y type zeolite. 3. Composition according to claim 1, characterized in that the amide is cocoisostearamide (CISA), that the anionic surfactant is a higher alkylbenzenesulfonate in which the alkyl group has 10 to 18 carbon atoms, that the polyacetal carboxylate has sodium carboxylate as the carboxylate, and that the zeolite is a type A zeolite of the formula (Na2Û) x- (ALOsV (SiÛ2) z-w HzO is where x = 1, y is 0.8 to 1.2, z is 1.5 to 3.5 and w is 0 to 9. 4. The composition according to claim 3, characterized in that the anionic surfactant is a higher alkylbenzenesulfonate with a linear alkyl group having 12 to 16 carbon atoms, and that in the zeolite y means about 1, z in the range from 2 to 3 and w in is in the range of 2.5 to 6. 5. Composition according to claim 4, characterized by about 5 to 30% sodium (linear, higher) alkylbenzenesulfonate, the higher alkyl having 12 to 14 carbon atoms, 5 to 40% polyacetal carboxylate builder or a mixture thereof with zeolite builder, 2 to 20% CISA, 2 to 20% moisture and, if appropriate, the remainder filler (s) and / or other builders and / or auxiliaries). 6. The composition according to claim 5, characterized by 10 to 25% sodium (linear) tridecylbenzenesulfonate, 12 to 30% polyacetal carboxylate builder of a calculated weight average molecular weight in the range from 5000 to 9000, or a mixture of this builder with zeolite builder, at least 4 % of the composition are polyacetal carboxylate builders, 3 to 15% CISA, 3 to 15% moisture, 8 to 20% sodium carbonate, 5 to 12% sodium silicate with a Na20: SiÛ2 weight ratio in the range of 1: 1.6 to 1: 3.0 , and 20 to 35% sodium sulfate. 7. The composition according to claim 6, characterized in that it contains 13 to 23% sodium (linear) tridecylbenzenesulfonate, 13 to 26% sodium polyacetal carboxylate builder of a calculated weight average molecular weight of about 8000.4 to 13% CISA, 4 to 12% moisture, Contains 10 to 18% sodium carbonate, 5 to 10% sodium silicate with a Na2Û: Si02 weight ratio in the range of 1: 2.0 to 1: 2.6 and 20 to 30% sodium sulfate. 8. The composition according to claim 6, characterized in that it contains 13 to 23% sodium (linear) tridecylbenzenesulfonate, 13 to 26% of a mixture of sodium polyacetal carboxylate buil- a calculated weight average molecular weight of about 8000 and type A zeolite in a weight ratio the range of 1: 2 to 4: 1.4 to 13% CISA, 4 to 12% moisture, 10 to 18% sodium carbonate, 5 to 10% sodium silicate with a Na20: SiCh weight ratio in the range of 1: 2.0 to 1: 2.6, and contains 20 to 30% sodium sulfate. 9. A method for producing an antistatic, builder-containing, particulate detergent composition according to claim 1, characterized by spray-drying an aqueous slurry containing surfactant, polyacetal carboxylate builder or polyacetal carboxylate and zeolite builder to substantially spherical granules with particle sizes in the range from 2.00 to 0.149 mm (numbers 10 to 100 US sieve series) and then coating these spray-dried grains with an antistatic amount of the isostearamide which is more aliphatically substituted on nitrogen. 10. The method according to claim 9, characterized in that the aqueous slurry contains a filler. 11. The method according to claim 9, characterized in that the surfactant is an anionic surfactant, namely a sodium (linear, higher) alkylbenzenesulfonate having 12 to 14 carbon atoms in the alkyl radical, and that the polyacetal carboxylate builder is a sodium polyacetal carboxylate with a calculated weight average molecular weight in the range of 5000 to 9000. 12. The method according to claim 11, characterized in that the anionic surfactant is sodium (linear) tridecylbenzenesulfonate, that the polyacetal carboxylate builder is a sodium polyacetal carboxylate with a calculated weight average molecular weight of about 8000, that the aqueous slurry is sodium (linear) tridecylbenzenesulfonate , called polyacetal carboxylate, hydrated zeolite A, sodium silicate with a Na20: Si02 weight ratio in the range from 1: 2.0 to 1: 2.6, sodium carbonate and sodium sulfate, comprising isostearamide substituted with higher alkyl as the amide, the alkyl of which is 7 has to 18 carbon atoms, applied and coated on the spray-dried beads, and that the detergent composition obtained contains 13 to 23% sodium (linear) tridecylbenzenesulfonate, a total of 13 to 26% mentioned polyacetal carboxylate builder and zeolite A builder in a corresponding polyacetal carboxylate to zeolite A weight ratio from 1: 2 to 4: 1.4 to 13% isostearamide substituted with C7-C18 alkyl on nitrogen, 4 to 12% moisture, 10 to 18% sodium carbonate, 5 to 10% sodium silicate with a Na20: SiC> 2 weight ratio of 1 : 2.0 to 1: 2.6 and 20 to 30% sodium sulfate. 13. The method according to claim 12, characterized in that the amide is N-cocoisostearamide and that the bulk densities of the spray-dried beads and the product are 0.25 to 0.5 g / ml. 14. Commercial process for removing difficult-to-remove dirt and stains from fiber materials, characterized by washing the dirty and stained materials in water of a mixed calcium and magnesium hardness in the range from 50 to 250 ppm, as calcium carbonate, at a temperature of 10 to 35 ° C with 0.05 to 0.5% a detergent composition according to claim 1, which contains a cleaning amount of anionic surfactant, a builder-effective amount of a polyacetal carboxylate builder or a mixture thereof with a zeolite builder and an antistatic amount of cocoisostearamide (CISA). 15. The method according to claim 14, characterized in that the washing water temperature is 15 to 25 ° C, that the concentration of the detergent composition in the washing water is 0.1 to 0.2% and that the detergent composition is 13 to 23% sodium (linear) tridecylbenzenesulfonate , 13 to 26% of a mixture of sodium polyacetal carboxylate builder with a calculated weight average molecular weight of about 8000 and type A zeolite of the formula (Na20) x • (Al203) y • (Si02) z • w H2O where x = 1, y = 1, z is 2 to 3 and w is 2.5 to 6, where 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 3rd 670 652 Weight ratio of the polyacetal carboxylate builder to the zeolite builder is in the range of 1: 2 to 4: 1, 4 to 13% CISA, 4 to 12% moisture, 10 to 18% sodium carbonate, 5 to 10% sodium silicate with a Na20: SiCh weight ratio in that Contains from 1: 2.0 to 1: 2.6, and 20 to 30% sodium sulfate. 16. The method according to claim 15, characterized in that the detergent composition contains approximately equal amounts of the polyacetal carboxylate and type A zeolite as a builder.