LU85929A1 - ANTISTATIC SYNTHETIC ORGANIC DETERGENT COMPOSITION, ITS MANUFACTURING METHOD AND WASHING METHOD - Google Patents

Description

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The present invention relates to detergent compositions. More particularly, it relates to detergent compositions comprising an anionic synthetic organic detergent or a mixture of such detergents, a detergency builder 5 for this detergent (s) consisting of polyacetal carboxylate and a cationic antistatic agent. The invention also includes a method for washing fibrous materials which have been soiled and / or stained, to remove such soils and / or stains and to prevent static "adhesion" of the materials.

The need to remove stains and stains from fibrous materials has been around for centuries and a multitude of compositions have been described to achieve this. Whereas soap was once the universal detergent, today almost all household laundry detergent compositions are based on one or more synthetic organic detergents. Among such detergents, anionic and nonionic detergents are the most effective, and anionic detergents are the most used. These ampholytic or amphoteric detergents and cationic detergents can also be used. Cationic compounds which have detersive activity are often also germicidal and act as antistatic agents ("antistatic") which is particularly important as they decrease the static adhesion of articles washed from synthetic organic polymeric plastics , for example, materials of "

Nylon, acrylic and polyester materials. Cationic compounds also have fabric softening properties. However, a disadvantage of cationic detergents is their reactivity towards anionic substances such as anionic detergents, which can be the cause of large decreases in detersive action. In recent years, cationic detergents such as quaternary ammonium halides have been used in detergent compositions to impart softening and antistatic properties to washed fabrics or fabrics made of ma-.

* 2 third plastic synthetic organic polymers, without having - a serious unfavorable effect on the detersive activities of 'JC. .'jr -y compositions. Recently also, polyacetal-carboxylate type detergency builders have been used in detergent compositions in place of polyphosphate type builders because they do not contain phosphorus and therefore were not intended to promote eutrophication of river water. Another advantage of such a detergency builder is that they are easily degradable in Ί0 normally acidic waste water.

Although the main components of the present detergent compositions have been used in other such compositions, the present compositions are novel, not obvious and useful, and have surprisingly good stain removal properties. and dirt.

Particularly important is the highly improved ability of the present compositions, in particular the phosphate-free compositions, to remove various stains and soils from synthetic textile materials and to give softening and antistatic properties to them. such materials during conventional machine washing, which antistatic properties prevent the washed materials from sticking to each other after automatic drying of the laundry.

According to the present invention, an anti-static detergent composition comprises a detergent proportion of a synthetic organic detergent or of a mixture of such detergents, a proportion which enhances the detergency of an adjuvant; amount of detergency of the polyacetal-carboxylate type suitable for this detergent (s) or a proportion reinforcing the detergency of a mixture of a detergency builder of the polyacetal-carboxylate type and of an adjuvant of detergency of the zeolite type, and an antistatic proportion to a - '' e »I cationic antistatic component. Such compositions pr§- 3t> feres include about 5 to 30% of al kyl ber.zene-sul f or.ate higher linear sodium in which the r ~ o '; r "z ~. iy *! e 3 higher has from 12 to ^ l4 carbon atoms, approximately 5 to ^ 40% of detergency builder of polyacetal-carboxylate- sodium type of a weighted average molecular weight calculated from 3500 to 10 000, or a mixture of such a detergency builder and a detergency builder of the zeolite A type, about 2 to 10% of distearyl dimethyl ammonium chloride, about 2 to 20% of humidity, the remainder consisting of inert charge (s) and / or other detergency builder (s) and / or other additive (s). also includes a method for removing blended stains and stains from fibrous materials, particularly cellulose acetate, which includes washing such stained and soiled fibrous materials in washing water which contains a composition detergent comprising a detergent proportion of a synthetic organic detergent or of a mixture of such detergents, a proportion reinforcing the detergency of a detergent adjuvant this polyaceta! -carboxylate type suitable for this detergent and an antistatic proportion of a cationic antistatic product, at a concentration of such a detergent composition in washing water from 0.05 to 0.5%. The invention further comprises a process for the manufacture of the compositions described.

The anionic synthetic organic detergent according to the present invention normally consists of lipophilic substance (s) sulfated (s) and / or sulfonated (s) having an alkyl chain of 8 to 20, preferably 10 to 18 and more preferably from 12 to 16 carbon atoms. Although various water soluble salt-forming cations can be used to form the desired soluble sulfated and sulfonated detergents, including ammonium and lower born friendly canol (such as tri ethanol friendly), and magnesium , an alkali metal such as sodium or potassium is usually used, and most preferably one such cation is sodium.

Among the various anionic detergents which can be used in the practice of this invention, the linear higher alkylbenzere-sulforates, the alkyl chain of which is | i * 3 "t · 4 - λ consisting of 10 to 18, preferably 12 to 16 and very preferably about 12 to 14 carbon atoms, are considered very suitable. Also usable, among others, are monoglyceride sulfates, sulfates of higher fatty alcohols, sulfated polyethoxylated higher alkanols, such alkanols which may be synthetic or natural, containing from 3 to 20 or 30 ethoxy groups per mole , paraffin sulfonates and olefin sulfonates, the alkyl group present in all these compounds containing from 10 to 18 carbon atoms. Some of these alkyl groups may be slightly branched, but they always have a carbon chain length in the range described.

The cationic antistatic products which can be used, usually in a limited proportion, that is to say not more than 20% and preferably only up to 15%, are preferably halides of upper dialkyl, lower dialkyl-ammonium, in which the upper alkyl radicals have from 10 to 18, preferably from 16 to 18 carbon atoms, the lower alkyl radicals have from 1 to 3 carbon atoms, preferably 1 carbon atom, and the halogens are chromium or bromine. Among such products, there may be mentioned distearyl dimethyl ammonium chloride, di sidf-dimethyl ammonium chloride (in which the alkyl radical originates from animal fats) and oi bromide (hydrogenated tallow) - dimethyl ammonium. However, various other such cationic products, including N-cetyl-ethyl-morpholini um ethosulfate, which often also have deodorant and germicidal properties, may also be used.

Descriptions of the various suitable anionic and cationic detergents are given in various annual publications - "” entitled McCutcheon's Detergents and Emulsifiers, for example, in that published in 1969. Such cationic products also form a well-known and they are w described in detail in the literature (as are the anionic detergents) and therefore it is not necessary to be explained in more detail here. In addition, non-ionic and amphoteric detergents, also described in 1e $ | £ McCutcheon texts, may be present with detergent; anionic and the cationic antistatic product, usually in lower proportions than the anionic detergent, and usually also in lower proportions than the cationic antistatic product present.

The polyketal carboxylate can be considered to be that described in US Pat. No. 4,144,226 and it can be prepared by the method mentioned therein. A characteristic product ^ of this kind corresponds to the formula: I R1 - <iH0) n - R2

COOM

I in which M is chosen from alkali metals, ammonium. ^ nium, alkyl groups having 1 to 4 carbon atoms, ^ tetraalkylammonium groups and alkanolamine groups? both having from 1 to 4 carbon atoms in the alkyl radicals; n averages at least 4; and R, and are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. Preferably, the polyacetal-carboxylate is that in which M is an alkali metal, sodium for example; n is between 20 and 100: R1 is

CH, CH90 M00C

I 25 3 2.

} HC0- or H.C-CO- i ^ * H3C kooc I or a mixture thereof; is \ 30 0 C H _ C H 9 '* ji. ά ό

I -CH

f "CH3 £: j? and n is on average between 20 and 100, more preferably between 30 and 80. The molecular weights on a calculated weighted average basis of the polymers are normally 2 G0Q at t 6 20 000, preferably from 3,500 to 10,000 and more preferably from 5,000 to 9,000, for example being about 8,000.

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Although the preferred polyacetal carboxylates have been described above, it should be understood that they may be completely or partially replaced by other polyacetal carboxylates or by related organic detergent builder salts described in a number of Monsanto patents dealing with such compounds, processes for their manufacture and compositions in which they are used. Likewise, the end groups of the chains described in the cited Monsanto patents, in particular in US Pat. No. 4,144,226, can be used provided that they have the desired stabilization properties which allow the mentioned detergency builders to be depolymerized. -15 risks in acidic media, which facilitates their biodegradation in waste water courses, but ensures their stability in alkaline media such as washing solutions.

The zeolite component usually has the formula (Na2O) x. (AljjO ^ y. (Si 0g) .wf ^ O, in which x is 1; y lu is between 0.8 and 1.2, preferably being equal to 1; z is between 1.5 and 3, 5, preferably between 2 and 3 or is equal to approximately 2; and w is between 0 and 9, preferably between 2.5 and 6. Such zeolites are cation exchangers and they have an exchange capacity 25 for the calcium ion of about 200 to 400 mg-equivalent of calcium carbonate hardness per g or more. They are preferably hydrated to a degree of 5 to 30%, preferably 10 to 25% of moisture, per example at 20% humidity. Zeolite A is preferred (X and Y are also useful) and in this type of zeolite, 4A is particularly preferred. Corresponding particle sizes of zeolite (s) usually lay at 149 to 37 ym, preferably 110 or 74 to 44 ym, but their ultimate sizes are less than one micron The various zeolites are described in detail in the text Zeolite Mr ^ ecular Sieves by Dona ld K. Breck, published by John Ville · ”! er particular on pages 747-749. "V" 7 In the compositions of the invention, other detergency builders than the polyacetal carboxylate may also be present although they are not necessary.

It is often desirable to avoid the presence of phosphorus in the detergent composition; thus polyphosphates, which have been the detergency adjuvants of choice in the detergent field for many years (in particular pentasodium tripolyphosphate), are preferably omitted from the present formulations. They can however be present in certain cases, if they are kept in relatively small proportions, for example up to 5 or 10%. Among detergency builders other than polyphosphates such as sodium tripolyphosphate and tetra-sodium pyrophosphate, those which it may be desirable to incorporate into the present compositions to complement the reinforcing action of the polyacetal carboxylate include sodium carbonate , sodium bicarbonate, sodium sesquicarbonate, sodium silicate, zeolites, 2eolite A for example, NTA, sodium citrate, sodium gluconate, borax, other borates and other other detergency builders known in the detergent field. Inert fillers may be present, such as sodium sulfate and sodium chloride, to give volume to the product when considered desirable. Among the detergency builders, zeolites are considered to be particularly effective in these compositions, as previously indicated, and among the inert fillers, sodium sulfate is usually preferred.

Among the various additives which can be used are dyes such as these dyes and pigments, perfumes, enzymes, stabilizers, activators, fluorescent optical brighteners, buffers, fungicides, germicides and fluidizers . Also included among the additives are detergency builders and inert fillers, unless they are found in other mentioned categories, various other components or.

8 additional impurities which accompany other ingredients. For example, it is recognized that sodium carbonate and 'water frequently accompany the polyacetal-carboxylate in Builder U, the product is the present source of 5-polyacetal -carboxylate.

Moisture is usually present in the compositions according to the invention, either as free moisture or in one or more hydrates. Although moisture is not an essential component of the present detergent compositions, it is normally present due to the use of water in the manufacture and it can help to solubilize and bind components of the composition.

The proportions of components of the compositions according to the invention given below are those for particulate products which usually have particle sizes in the range of 2.38 or 1.68 mm to 0.149 or 0.110 mm.

* However, such proportions also apply to other solid forms such as bars or breads, to more finely divided powders or to larger grains, to granular compositions and to agglomerates. They can also be applied to liquid preparations. However, due to their relatively low stability (due to interactions between anionic and cationic components) aqueous liquid preparations should be used relatively quickly after their preparation. Likewise, although the ratios between pairs of components, except water, can be about the same in liquid or pasty preparations as in solids, liquid products are often much more dilute, so that the proportion 30 of water or other solvent or mixture of solvents present can be much higher. In certain aspects of the invention, the components can be added directly to the wash water, in which case it may be considered that the detergent position is the wash water containing the various active and other components.

In particular solid detergent compositions.

ir 9 laires and other solid detergent compositions of this invention, the total proportion of detergent present is \ y: normally from 5 to 40 2, preferably from 5 to 30 2, more preferably from 10 to 25 2, particularly pre-5 13% 23% fairy, for example about 19 2. Such a detergent is normally an anionic detergent and among these the higher alkylbenzene sulfonates are preferred, for example, sodium tridylbenzene sulfonate. However, it may be present with other anionic detergents or it may be replaced in whole or in part by one or more of these other anionic products. The proportion of detergency builder of polyacetal-carbo-xylate type is usually from 5 to 50 2, preferably from 5 to 40 2, more preferably from 15 to 30 2 and, particularly preferably, from 17 to 23 2 , for example, about 19 2, when it is the only detergency builder present or - '* Γ' when up to 50 2 other detergency builder (s) than the zeolite is / are also present (s). When zeolite is present, the sum of the polyacetal-carboxylate and the zeo-lite is in the proportions given above for the polyacetal-carboxylate alone and, if zeolite is present, the polyacetal-carboxyla represents you at least 5 2 of 1 has a detergent composition. Likewise, the ratio of the polyacetal carboxylate to the zeolite is in the range of 1: 3 to 3: 1, preferably 2: 3 to 2: 1 and more preferably about 3: 4 to 7 : 4, for example, from about 1: 1 to 3: 2.

The cationic compound which acts as an antistatic (and which also has softening properties) is present in an antistatic proportion in the compositions according to the invention, at least as far as certain materials are concerned. The present detergent compositions have been found to be particularly effective in reducing electrical charges (and resulting static adhesion) on acetate materials, but they are known to be effective against other types synthetic fabrics such as acryllous and polyester fabrics. The proportion i.

10: cationic antistatic product is usually in the range of 2 to 10%, preferably 3 to 8% and more preferably 4 to 6%, for example, about 4 or 5%. The humidity is normally 2 to 20%, prealy 5 to 3 to 15% and more preferably 5 to 12%, for example, about 6 or 8%. Such percentages include moisture in the form hydrate which is released during heating for 2 hours at 105 ° C (the standard method of moisture analyzer). The proportions of other components such as inert fillers are normally limited to 50% and are often in the range from 5 to 35%. Similarly, contents of non-phosphate detergency builders other than polyacetal carboxylate are limited, being generally less than 40 £, such as from 3 to 30% or from 5 to 25% , but no such additional detergency builders are required, however, the presence of other detergency and load builders inert is often desirable. Thus, sodium carbonate is a preferred non-phosphatic detergency builder, as is sodium silicate. Preferred silicas are the sodium salts in which the Na 2 OrSiOg ratio is from 1: 1.6 to 1: 3.0, preferably from 1: 2.0 to 1: 2.6, for example from 1 : 2.4. The proportions of carbonate and silicate, if they exist, can range from 3 to 25%, preferably from 8 to 18%, and more preferably from 1D to 15%, 25 and from 2 to 15 X, preferably from 5 to 10 %, and more preferably 6 to 9%, respectively. The proportion of inert filler, if present, is usually 5 to 35%, preferably 20 to 35%, and more preferably 22 to 30%.

The total content of additives usually does not exceed 10 or 20%, and is preferably less than £ 5, the separate contents of usual additives generally not exceeding 3 or 5%, and often preferably being less than 1 or 2%. For example, sodium carboxyethyl-lose sodium, which is a desirable anti-redeposition agent, is usually present in the range of i η 0.3 to 3%, preferably 0.5 to 2%, for example. example, of 1% * of the composition, when the latter is included.

In preferred embodiments of the invention, particulate solid compositions of particle size such as those described above, it is often preferred to spray-dry the formulation as much as possible in order to obtain spherical particles of substantially shaped constants. Since the cationic antistatic product can react with anionic substances such as with the anionic detergent, it is normally added later to the rest of the composition. To avoid segregation during transport and storage of the final product, it is desirable that all subsequently added components, such as the cationic compound, the polyacetal-carboxy1 a te and the enzyme, be in the form of dimensions. of particles and apparent density similar to * * those of the rest of the composition. However, even when this is not the case and when the materials added later are in finely divided form, such as di-20 particle sizes in the range of 95-44 µm, and higher bulk density, they can be added subsequently to spray dried beads or other particles of the basic detergent composition which has a larger particle size, and they frequently adhere to such particles to provide a desired product of dimensional range from 1.58 to 0.149 mm.

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The polyacetal carboxylate can sometimes be spray-dried with the detergent composition, provided that care is taken to prevent it from being decomposed by heat.

In a variant of the manufacturing process, the various components in finely divided form can be simply mixed together. Also, when the party dimensions

initial particles of the various components or of some of them are less than those desired, for example in the range of 110 to 44 μm, their particles can be agglomerated to the desired size, sometimes in the e-'re C ' eg agglomerating such as a muddy solution above.:. s 1 -: a te I

12 „of sodium, and other times with only water to facilitate agglomeration V Anionic detergent or the mixture of such detergents, which is / are the main detergent (s) 5 of the desired composition, can / can be spray-dried with inert fillers such as sodium sulphate, detergency builders such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and additives such as fluorescent optical brighteners, pigments and dyes, in a normal manner, using a conventional spray drying or counter-current drying column, with drying air entering around 200 at 600 ° C (Preferably 150 to 300 or 350 ° C when polyacetal-carboxyla is present). The polyacetal carboxylate and the antistatic product can then be mixed by adding them either one

'i-V

after the other either simultaneously, or the antistatic product and the polyacetal-carboxylate can be mixed beforehand and then mixed with the beads dried by atomization. When a relatively small proportion of non-ionic detergent is to be present with the anionic detergent, it can be spray dried with this anionic detergent, inert fillers, etc., and other stable substances which must be present can also be used. be incorporated in the "mixer" 1 and then be spray-dried with the anionic detergent. However, when more than approximately 4 or 5% (sometimes more than 2%) of nonionic detergent are present in the formula, any additional proportion is usually added later, as by spraying on particles of pearls of detergent in motion. The polyacetal carboxylate and the antistatic product can then be added later. In some cases, the polyacetal carboxylate may be dispersed and / or dissolved in the ionic detergent which is heated so as to be in the liquid state (or which may be dissolved in a solvent) and the combination nonionic detergent 13 and polyacetal carboxylate can be sprayed onto the detergent beads or the base beads, "which is followed by the addition of the cationic antistatic product. It is desirable that the particulate material prepared is of particle sizes in the range of 2.38 to 0.120 mm or 1.68 to 0.149 mm and the manufacturing process is designed accordingly, however screening can be used to remove particles that are too small or too large which can be reworked, crushed, agglomerated or otherwise treated to arrive at the desired dimensions (sometimes corresponding to 2.38 â; 0.177 mm).

In order to manufacture the present products in the form of bars, breads or bricks, the compositions can be extruded, compressed or molded to the desired shapes according to known methods. To convert them into liquid preparations, the components can be dissolved and / or dispersed! in liquid media such as water and / or one or more suitable solvents such as ethanol, glycerol and isopropanol.

In order to practice the methods for removing stains and stains of the invention, which result in non-adherent and clean (and also soft) washed articles, one of the compositions described can be added to a washing water or well we can add the different components as well.

i: 25 Normally, the concentration of the compositions used is from 0.05 or from 0.1 to 0.4 or 0.5% t, preferably from 0.1 to 0.35 £, and more preferably from 0.15 to 0 , 25 or 0.35%. Higher concentrations such as 0.25-0.45% or more (and less wash water) are often used in machine washes following European practice which normally uses higher wash water temperature. In American practice, lower concentrations of the compositions are used, such as from 0.05 to 0.25%> often preferably around 0.1 to 0.2%.

35 Usually the washing temperature in America is from 10 to 55 PC, preferably from 35 to 55 CC, compared to 14 60 to 99 6C, often from 70 to 90 or 95 ° C in Europe. However, it is considered that the compositions of the present invention can be used to remove stains and stains from laundry from different types of fabrics and materials, and to result in such a laundry free of static charges and soft, whatever the washing method used.

In carrying out the present invention, sufficient detergent composition according to the invention is added to washing water in a conventional household washing machine (industrial machines can also be used) in the desired proportion in the limits given, for example, 0.2% (130 g per 65 liters of wash water), to wash water at normal wash temperature, for example, 49 ° C, and of normal hardness ( at around 50 to 250 or 300 ppm, expressed as calcium carbonate). The linen is then added, the normal loading weight -3 ranging from 2.7 to 4.5 kg, for example 3.6 kg. Washing of the laundry is carried out in a normal cycle of 2 to 30 minutes, for example 5 to 20 minutes, as desired, usually depending on the soiling of the laundry. Surprisingly, the compositions of this invention have, in relatively soft water and in water of medium hardness, of hardness from about 50 to 150 ppm, about the same stain and soil removal properties. than control compositions in which the polyacetal-carboxyla is replaced by an equal (even greater) proportion of sodium tripoly-phosphate, but they are clearly better than these at higher hardnesses (250 ppm). Also, terry cloth towels washed either with a composite according to the invention or with a control composition (the composition according to the invention contains polyacetal-carbo-xylate and zeolite and in the control composition these are replaced by an equal weight of sodium tripolyphosphate) appear to have about the same flexibility and the same overall electrostatic charges. However, such compositions according to 1 * * enti or are clearly superior to

F

F

15 * ^ riors to the witness with regard to the decrease in the electrostatic charge {and the decrease in the adhesion of tis- 'J ".

"I sus) for acetate fabrics.

♦

The invention is illustrated with the aid of the following examples which are not limiting. Unless otherwise indicated, all parts represent weights and all temperatures are given in DC, in these examples, in the rest of the specification and in the claims.

EXAMPLE 1 10 Percentage component

Linear sodium tridecylbenzene sulfonate 19.0 Builder U (79.7% sodium polyacetal carboxylate, supplied by Monsanto Co (lot N ° 2538422, weighted average molecular weight calculated from 8,034) 23.8

Sodium carbonate (anhydrous) 12.4

Sodium silicate (I ^ OiSiOg = 1: 2.4) 7.6

Sodium sulfate (anhydrous) 26.7

Water 5.7 20 Distearyl dimethyl ammonium chloride (Arosurf TA-100, about 90% active, supplied by Sherex Chemical Company) 4.8 100.0

A particulate detergent in the form of spray-dried beads consists of all of the above components except the cationic compound by preparing an aqueous mixture of "mixer11 (solids concentration = 55%) consisting of the components listed at one temperature of about 55 ° C and spray drying.

30 such mixture of "mixer". The drying column used is a counter-current column operating under mild conditions, with drying air at an inlet temperature of approximately 300 ° C. and taking other measures to prevent the pearls from carbon and decomposition 3- of sodium polyacetal carboxylate (preventing the formation of deposits on the walls of the column, using 16 cooling air and controlled spraying to avoid contact of material sprayed with the walls - r · y of the column). The resulting product has particle sizes in the range of 1.68 to 0.149 mm, an apparent specific mass of about 0.3 g / ml and has a moisture content of about 8 %. A part of the product Sherex Chemical Co described is mixed with 20 parts of the detergent composition thus prepared. It is desirable that such a product have particle sizes similar to those of the basic detergent composition, but even when it is finer powder, with particle sizes of 149 to 44 µm, the product antistatic is well distributed within the detergent composition and it adheres to the particles thereof, providing a product which is always in the range of di-15 mensions from 1.68 to 0.149 mm and which still has an apparent specific gravity d '' about 0.3 g / ml. The prepared product is examined from the point of view of removing stains and soiling, using a Tergotometer laboratory type test washing machine in which standardized batches of various materials, stained and soiled in a standardized manner , are washed in washing water at a composition concentration of 0.21%, at a washing temperature of 49 ° C, and for a washing time of 10 minutes, with the agitator rotating at 100 revolutions / minute. The hardnesses of the water used are hardnesses of calcium and magnesium in the Ca: Mg ratio of 3: 2, at hardnesses of 50, 150 and 250 ppm.

Readings of the reflectance of the washed and dried batches are taken and indices indicative of the weighted sums of the reflectances are calculated, which indices, based on experience, have been found to be representative of the stain removal capacity and soiling of a detergent composition examined (the higher the index, the better the detergency). At hardness levels of 50, t ': - 150 and 250 ppm, the experimental product of this previously described example gives indices of 256, 242 and 234 respectively. When the same composition is prepared with • r

HE

17 sodium tripolyphosphate replacing Builder U in the formula (which gives a product with an adjuvant content higher than that of the experimental formula) the indices are 254, 240 and 5 222 respectively. It is therefore seen that the efficiency of stain removal and cleaning of the composition according to the invention in hard water (hardness 250 ppm) is greater than that of a control composition which contains penta-sodium tripolyphosphate , the most successful commercial detergency builder in this field, even when more polyphosphate is used in the control composition.

EXAMPLE 2

When half of Builder U is replaced in the formula of Example 1 by Zeolite 4A (hydrated at 20%), which is added to the "mixer" in the form of a finely divided powder having a particle size in the range of 149 to 44 µm, and that the quaternary ammonium halide is mixed with the spray dried beads as described in Example 1, the resulting antistatic detergent composition was essentially the same cleaning properties (as measured by the same stain and soil removal index) as a control composition based on detergency builder of the sodium tripo-lyphosphate type in place of Builder U and zeolite.

Likewise, when examined from the point of view of the electrostatic charge, which reveals the "adhesion" of washed materials, the product according to the invention, containing Builder U and zeolite, gives essentially the same improvement. given by the "control", in comparison to detergent comparisons which do not contain the cationic compound. There is superiority in the reduction of electrostatic charge for acetate tissues with the experimental formula, compared to a control containing as detergency adjuvant of sodium tripolyphosphate and the composition

35 cationic mentioned (but not Builder U or zeolite). Thus, after washing with the compositions subject to c: .r- J

fi; i: »* j * 18 parison and drying in an automatic dryer, the acetate batch has an electrostatic charge of 5.5 kV after washing with the control, and 1.6 kV after washing with the experimental product according to the invention, and similar drying.

5 When examining their softening properties, the mentioned control composition and the mentioned experimental composition rank about the same in a test in which six people arranged, in the softest and roughest way, a series of towels terry cloth washed with either of the compositions. The conditions of the test are the same as those described above for the examination of the detergency, except that small washing loads are used (approximately 0.5 kg of loading for 65 1 of washing water) and lower the concentration of the detergent composition to 0.15% (100 g in 65 l of washing water).

In another modification of this example, we bring the proportions of Builder U and zeolite to 3: 2. The stain and soiling removal indices obtained are essentially the same as those of the control which instead contains as a detergency builder for the polyphosphate.

From the above experiments, it appears that the experimental compositions of these examples are equal to or better from the standpoint of removing heavy stains and soiling, reducing electrostatic charge and softening properties, compared to a control composition in which sodium tripolyphos-phate is used in place of Builder U or in place of a mixture of Builder U and zeclite.

It is believed that such results can also be obtained when changes are made to the experimental formula and / or when changes are made in the manufacturing and / or washing processes. Thus, the anti-static product mentioned can be replaced by other similar substances, such as di (hydrogenated tallow) -dimethyl ammonium chloride, the corresponding quaternary ammonium tates and other agents. known antistatic agents. Likewise, when sodium tridecylbenzene sulfonate is replaced by other higher water-soluble alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate or mixtures of linear tridecylbenzene sulfonate sodium and sodium auryl sulfate (in equal parts) or by other anionic detergents as described above, satisfactory products within the scope of the invention can thus be obtained. The particular sodium polyacetal-10-carboxylate can be replaced by other similar products of different molecular weights, for example, by that having a molecular weight of 5,250 (Monsanto, lot No. 2547321) or by other compounds similar in the given molecular weight ranges and having the end groups described, and useful antistatic detergents are obtained. Similarly, we can change the detergency adjuvants,, the inert fillers and the additives, as described here. For example, Zeolite 4A can be changed for other A zeolites or for X and / or Y zeolites.

In addition, the proportions of the various components can also be changed, usually ± 10 or ± 25%, without losing the advantages of the present invention, as long as the proportions remain within the above ranges.

In modifications to the manufacturing process, the compositions described are prepared by subsequent addition of Builcer U powder, in particles having the size of spray-dried beads or more finely divided (from 149 to 44 µm), to the beads dried by atomization, before, after gu at the same time as particles of antistatic product of similar dimensions or in finely divided powder. The polyacetal-carboxylate can be mixed beforehand with the antistatic product and then be mixed with the spray-dried product. In some aspects of the invention, the separate components can be mixed with each other without the majority of them being spray dried. In some cases, the various components can be added to the wash water as individual charges. In a preferred method, the polyacetal carboxylate is added later rather than spray-dried with various other components of the final product, in order to better maintain all of its effectiveness in detergent charging and in reducing electrostatic charge (in particular avoiding subjecting such a detergency builder to heat which may be excessive and thereby causing its degradation). When such a change is made in the manufacturing process described, the product obtained is equal or superior in terms of the characteristics described compared to those indicated above here. In the processes described, the products obtained have an apparent specific gravity of 0.25 to 0.5 g / ml, like the spray-dried pearls, both have particle sizes in the range * of 1, 68 to 0.149 mm, while the detergency builder of polycarboxylate and the antistatic product consisting of distearyl dimethyl ammonium chloride usually have a higher apparent specific gravity (from 0.6 to 0, 9 g / ml) and have smaller particle sizes (149 to 44 µm). However, in the final compositions, the smaller particles satisfactorily adhere to the larger ones, to provide the desired product.

The washing method of this example can also be changed, such as by using water of various hardnesses mixed with calcium / magnesium from 50 to 250 ppm and even more, sometimes up to 300 ppm or more, and the washing can be carried out in the temperature range from 10 to 55 CC, 30 and at concentrations of the detergent composition from 0.05. * to 0.5% t and satisfactory antistatic effects are obtained without excessive loss of detergency, and the products may be equal to or greater than "controls" containing sodium tripolyphosphate in place of polyacetal-carbo-35 xylste or in place of a combination of this detergency adjuvant and zeolite. DD 21 EXAMPLE 3

15 parts of dodecylbenzene sulfonate, linear sodium and 25 parts of sodium tripolyphosphate are mixed with 4.5 parts of Arosurf TA-100 (90% distearyl dimethyl ammonium chloride 90%), all components being in finely divided powder form, with particle sizes in the range of 149 to 74 µm. One such product, the control, is used to wash terry towels, using essentially the same method as described in Examples 1 and 2. The towels are then evaluated by an expert and given a degree of 9 for softness on a standardized scale ranging from 1 to 10, 10 corresponding to the softest. In another control experiment, 3 parts of Arosurf TA-100 were used with the 15 and 15 parts of the other constituents, and a similar smoothness test was carried out. Washed towels are rated> 8 on this softness scale.

When, instead of the 25 parts of sodium tripolyphos-phate, 25 parts are incorporated into such a composition. 20 ties of Builder U (lot 2538422), and that the examination is repeated, the degree of sweetness obtained is 10 and such a degree is also obtained when the content of Arosurf TA-100 is reduced in the formula mentioned to 3 parts.

The compositions described according to the invention are all satisfactory detergents and they have good antistatic and softening properties.

Instead of dry mixing the various components, other compositions of this example can be produced by spray drying and other operations described in Example 1 and in the preceding specification. Also, the compositions mentioned can be used to wash stained and soiled linen and to soften it, and to reduce the static adhesion which normally results, after washing of such a linen, from its drying in a dryer. automatic laundry. Instead of using linear sodium dodecylbenzene sulfonate, linear sodium tridecylbenzene sulfonate, sodium lauryl sulfate and fatty alcohol polyalkoxy sulfates can be used. superiors, and Zêolite A or Zëolite X can-! "can be used to replace half of Builder U.

î | Likewise, other agents among the antistatic agents mentioned can be used in place of the Arosurf TA-100, and the various proportions can be varied as described above, resulting in satisfactory detergents with good antistatic and softening properties.

The invention has been described in relation to various 3! illustrations and achievements thereof but should not be limited to them because it must be obvious that a specialist, in view of this specification, will be! 15 suitable for using equivalents or substitutes! r tution without departing from the scope of the invention.

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Claims (11)

23 "_ 1. Particulate detergent composition, reinforced by antistatic detergency builders, comprising V · * 'a detersive proportion of an anionic organic synthetic detergent, a proportion enhancing the detergency of a suitable polyacetal-carboxylate detergency builder for this detergent (s) or a proportion enhancing the detergency of a mixture of a detergency builder of polyacetal-carboxylate type and of a detergency builder of zeolite type, and an antistatic proportion of an antistatic cationic compound. 2. A detergent composition according to claim 1, wherein the cationic antistatic compound is a quaternary ammonium compound. 3. The detergent composition according to claim 2, which is essentially free of phosphate, and wherein the synthetic anionic organic detergent is a sulfated or sulfonated detergent, the polyacetal-carboxylate type detergency builder has a weighted average molecular weight. calculated from 3,500 to 10,000, the zeolite-type detergency builder is a hydrated zeolite of type A, type X or type Y, and the quaternary ammonium salt is an upper dialkyl halide - lower dialkyl - ammonium , in which the upper alkyl radical has from 10 5 to 18 carbon atoms and the lower alkyl radical has from 1 to 3 carbon atoms. 4. The detergent composition according to claim 3, wherein the synthetic anionic organic detergent is a higher alkylbenzene sulfonate in which the alkyl radical contains from 10 to 15 carbon atoms, the polyacetal carboxylate is a polyacetal carboxylate in which the carboxylate is sodium carboxylate, the zeolite is a type A zeolite of formula 35 (Na20) x. (Al203) y. (SiO2) 2.wH20 in which x is 1, y is between 0.5 and 1.2 ,, 9 * 24 preferably equal to about 1, z is 1.5 to 3.5, preferably 2 to 3 or equal to about 2, and w is 0 'ji. to 9, preferably 2.5 to 6, and the quaternary ammonium salt is an upper dialkyl-dimethyl-5 ammonium halide in which the upper alkyl radical contains from 10 to 18 carbon atoms. 5. A detergent composition according to claim 4, which comprises about 5 to 30% of linear sodium higher alkylbenzene sulfonate in which the higher alkyl radical has from 12 to 14 carbon atoms, from 5 to 40% of detergency builder. polyacetal-carboxylate type or of a mixture of such an alkaline filler and of zeolite filler, from 2 to 10% of distearyl-dimethyl-ammonium chloride, from 2 to 20% of humidity and the rest, if exists, is made up of inert filler (s) and / or other adjuvant (s) and / or additive (s). 6. A detergent composition according to claim 5, which comprises from 10 to 25% of linear sodium tridecylbenzene sulfonate, from 15 to 30% of detergency builder 20 of polyacetal-carboxyla type with a weighted average molecular weight calculated from 5,000 to 9,000 or a mixture of such a detergency builder and zeolite-type detergency builder, at least 5% of the composition consisting of polyacetal-carboxy-25 late detergency builder , from 3 to 8% of distearyl dimethyl ammonium chloride, from 3 to 15% of humidity, from 8 to 18% of sodium carbonate, from 5 to 10% of sodium silicate with Na ^ OrSiO ^ ratio 1: 1.6 to 1: 3.0, and 20 to 35% sodium sulfate. 7 - detergent composition according to claim 6, 30 comprising from 13 to 23% of linear sodium tridecylbenzene-sulfonate, from 17 to 23% of detergency builder of polyacetal-sodium carboxylate type with a weighted average molecular weight calculated from approximately 8,000, from 4 to 6% T of distearyl dimethyl ammonium chloride, from 5 to 12 * 35 of moisture, from 10 to 15% of sodium carbonate, from 6 to 9% of silicate of sod'-m Na ^ OrSiO ^ ratio of 1: 2.0 to 1: 2.6, V t 9 25 and 22 i 30% sodium sulfate. * 8. A detergent composition according to claim 'J 6, comprising from 13 to 23% of sodium tridecylbenzene-linear sulfonate from 17 to 23% of a mixture of detergency builder 5 of polyacetal-sodium carboxylate type by weight calculated weighted average molecular weight of about 8,000, and type A zeolite where x is 1, y is 1, z is 2 to 3, and w is 2.5 to 6, in which mixes the ratio between the polyacetal-carboxylate type 10 detergency builder and the zeolite load is 2: 3 to 2: 1, 4 to 6% distearyl dimethyl ammonium chloride, 5 to 12% moisture, from 10 to 15% of sodium carbonate, from 6 to 9% of sodium silicate with Na 2 O: SiO 2 ratio of 1: 2.0 to 1: 2.6, and from 22 to 30% of sodium sulfate. 9 - process for the manufacture of a particulate anti-static detergent composition reinforced with detergency builders, which comprises a deter-sive proportion of synthetic anionic organic detergent, ur.e proportion enhancing the detergency of a deter-gence adjuvant of polyacetal-carboxylate type suitable for this detergent (s) or a proportion enhancing the detergency of a mixture of a detergency builder of the polyacetal-carboxylate type and of a detergency builder of zeolite type, and an anti-static proportion of an anti-static quaternary ammonium salt, which comprises spray drying an aqueous suspension of synthetic anionic organic detergent, inert filler and / or detergency builder suitable for this detergent and d to achieve essentially spherical beads having particle sizes in the range of 1.68 to 0.149 mm, and mixing with such spray-dried beads of adjuvant polyacetal-carboxylate type "etergence and antistatic proportion of antistatic quaternary ammonium salt. 10 - Process according to claim 9, in which the synthetic anionic organic detergent is a linear higher alkyl-e-rene sul sulate this sodium in which the upper alkyl radical contains from 12 S 14 carbon atoms , the polyacetal-carbon xylate-type detergency builder is a sodium polyacetal-carboxylate with a weighted average molecular weight calculated from 5,000 to 9,000, the detergency builder in the "mixer" mixture comprises a Hydrated zeolite A, sodium silicate having a Na 2 O: SiO 2 ratio of 1: 2.0 S 1: 2.6, sodium carbonate and sodium sulfate, the detergency builder of polyacetal-carboxylate type and anti-static quaternary ammonium halide are mixed beforehand and added to the spray-dried beads, and the resulting detergency composition comprises from 13 to 23% of sodium linear tri-decylbenzene sulfonate, from 17 to 23% of a total polyaceta type detergency builder l-15 carboxylate of a weighted average molecular weight calculated of about 8000, and of detergency builder of the type * Zeolite A, the ratio between the polyacetal-carboxylate and the zeolite being from 2: 3 to 2: 1, from 4 to 6% of distearyl dimethyl ammonium chloride, from 5 to 12% of humidity, from 20 to 15% of sodium carbonate, from 6 to 9 2 of sodium silicate with Na20 ratio : Si02 from 1: 2.0 to 1: 2.6, and from 22 to 30% sodium sulfate. 11. The method of claim 10, wherein the apparent specific mass of the spray-dried beads is 0.25 to 0.5 g / ml, the apparent specific mass of the polyacetal -carboxyl ate detergency builder mixture. of antistatic distearyl dimethyl ammonium chloride and sodium being greater than the bulk density of the spray dried beads, and such a mixture having particle sizes in the range of 149 to 44 µm. 12. A method for removing difficult-to-remove stains and stains from fibrous materials, which comprises washing such stained and soiled materials in water of mixed hardness of calcium and magnesium from 50 to 250 ppm, expressed as calcium carbonate, at a tempe-. W t 27 "rature in the range of 10 to 55 ° C, and at a concentration of 0.05 to 0.5%, with a composition comprising a detersive proportion of anionic detergent, a proportion enhancing detergency of a polyacetal-carboxylate detergency builder suitable for this detergent or a proportion enhancing the detergency of a mixture of a polyacetal-carboxylate detergency builder and a detergency builder of the zeolite type, and an antistatic proportion of a cationic antistatic compound. TO 13 - The method of claim 12, wherein the temperature of the washing water is in the range of 35 to 55 ° C, the concentration of the detergent composition in the washing water is 0.1 to 0.35%, and the detergent composition comprises from 13 to 23% of linear sodium tridecyl-ben-zene-sulfonate from 17 to 23% of a mixture of detergency builder of polyacetal-carboxyl type ate-de sodium of a calculated weighted average molecular weight of about 8,000, and of type A zeolite, in which x is 1, y is 1, z is 2 to 3 and w is 2.5 to 6.20 in which the ratio of the polyacetal-carboxylate type detergent builder to the zeolite type detergency builder is 2: 3 to 2: 1, from 4 to 6% of distearyl dimethyl ammonium chloride, 5 to 12% moisture, 10 to 15% sodium carbonate, 6 to 9% sodium silicate with Na ^ OrSiO ^ ratio of 1: 2.0 to 1: 2.6, and 22 to 30% sodium sulfate. 14. The method of claim 13, wherein the washed materials consist of cellulose acetate. I! V,