SE462596B - ANTISTATIC FIRST PARTICULAR DETERGENT COMPOSITION, PROCEDURE FOR ITS PREPARATION AND ITS APPLICATION IN WASHING OF FIBER MATERIAL - Google Patents

Description

462,596 such anionic detergent compositions are appreciably negative. Recently, polyacetal carboxylate enhancers have been used in detergent compositions instead of polyphosphate enhancers, as they do not contain phosphorus and are therefore not believed to lead to eutrophication of lakes. Another advantage of these amplifiers is their readily degradable in normally acidic wastewater. Zeolites and other builders, both water-soluble and water-insoluble and both organic and inorganic, have been used for many years to improve the cleaning ability of synthetic organic detergents. Non-phosphate enhanced detergent compositions have been prepared in which polyphosphate enhancers are not present, and these detergent compositions are non-eutrophic. Although the main components of the present detergent compositions have been used in other detergent formulations, the present products are new, surprising and useful, and possess an unexpectedly good dirt and stain removal ability. Of particular importance is the considerably improved ability of the present compositions, especially non-phosphate-containing compositions, to remove a number of common and difficult stains and dirt from textile materials and to impart antistatic properties to these materials during conventional machine washing, which prevent antistatic properties. the washed materials to adhere to each other after automatic wash drying.

According to the present invention, an antistatic enhanced detergent composition, preferably in particulate form, comprises a detersive moiety of a synthetic organic detergent, preferably an anionic detergent, or a mixture of such detergents, a detergent enhancing moiety of a polyacetal carboxylate enhancer or those detergent therefor. or a fortifying 462,596 moiety of a mixture of such a polvacetal carboxylate builder and zeolite builder, and an antistatic moiety of an antistatic amide, such as N-coconut estearamide (CISA). Preferred compositions comprise about 5 to 30% sodium linear higher alkyl benzenesulfonate, wherein the higher alkyl has 12 to 14 carbon atoms, about 5 to 40% sodium polyacetal carboxylate builder with a calculated weight average molecular weight in the range of 3500 to 10,000, or a mixture of such an enhancer and zeolite A enhancer, about 2 - 20% CISA, about 2 - 20% moisture and any balance fillers and / or other enhancers and / or other additives. The invention also relates to processes for the preparation of such compositions and for the removal of dirt and stains from fibrous materials by washing the materials in washing water, which contains such a detergent composition or its components.

The anionic synthetic organic detergent of the present invention is normally sulfated and / or sulfonated lipophilic materials having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to 18 and more preferably 121 to 16 carbon atoms. While various water-soluble salt-forming cations may be used to form the desired soluble sulfated and sulfonated detergents, including ammonium and lower alkanolamine (such as triethanolamine) and magnesium, an alkali metal such as sodium or potassium is usually used, and preferably the cation is sodium. . Among the various anionic detergents useful in the practice of the present invention, the linear higher alkylbenzenesulfonates having 10 to 18 carbon atoms in the alkyl chain, preferably 12 to 16 and more preferably 12 to 14 carbon atoms, are considered to be most suitable. Also useful are monoglyceride sulfates, higher fatty alcohol sulfates, sulfated polyethoxylated higher alkanols, in which the alkanols may be synthetic or natural, containing 3 to 20 or 30 ethoxy groups per mole, paraffin sulfonates and olefin sulfonates, wherein in all compounds the the alkyl group present has 10 to 18 carbon atoms. Some of these alkyl groups may be slightly branched, but still have a carbon chain length within the specified range. Although the linear higher alkyl benzene sulfonates, in the form of the sodium salts, are the preferred anionic detergents in the practice of the present invention, mixtures of such detergents with other linear higher alkyl benzene sulfonates containing different cations may be used, as well as mixtures of such detergents with others. such as the fatty alcohol sulfates and the sulfated polyethoxylated higher alkanols. In some cases only minor proportions of the linear alkyl benzene sulfonates are present or the anionic synthetic organic detergent may be a mixture of other anionic detergents of the types described. Furthermore, other anionic detergents may be used, such as those well known in the art and described in various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example, the 1969 edition. Although the present invention is primarily concerned with anionic detergent compositions having antistatic properties, the desired results mentioned herein are also obtained with compositions containing other types of synthetic organic detergents with the anionic detergents, such as nonionic and amphoteric detergents, and in some cases cationic materials, such as di-higher alkyl, di-lower alkyl ammonium halides, di- -talloy1-dimethylammonium chloride, other quaternary ammonium halides, and other cationic materials may be present, primarily for fabric softening effects (although bentonite or other fabric softening clay is preferably used instead for this purpose, sometimes with additional cationic plasticizer). The said nonionic, amphoteric and cationic materials are normally present only in minor proportions, if present at all, and are usually used at most half as much of them as by the synthetic anionic organic detergent. Preferred nonionic detergents are the ethylene oxide condensation products of higher fatty alcohols, such as condensation products of higher fatty alcohols having 12 to 18 carbon atoms with 3 to 20 moles of ethylene oxide, preferably condensation products of higher fatty alcohols having 12 to 15 carbon atoms with 5 to 15 moles of ethylene oxide.

The polyacetal carboxylate can be considered as described in U.S. Patent No. 4,144,226 and can be prepared by the method mentioned therein. A typical such product has the formula R 1 - (ïHO) COOM n - R 2 in which M is selected from the group consisting of alkali metal, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups having 1 to 4 carbon atoms in the respective alkyl groups , n is on average at least 4, and R 1 and R 2 are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution.

Preferably the polyacetal carboxylate is one in which M is alkali metal, eg sodium, n is 20 - 200, R 1 is 462 596 6 CHBCH 2? MOO? HCO- or H3C-CO- H3C MOOC or a mixture thereof, R2 is ïCH2CH3 -CH CH3 and n averages 20-100, more preferably 30-80.

The calculated weight average molecular weights of the polymers are normally in the range 2000 - 20,000, preferably 3500 - 10,000 and more preferably 5000 - 9000, eg about 8000. Although the preferred polyacetal carboxylates are described above, it is understood that they may be completely or partially replaced by other similar polyacetal carboxylates or related organic builder salts described in various Monsanto patents relating to these compounds, processes for their preparation and compositions in which they are used. Furthermore, chain terminating groups described in the cited Monsanto patents, in particular US 4,144,226, can also be used, provided that they have the desired stabilizing properties which allow said enhancers to be depolymerized in acidic medium, facilitate biodegradation thereof in effluent streams, but maintain their stability in alkaline media, such as washing solutions.

The zeolite component may usually have the formula (Nazmx '(Al2 O3) y' (S102) ° w Hzø, in which x is 1, y is 0.8 - 1.2, preferably about 1, z is 1.5 - 3.5, preferably 2 - 3 or about 2, and 462 596 w are 0 - 9, preferably 2.5 - 6. These zeolites are cation exchanging and have a calcium ion exchange capacity in the range of about 200 - 400 or more milligram equivalents of calcium carbonate hardness per gram They are very often hydrated to 5 - 30%, preferably - 25% moisture, eg about 20% thereof. Zeolite A is preferred (but X and Y are useful) and of this zeolite type 4A is most preferred. the zeolites are usually in the range of 100 - 400, preferably 140 or 200 - 325 mesh (0, 105 or 0.074 - 0.044 mm), but their optimal sizes are submicron.The various zeolites are described exhaustively in Zeolite Molecular Sieves, by Donald W Breck, published 1974 by John Wiley & Sons, and in particular pages 747 - 749 thereof. In the compositions of the invention one may also include builders other than the polyacetal carboxylate (and the zeolite), although such are not necessary. In general, it is desirable to avoid the presence of phosphorus in the detergent composition, so the polyphosphates, which have been the preferred builders of detergents for many years (especially pentasodium tripolyphosphate), are preferably omitted from the present formulations. However, in some cases they may be present if the shares are kept relatively low, for example up to 5 or 10%. Among builders, in addition to polyphosphates such as sodium tripolyphosphate and tetrasodium pyrophosphate and in addition to the aforementioned polyacetal carboxylates and zeolites, the builders which may desirably be incorporated into the present compositions to enhance the , sodium citrate, sodium gluconate, borax, other borates and other enhancers known in the art of detergents. Fillers may be present, such as sodium sulfate and sodium chloride to add bulk to the product, when this is considered desirable, and they also serve other purposes. Of the builders, the zeolites are considered to be particularly effective together with the polyacetal carboxylates in these compositions, as previously indicated, and of the fillers, sodium sulphate is usually preferred.

The preferred antistatic agent in the practice of the present invention is N-coconut ostearamide. This antistatic agent is an amide, which is chemically derived from isostearic acid and coconut amine by the condensation reaction shown below: 0 O Raw + RWTHZ-ê fi- RQNHR '+ H20 å? Isostearic acid, RC-OH, is a saturated fatty acid of the formula C17H35COOH, which is a complex mixture of isomers, primarily of the methyl branched series, which are mutually soluble and practically inseparable. While this acid can normally be used in a manner similar to stearic acid or oleic acid, it is considered to be very superior to such materials in the manufacture of effective antistatic agents which are suitable for incorporation into the applicant's synthetic organic anionic detergent compositions. Cocosamine 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 the alkyl group, such as R'NHα, where R 'is such a higher alkyl, may also be used, but coconut amine provides an isostearamide having the best properties for incorporation into detergent compositions.

While CISA (coconut ostearamide) is the most preferred antistatic agent, it is within the further scope of the present invention to use other 462,596 N-aliphatic isostearamides, such as those derived from primary aliphatic amines containing 7 to 18 carbon atoms, whose aliphatic moieties may be or not be hydrogenated, provided that the amides have sufficient antistatic effect in the use described. Some examples of this are N-alkylisostearamides derived from N-tallowamine, N-decylamine and N-octylamine. However, in addition to CISA, N-alkylisostearamides are considered to be inferior in antistatic effect to CISA and, if used at all, are therefore preferably present in a smaller proportion relative to CISA. In some cases the hydrogen atom of the amide nitrogen may be replaced by suitable radicals such as lower alkyl, eg methyl, provided that the desired antistatic effect is still obtained, but it has been found that the tertiary isostearamides usually have little antistatic activity.

Among the various additives that may be present in the present compositions are coloring agents, such as dyes and pigments, perfumes, enzymes, stabilizers, activators, fluorescent whitening agents, bleaching agents, buffering, fungicides, germicides, defoamers and flow enhancers. Additives, builders and fillers also include, unless they are included in other of the classes mentioned, various additional components or contaminants that are present along with the components of the composition. For example, it is known that sodium carbonate and water are often present together with polyacetal carboxylate in Builder U, the product which is the present source of the polyacetal carboxylate.

Moisture is usually present in the compositions of the invention, either as free moisture or in one or more hydrates. While moisture is not an essential component of the present solid detergent compositions, it is normally present depending on the use of water in preparation, and the moisture may help to solubilize the components of the composition and help bind them together.

The proportions of the components of the compositions of the invention given below relate to particulate products which normally have particle sizes in the range of 8 or 10 to 100 or 140 mesh, which corresponds to 2.38 or 2.00 to 0.149 or 0.105 mm. However, these proportions are also applicable to other solid forms, such as sticks or cakes, finer or coarser powders, granular compositions and agglomerates. They can also be applied to liquid, gel and paste formulations. The ratios of component pairs, with the exception of water, may be approximately the same in liquid, gel and paste formulations as in solid formulations, but since the liquid products are often more dilute, the proportion of water or other solvent or mixture of solvents is present. usually significantly larger. According to certain aspects of the invention, the product components can be added directly to the washing water, in which case the washing water containing the various active and other components can be considered as the detergent composition.

In the particulate solid or other solid detergent compositions of the invention, the total proportion of detergent present is normally 5 - 40%, preferably - 30%, more preferably 10 - 25% and most preferably 13 - 23%, eg about 18%. This detergent is normally an anionic detergent and of these the higher alkylbenzenesulfonates, for example sodium linear tridecylbenzenesulfonate, are preferred. However, it may be present together with other anionic detergents or it may be completely or partially replaced by one or more such anionic detergents. The proportion of polyacetal carboxylate builder is normally in the range 5 - 50%, preferably 5 - 40%, more preferably 12 - 30% and most preferably 13 - 26%, eg about 17%, when it is the only builder present or reaches up to 50% of enhancers other than zeolite, such as 15-40%, are also present. When zeolite is used, the sum of the polyacetal carboxylate and the zeolite is the above proportion for polyacetal carboxylate alone and if zeolite is present, the polyacetal carboxylate constitutes at least 4% of the detergent composition. In addition, the ratio of polyacetal carboxylate to zeolite is in the range 1: 2 - 4: 1, preferably 1: 2 - 3: 1, more preferably about 2: 3 - 3: 2, eg about 1: 1. The CISA antistatic agent, which also has fabric softening properties in the compositions described, is present in an antistatic proportion in the compositions of the invention, so that it substantially reduces the static electricity, at least for some synthetic fibers and fabrics. The present detergent compositions have been found to be particularly effective in reducing electrical charges (and thus static adhesion) of polymeric materials, but they also effectively reduce such undesirable effects of machine drying for fabrics made from natural fibers and natural / synthetic blends. The proportion of antistatic agents is usually in the range 2-20%, preferably 3 - 15% and more preferably 4 - 13%, eg about 9%.

The percentage of moisture normally amounts to 2 - 20%, preferably 3 - 15% and more preferably 4 - 12%, eg about 5 or 6%. These percentages include moisture in hydrate form, which is released under heating for two hours at 105 ° C (the standard moisture analysis method). 462 596 12 The proportion of fillers is normally limited to a maximum of 50% and is often in the range 5 - 40%, preferably - 35%, eg about 25%. The content of non-phosphate-containing builders in addition to the polyacetal carboxylate and any zeolite present is generally limited to less than 40%, such as 3 to 30% or 5 to 25%. Such supplementary enhancers are not required but their presence, often together with filler salt, is often desirable. Thus, sodium carbonate is a preferred non-phosphate builder, as is sodium silicate. The pre-: SiO2 ratio is in the range 1: 1.6 - 1: 3.0, more preferably 1: 2.0 - 1: 2.6, eg 1: 2.4. The proportions of the carbonate and the silicate, if present, may amount to 3 - 25%, preferably 8 - 20% and more preferably - 18% for the carbonate, and 2 - 15%, preferably - 10% and more preferably 6 - 9% for the silicate. The total content of additives usually does not exceed 10 or 20%, and is preferably less than 5%, drawn silicates are the sodium salts, in which Na wherein the content of the usual individual additives generally does not exceed 3 or 5%, and often preferably is less than 1 or 2%. For example, the proportion of sodium carboxymethylcellulose, which is a desirable antifoulant, is 0.3 - 3%, preferably 0.5 - 2%, eg 1% of the composition, if present.

In preferred forms of the invention comprising particulate solid compositions having particle sizes within the above ranges, it is often preferred to spray dry as much of the formulation as possible to obtain substantially uniformly shaped spherical particles. The antistatic agent can be added to the remainder of the composition such as by spray coating on it, in liquid form, on tumbling spray-dried detergent base granules. To prevent segregation during shipping and storage of the final product, it is desirable that any added components such as enzyme, bleach, bentonite (if not spray dried) and polyacetal carboxylate (if not spray dried) have a shape, particle sizes and bulk density similar thereto. the remainder of the composition.

However, when this is not the case and when the post-added materials are in finely divided form such as particle sizes in the range 160 - 325 mesh and with higher bulk density, they can be added to the spray dried grains or other particles of the base detergent composition, which often have larger particle sizes. , and often they adhere to these particles to give a desired product with sizes in the range - 100 mesh. The polyacetal carboxylate can be spray-dried with the detergent composition provided that care is taken to prevent it from decomposing on heat. Alternatively, in the preparation method, the various components are mixed together in finely divided form. Even when the initial particle sizes of the various components or of some of them are smaller than the desired one, such as in the range 160 - 325 mesh, the particles thereof can be agglomerated to the desired size, sometimes by means of agglomerating agents, such as a dilute aqueous solution of sodium silicate, and at other times with water only to aid in agglomeration; Such agglomeration can take place only of the sub-large particles or these particles can be agglomerated with the larger spray-dried grains or with larger particles of the components of the composition or mixtures of these components.

The anionic detergent or mixture of such detergents, which are the primary detergents in the desired compositions, may be spray dried with fillers such as sodium sulfate, builders such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and additives such as fluorescent whitening agents, pigments and dyes, normally with a conventional countercurrent or cocurrent spray dryer with drying air entering at about 200 - 600 ° C (preferably 150 - 300 or 350 ° C when polyacetal carboxylate is present). Thereafter, the polyacetal carboxylate and the antistatic agent may be mixed in, in any order or together, or the antistatic agent and the polyacetal carboxylate may be premixed and then sprayed or dropped on the spray-dried granules, or mixed therewith, or the antistatic agent alone may be sprayed on or mixed with the granules. these, when the polyacetal carboxylate is included in the spray-dried granules. In some cases, the polyacetal carboxylate and / or antistatic agent may be spray dried with other components that are stable enough to withstand the spray drying conditions used, which conditions are preferably mild.

Often, however, the starting mixture and spray-drying operation reduce the antistatic activity of the isostearamide and therefore it is preferred that polyacetal carboxylate and / or CISA be added, often by coating on the components of the composition present in particulate form or on the spray-dried base granules. When CISA is coated on, mixed with or agglomerated with a component of the product, such as borax grains, agglomerated zeolite, Microcell C (a synthetic calcium silicate) or bentonite, a flowable product is obtained which can be easily mixed with the spray dried grains to give the final product.

When a relatively small proportion of nonionic detergent is to be present together with the anionic detergent, it can be spray dried with this anionic detergent, fillers and other stable materials. However, when more than about 4 or 5% (sometimes more than 2%) of nonionic detergent is to be present in the final product, any additional proportion is usually added afterwards, such as by spraying on tumbling detergent granules with or without CISA and / or polyacetal carboxylate. and any other suitable liquids, such as perfume, although perfume is usually applied last. In some cases, the polyacetal carboxylate may be dispersed and / or dissolved in the nonionic detergent to be sprayed onto the base grains, which nonionic detergent is heated to a liquid state (or it may be dissolved in a solvent), and the combination nonionic detergent and polyacetal carboxylate can be sprayed on the detergent granules or base granules, followed by the addition of the antistatic agent, preferably by spray coating the spray-dried detergent composition granules. It is desirable that the produced particulate material have particle sizes in the range of 8 - 120 or 10 - 100 mesh, corresponding to 2.38 - 0.125 mm or 2.00 - 0.149 mm, and the manufacturing process be adjusted accordingly.

However, screening can be used to remove undersized and oversized particles, which can be reprocessed, ground, agglomerated or otherwise treated to desired sizes (sometimes 2.38 - 0.177 mm). The bulk densities of the spray-dried granules and the final product granules are often in the range of about 0.2 - 0.6 g / ml, preferably 0.25 - 0.5 g / ml, eg 0.3 or 0.4 g / ml. For the production of the present products in bar, cake or briquette form, the compositions can be extruded or pressed or cast into the correct shape in a known manner. To convert them to liquid, gel or paste formulations, the components may be dissolved and / or dispersed in liquid medium, such as water and / or suitable solvents, such as ethanol, glycerol and / or isopropanol. and a gelling agent may be used. Dissolution of CISA or similar isostearamide in alcohol or other similarly acting solvents is sometimes avoided, as this sometimes reduces the antistatic effect.

To perform the dirt and stain removal processes of the present invention, which leave the washed garments non-adherent and clean (and also with improved softness compared to a control sample), one of the compositions described may be added to a wash water or its various components are added to the wash water. Normally the concentrations of the compositions used are in the range 0.05 or 0.1 - 0.4 or 0.5%, preferably 0.1 - 0.35% and more preferably 0.1 - 0.2% of the wash water. . Higher concentrations, such as 0.25 - 0.45% or higher (and less washing water) are often used in machine washes according to European practice, which normally use a washing water with a higher temperature. According to US practice, lower concentrations of the detergent compositions are normally used such as 0.05 - - 0.25%, often preferably about 0.1 - 0.2%. The washing temperature in America is usually in the range of 10 - 55 ° C. Although the higher temperatures within this range, such as 35 - 55 ° C may be best in terms of cleaning ability, the lower temperatures such as 10 - 35 ° C and 15 - 2s ° c are best for washing delicate fabrics and certain dyed fabrics. fabrics, for energy saving, which is why good cleaning at such lower temperatures is important.

The compositions of the present invention are useful for removing dirt and stains from laundry of various textiles and materials, leaving this laundry free from static charge and with improved softness, even after low temperature washing. In the practice of the present invention, a sufficient amount of the detergent composition of the invention is added to wash water in a conventional home washing machine (commercial machines may also be used) in the desired proportion within the stated ranges, eg 0.15% (100 g / l). 65 l of washing water), the washing water having a normal washing temperature, eg 21 ° C and normal hardness (about 50 - 250 ppm such as calcium carbonate, eg 150 ppm). The laundry is then added, the normal weight being loaded being 2.7 - 4.5 kg, eg 3.6 kg. Washing of the laundry is accomplished in a normal cycle over a period of 2 minutes to 30 minutes, such as 5-20 minutes, eg about 10 minutes, usually depending on the degree of soiling of the laundry.

It is surprising that the compositions of the present invention exhibit approximately the same cleaning ability as a control sample (from which CISA was omitted) in medium hard water of about 150 ppm hardness, when the wash water has a temperature of 41 ° C but is noticeably better than said control at lower temperatures such as 15 - 25 ° C.

In such control compositions, the polyacetal carboxylate or zeolite + polyacetal carboxylate is replaced by an equal proportion of sodium tripolyphosphate. Also terry towels washed with the composition of the invention, containing polyacetal carboxylate, zeolite and CISA, are softer than non-CISA control composition (in which the polyacetal carboxylate and the zeolite are replaced by a corresponding amount by weight of sodium tripolyphosphate according to the invention). clearly superior in non-adhesive properties, especially for acrylic fabrics.

The advantages of the present invention are significant.

Use of CISA enables the preparation of an antistatic non-phosphate or substantially non-phosphate-containing detergent composition which has substantially the same detersive activity as phosphate-containing detergent compositions. Unlike detergent compositions now on the market, which include polyphosphate enhancers and quaternary ammonium halide as antistatic agents (and plasticizers), in which the quaternary ammonium halide reacts with the anionic detergent, thereby reducing its detersive activity, CISA does not adversely affect the anionic detergent (or phosphate).

Thus, using CISA in detergent compositions in which polyacetal carboxylate builders or a mixture of polyacetal carboxylate and zeolite builders are used, normally as primary builders, it is possible to prepare an antistatic non-phosphate-containing detergent composition having a product which does not contain a cleaning agent. , in which the primary builder is a corresponding proportion of pentasodium tripolyphosphate or other sodium tripolyphosphate (equal to the total amount of polyacetal carboxylate and water softening or cation exchange zeolite present). The antistatic activity of the present compositions is comparable to that of rinse-cycle plasticizers. In addition, the present detergent compositions soften measurable laundry washed therewith.

Among the important effects that can be noted during various washing tests are the following: 1) In a washing machine test, in which a 9% CISA anionic detergent composition based on polyacetal carboxylate and zeolite enhancer for the anionic detergent was used, it was washed as well as a control detergent without CISA and with sodium tripolyphosphate as a substitute for the polyacetal carboxylate-aeolite builder mixture. Significantly better cleaning was also obtained compared to such a phosphate-enhanced control composition containing 5% distearyldimethylammonium chloride, and it could be expected that the use of 9% of the distearyldimethylammonium chloride would adversely affect purification. 2) 3) 4) 462 596 The performance of such a control composition to an even greater degree.

In Tergotometer samples, the compositions of the present invention were as good or better than control compositions in which polyphosphate was used as a builder, in cold water washing in medium hard water (normal washing conditions).

Compositions of the present invention are very superior control compositions in controlling static charge, especially in the case of textiles of polyester-cotton blends and double-knit polyester. The compositions of the invention also control the static charge better than a control sample with 5% quaternary ammonium halide added, when washing polyester-cotton blended fabrics. The non-phosphate-containing compositions of the invention containing CISA are significantly better than similar compositions in which polyphosphate builders replace the polyacetal carboxylate-zeolite mixture with respect to limiting static charge of acrylic material.

Non-phosphate-containing compositions of the present invention significantly soften washable cotton-polyester blend towels more than a CISA-free polyphosphate-reinforced detergent control.

The following examples illustrate but do not limit the invention. Unless otherwise indicated, all parts are by weight and all temperatures are in OC in the examples, in the description and in the appended claims. 462 596 Example 1 Component Percent Sodium linear tridecylbenzenesulfonate 18.2 Builder U (79.7% sodium polyacetal carboxylate, supplied by Monsanto Co (lot No. 2538422, with a calculated weight average molecular weight of about 8030) 10.9 Zeolite 4A (20 % hydrated) 10.9 Sodium carbonate (anhydrous) 12.7 Sodium silicate (Na 2 O: SiO 2 = 1: 2.4) 7.3 Sodium sulphate (anhydrous) 25.4 CISA (N-coconut ostearamide) 9.1 Moisture 5.5 100, A particulate detergent in spray-dried granule form is prepared from all of the above components except CISA by preparing an aqueous crutcher mixture (55% solids concentration) of the enumerated materials at a temperature of about 50 ° C and spray-drying said crutches. mixture under mild conditions, taking care to prevent decomposition of the polyacetal carboxylate, and by keeping the walls of the spray tower as clean as possible during the spraying operation.The spray tower used is a countercurrent tower operating under mild conditions with drying air of about 220 ° C inlet temperature and with other devices to prevent damage to the grains and to prevent decomposition of the polyacetal carboxylate (by preventing build-up on the tower walls, use of cooling air and / or controlled spraying to prevent contact between spray and tower walls).

The resulting product has particle sizes in the range of 2.00 - 0.149 mm, a bulk density of about 0.3 g / ml and a moisture content of about 6%. 10 parts of the detergent composition thus prepared are sprayed with one part of CISA in liquid form, so that CISA coats the particles. The temperature at which CISA is applied is normally about 5 ° C above its melting point or 5 ° C above the highest part of its solid-liquid phase conversion range. Such a temperature is used that upon contact with the cooler detergent particles, normally at about room temperature (but they may also have higher temperatures), CISA solidifies rapidly without agglomerating the spray dried grains into undesirably larger aggregates. Alternatively, CISA with the desired particle sizes in the range of 2.00 - 0.149 mm can be mixed with the spray dried particles. Although more finely powdered with particle sizes in the range of 0.149 - 0.044 mm, the antistatic agent may well be distributed throughout the detergent composition and normally adheres sufficiently to its particles to give a product which is within the desired size range and which has the desired range usually within the desired range. range 0.3 - 0.4 g / ml, just like the coated product.

The coated product is tested for dirt and stain removal, using a laboratory-type tergotometer washing machine in which standard samples of the various materials, soiled and stained in a standardized manner, are washed for 10 minutes in water with a hardness of 150 ppm as calcium carbonate, using a detergent composition concentration of 0.15% based on the wash water and at a wash temperature of 21 ° C.

The water hardness is a mixed calcium and magnesium hardness with a Ca: Mg ratio of 3: 2. Reflection measurements on the washed and dried samples of the different materials with different stains thereon according to a "standard soil removal index (SRI) test" are taken and 462 596 22 index indicating the weighted reflectance sums are calculated, which indices based on experience proved to be measures of dirt and stain removal capacity for a tested detergent composition, (the higher the index, the better the cleaning ability). Similar compositions are prepared in which 21.8% of total polyacetal carboxylate and zeolite are maintained but where the weight ratio of polyacetal carboxylate to zeolite is changed to 3 = 2 respectively 2: 1. The SRI values obtained are +6, +12 and +9, respectively, compared to a control detergent composition having a formula similar to that of the base detergent (without CISA), with the polyacetal carboxylate and the zeolite replaced by sodium tripolyphosphate. When the same tests are repeated with the only change being the wash water temperature, 41 ° C, the index is 0.4 and 3, respectively. It is considered that the index differences noted when the washing is carried out at 21 ° C are significant, and show that the present compositions are superior in terms of dirt. and stain removal at these lower temperatures.

In other experiments described below, detergent composition systems were used for washing two test pieces each (36 x 36 cm) of textiles having the following compositions: polyester-cotton blend; acetate; acrylate; and double-knit polyester. The detergent systems used are: a) 100 g of 24% polyphosphate-reinforced anionic detergent without CISA (base grain [BB]); b) 100 g polyphosphate BB + 10 g CISA (CISA overcoated on BB); c) 100 g 12% polyacetal carboxylate + 12% zeolite (instead of 24% polyphosphate) BB + 10 g CISA (CISA overcoated on the spray-dried product); d) 100 g polyphosphate BB + rinse cycle plasticizer (with Downy fabric softener); and e) 100 g of polyphosphate BB + 5 g of dimethyl distearylammonium chloride. The given amounts of the detergent composition were used to wash test fabrics in 60 liters of 150 ppm hardness 462 596 23 water in a General Electric Co washing machine at 43 ° C for 10 minutes. Static charge measurements were performed by reading the structure of the static charge generated by rubbing the respective test textiles against a piece of wool in a controlled manner for 5 seconds. Static charge measurements were performed in a room with controlled conditions (ie with constant temperature and low moisture content) using an electrostatic voltmeter. The following table shows the static charge measurements after machine drying. 462 596 24 Å. M. ~ H m_ = H. ~ @. = Mw .w m.mH>. = M. «=.«> _ «.U ~ .wH mH wm °.« W. ° .u «.- w. ~ O.mH °.« @ .O .n ~ .m «~. ° ~ ° .wH ° .m Q. ~ H Am umumwæ fl om mc fl cwcm fi n QHMUOH. ÜMMUHMNHQDDSD .ÉWHOÉ QMUUOÉ lm fiflflfi0 n ~ lhü fl wwä fl üü xwO-Hmn. »~ O> oH« x. mn fi cw fl m fi Mm fi umuw> m mGwcmmH> 4 H H fi w fl mü 462 596 The above table shows that the compositions of the present invention (c) give results comparable to a static control rinse cycle softener.

Also note that the composition according to the invention (c) is considerably better than the composition (b) in this respect, the difference being most pronounced with respect to static charge of acrylic. Furthermore, the static charge of blended polyester-cotton fabrics is significantly lower after washing with the compositions of the invention than after washing with a polyphosphate-containing detergent plus quaternary ammonium halide (e).

When interpreting the above data, charge differences greater than 4 kilovolts are considered significant.

In the washing waters in which the above detergent composition systems and / or treatments were used, tests were also performed with respect to cleaning ability. A number of standard SRI specimens were included in each wash and the samples were read for reflectance after washing. Four samples of each Test Fabric Nylon, Test Fabric Cotton, Piscataway (N.J.) clay on cotton, Piscataway clay on dacron / cotton blend, and EMPA 101 were included in each sample set. The highest removal obtained was that of the composition of the present invention containing polyacetal carboxylate, zeolite and CISA, and all other treatments being substantially the same with the exception of treatment e), which was significantly inferior.

Terry towels, which were washed in the same wash water as the test fabrics, were softer when washed with the detergent composition c) of the invention compared to a non-CISA-containing control a) in which the builder was sodium tripolyphosphate. 462 596 26 This example shows that high performance detergent compositions of the present invention containing CISA, polyacetal carboxylate and zeolite A with a non-phosphate-containing anionic detergent fortified with carbonate and silicate have a detersive effect similar to that of phosphate detergents and have antistatic effects. which are far superior to those of a comparative phosphate detergent.

Clothes washed with the composition according to the invention are softer than when washed with the control composition and the best cleaning compared to the control composition is obtained in cold water. Furthermore, the cleaning ability is significantly better for the product of the present invention when CISA is included in the present composition instead of a quaternary ammonium halide.

Example 2 In Example 1, data for CISA-containing detergent composition with polyacetal carboxylate to zeolite ratio of 1: 1 - 2: 1 were given. When the polyacetal carboxylate completely replaces the zeolite, similar results are obtained, with CISA contributing to the antistatic activity and the polyacetal carboxylate acting as an effective builder. Such compositions also cause an improved softness of washed towels compared to a control in which the enhancer is sodium tripolyphosphate and in which CISA is not present.

Example 3 When the compositions of the present invention as described in Examples 1 and 2 are modified by replacing the Builder U lot No. 2538422 material with Builder U lot No. 2547312 material, substantially the same result is obtained. This Builder U material has a weight average molecular weight of 5200 for the polyacetal carboxylate, of which it contains about 83%. In these experiments using the lower molecular weight polyacetal carboxylate and in experiments according to Examples 1 and 2 where other N-higher alkyl isostearamides were used, such as those derived from N-tallowamine or N-octylamine or mixtures thereof with either one or both Builder U types, useful antistatic activity, softening and cleaning are obtained without loss of cleaning ability due to the presence of the amide. However, it is generally considered that the results are not as good when other amides are used as when CISA is used. Also when a certain portion of the anionic detergent of Examples 1 and 2 is replaced with nonionic detergent such as Neodol 23-6.5, Neodol 25-7 or Neodol 45-1, all of which are condensation products of ethylene oxide and higher fatty alcohols, comparable desirable results. In these experiments, the proportion of sodium linear tridecylbenzenesulfonate can be reduced proportionally with respect to the addition of 2, 4 and 6% of the nonionic detergent. Such results can also be obtained when CISA or a similar amide is mixed with the remaining part of the composition, instead of being applied to the surfaces of the particles.

Example 4 The various proportions of the components of the compositions of the invention according to Examples 1 to 3 can be modified by +/- 10% and +/- 30% of the given proportions, provided that the proportions are kept within the ranges specified in the description, and useful products with the desired cleaning and antistatic properties are obtained. Similarly, the methods of manufacture and use can be modified and the spray drying, spray coating and washing operations can be changed, in accordance with the previous description, and now only products are obtained, manufactured and used satisfactorily. The invention has been described in connection with working examples and various illustrations and embodiments thereof, but it is not limited thereto, as it will be apparent to those skilled in the art upon reading the present disclosure that equivalent materials and substitutes may be used without deviates from the invention.

H »4 !!

Claims (14)

10 15 20 25 30 35 462 596 29 P a t e n t k r a v An antistatic reinforced particulate detergent composition, characterized in that it contains ionic detergent, a reinforcing moiety of a polyacetal carboxylate builder for said detergent or a reinforcing moiety of a mixture of a detergent moiety of a synthetic polyacetal carboxylate and zeolite enhancers, and an antistatic moiety of an N-higher aliphatic moiety of an N-higher aliphatic isostearamide. Detergent composition according to claim 1, which is substantially free of phosphate, characterized in that the amide is N-higher alkyl isostearamide in which the alkyl has 7 to 18 carbon atoms, the synthetic anionic detergent is a sulfate or a sulfonate, the polyacetal carboxylate has a calculated weight average molecular weight in the range 3,500 - 10,000 and the zeolite builder is a hydrated zeolite of type A, type X or type Y. Detergent composition according to claim 2, characterized in that the amide is coconut estearamide (CISA), the synthetic anionic organic detergent is a higher alkylbenzene sulfonate in which the alkyl group has 10 to 18 carbon atoms, that the carboxylate in the polyacetal carboxylate is sodium carboxylate and is a type A zeolite of the formula (Na2O) x. (A1203) Y. (SiO2) z. w H 2 O where x is 1, y is 0.8 - 1.2, z is 1.5 - 3.5 and w is. o-go 462 596 10 15 20 25 30 30 Detergent composition according to claim 3, characterized in that the synthetic anionic organic detergent is a higher alkylbenzene sulfonate in which n the alkyl group is linear and has 12 to 16 carbon atoms, and that the zeolite has the given formula, wherein y is about 1, z is in the range 2 - 3 and w is in the range 2.5 - 6. Detergent composition according to claim 4, characterized in that it comprises about 5 - 30% sodium linear higher alkyl benzene sulfonate, in which the higher alkyl has 12 - 14 carbon atoms, 5 - 40% polyacetal carboxylate builder or a mixture of a such enhancers and zeolite enhancers, 2 - 20% CISA, 2 - 20% moisture and any remaining fillers and / or other enhancers and / or additives. Detergent composition according to claim 5, characterized in that it comprises 10 - 25% sodium linear tridecylbenzenesulfonate, 12 - 30% polyacetal carboxylate builder with a calculated weight average molecular weight in the range of 5,000 - 9,000 or a mixture of a such enhancers and zeolite enhancers, wherein at least 4% of the composition is polyacetal carboxylate enhancer, 3 - 15% CISA, 3 - 15% moisture, 8 - 20% sodium carbonate, 5 - 12% sodium silicate with a Na 2 O: SiO 2 ratio in the range 1: 1.6 to 1: 3.0 and 20-35% sodium sulfate. t! Detergent composition according to claim 6, characterized in that it comprises 13 - 23% sodium linear tridecylbenzenesulfonate, 13 - 26% sodium polyacetal carboxylate builder with an estimated weight average molecular weight of about 8,000, 4 - 13% CISA, 4 - 12% moisture, 10 - 18% sodium carbonate, 5 - 10% sodium silicate with a Na2O: SiO2 ratio in the range 1: 2.0 to p 10 15 20 25 30 462 596 31 l: 2.6 and 20 - 30 % sodium sulfate. Detergent composition according to claim 6, characterized in that it comprises 13 - 23% sodium linear tridecylbenzenesulfonate, 13 - 26% of a mixture of sodium polyacetal carboxylate builder with an estimated weight average molecular weight of about 8,000 and type A zeolite , in which mixture the ratio of polyacetal carboxylate builder to zeolite builder is in the range 1: 2 - 4: 1, 4 - 13% CISA, 4 - 12% moisture, 10 - 18% sodium carbonate, 5 - 10% sodium silicate with a Na 2 O: SiO2 ratio in the range 1: 2.0 - 1: 2.6 and 20 - 30% sodium sulfate. A process for preparing an antistatic reinforced particulate detergent composition, which comprises a detergent moiety of a synthetic organic detergent, a reinforcing moiety of a polyacetal carboxylate builder for said detergent or a reinforcing moiety of a mixture of said polyacetal carcarbon carboxylate precursor , and an antistatic moiety of an N-higher aliphatic isostearamide, characterized in that it comprises spray drying an aqueous slurry of synthetic organic detergent, polyacetal carboxylate or polyacetal carboxylate and zeolite enhancers, fillers and / or other enhancers for said water. , to substantially spherical grains with particle sizes in the range of 10-- 100, US Sieve Series, (corresponding to 2.00 - 0.149 mm), and then coating said spray-dried grains with an antistatic proportion of N-higher aliphatic isostearamide. 462 10 15 20 25 30 596 32 Process according to claim 9, characterized in that the synthetic organic detergent is an anionic detergent, which is a sodium-linear higher alkyl benzene sulfonate in which the higher alkyl has 12 to 14 carbon atoms, the polyacetal carboxylate builder is a sodium polyacetal carboxylate with a calculated average weight molecular weight in the range 5,000 - 9,000, the aqueous slurry comprises sodium linear higher alkyl benzene sulfonate, polyacetal carboxylate, hydrated zeolite A, sodium silicate having a Na 2 O: SiO 2 ratio in the range 1: 2.0 - 1: 2, 6, sodium carbonate and sodium sulphate, that the amide is N-higher alkyl isostearamide in which the alkyl group has 7 to 18 carbon atoms, and is spray coated on the spray dried grains, and that the resulting detergent composition comprises 13 to 23% sodium linear tri-decylbenzenesulfonate, a total of 13 - 26% of polyacetal carboxylate enhancers with an estimated weight average molecular weight of about 8,000 and zeolite A enhancers, wherein ratio of polyacetal carboxylate to zeolite is in the range 1: 2 - 4: 1, 4 - 13% N-higher alkyl isostearamide, 4 - 12% moisture, 10 - 18% sodium carbonate, 5 - 10% sodium silicate with a Na 2 O: SiO 2 ratio in the range 1: 2.0 - 1: 2.6, and 20 - 30% sodium sulfate. Process according to Claim 10, characterized in that the amide is N-coconut ostearamide and that the bulk densities of the spray-dried granules and of the product are in the range 0.25 - 0.5 g / ml. A method of removing difficult-to-remove dirt and stains from fibrous materials, characterized in that it comprises washing said soiled and stained materials in water with mixed calcium and magnesium hardness in the range of 50 - 250 ppm, measured as calcium carbonate, at a temperature in the range of 10 - 35 ° C eg for example and at a concentration in the range of 0.05 - 0.5%, with a composition comprising a detersive proportion of anionic detergent, a reinforcing part of a polyacetal carboxy latent enhancer for said detergent or a reinforcing moiety of a mixture of said polyacetal carboxylate enhancer and zeolite enhancer, and an antistatic content of CISA. A method according to claim 12, that the wash water temperature is in the range characterized by 15 - 25 ° C, that the concentration of the detergent composition in the wash water is in the range 0.1 - 0.2% and that the detergent composition comprises 13 - 23% sodium linear. tridecylbenzenesulfonate, 13 - 26% of a mixture of sodium polyacetal carboxylate builder with an estimated weight average molecular weight of about 8,000 and zeolite type A of the formula (Nazmx - (a12o3) y - (sio2) z - w H2O where x is 1, y is 1, z is 2 - 3 and w is 2.5 - 6, in which mixture the ratio of polyacetal carboxylate builder to zeolite builder is in the range 1: 2 - 4: 1, 4 - 13% CISA, 4 - 12% moisture, 10 - 18% sodium carbonate, 5 - 10% sodium silicate with a Na 2 O: SiO 2 ratio in the range 1: 2.0 - 1: 2.6 and 20 - 30% sodium sulphate. 14. The method of claim 13, wherein the detergent composition comprises approximately equal proportions of polyacetal carboxylate builder and zeolite type A builder.