LU85926A1 - SYNTHETIC DETERGENT COMPOSITION REINFORCED BY A DETERGENCE ADJUVANT AND WASHING METHOD - Google Patents

Description

* * The present invention relates to a synthetic organic detergent composition reinforced with a detergency builder. More particularly, it relates to such a composition containing a proportion with reinforcing effect 5. of a detergency builder of the polyacetal-carboxylate type of lower molecular weight suitable for the synthetic organic detergent. The invention also relates to methods for washing soiled fibrous materials in which the compositions described or their components are used. Synthetic organic detergent compositions in which anionic and / or nonionic detergents have been used as detersive components and containing mineral or organic detergency builder salts have been on the market for a long time. Among the synthetic organic detergents, those which have generally been preferred in the past were anionic detergents, but non-ionic detergent compositions and mixed anionic-nonionic products have also been successfully marketed. Various organic and mineral salts as adjuvants for detergency have been incorporated into commercial detergent compositions for washing household laundry and, among them, until very recently, the tripolyphosphate was almost invariably preferred. sodium. This polyphosphate is an excellent detergency builder which is sDr for the user and inexpensive, while still being extremely effective for the expected strengthening. However, in recent years phosphorus has been discredited for polluting inland waters by eutrophication and, for this reason, its use in detergent compositions has been regulated, limited or prohibited by various political jurisdictions. Therefore, efforts have been made to make phosphate-free detergent compositions which are, however, effective as very strong detergents.

35 Among the phosphate-free compounds that have been proposed for use as detergency builders in Λ 2. detergent compositions, there are polyacetal carboxyates. These compounds have been described in various patents of the United States of America and other countries. For example, detailed descriptions are given in U.S. Patents 4,144,226 and 4,146,495. Normally, according to these patents, the molecular weights of these materials are within the range of 1000 to 40,000 or more, preferably 1000 to 20,000, and more preferably 5000 to 10,000. However, although the anionic and nonionic synthetic organic detergents and the polyacetal carboxy-lates of the present invention have been described in the prior art as components of detergent compositions, the prior art in question has not suggested or made evident the use of a combination of synthetic organic detergent having an ethoxy group with a polyacetal- carboxylate whose molecular weight is in a relatively narrow low range. These compositions have, according to the Applicant, better cleaning effects, they better remove difficult-to-remove dirt and stains from various fibrous substrates during washing with cold water in water of medium hardness, compared to similar compositions. containing a polyacetal carboxylate of higher molecular weight, and they are also superior to control compositions in which the polyacetal carboxylate is replaced by a detergency builder of the polyphosphate type.

According to the present invention, a synthetic organic detergent composition reinforced with a detergency builder, useful in particular for washing laundry in cold water with a hardness of between 50 and 150 ppm expressed as calcium carbonate equivalent, comprises 5 to 30% of a synthetic organic detergent chosen from anionic and nonionic synthetic organic detergents and mixtures thereof, which detergent (s) contain at least one ethoxy group per molecule, 5% 95% detergency builder of the polyacetal-carboxylate type having an average molecular weight by weight calculated from 3000 to 6000, the possible remainder of the said composition consisting of one or more additives and / or one or several inert fillers and / or one or more detergency builders and / or one or more diluents, preferably the anionic detergent is an ethoxylated sulfated higher fatty alcohol and the nonionic detergent is a product of co ndensation of ethylene oxide and of a higher fatty alcohol Although detergent compositions in particles are preferred, these compositions can also be presented in other forms, for example breads, cakes, liquids, pastes and powders. When making particulate products, various processes can be used, for example spray drying, spray cooling, agglomerate, granulation, fine grinding and compaction.

The invention also contemplates methods for washing soiled fibrous materials using the described compositions for washing the soiled materials in wash waters of 50 to 150 ppm hardness and at temperatures of 10 to 70 ° C, preferably 10 to 30 ° C. In addition, the methods of washing the laundry with the synthetic organic detergent and the polyacetal-carboxylate of the compositions described form part of the present invention.

Although minor amounts of ca-ionic and / or amphoteric detergents may be present in the compositions of the present invention, they are normally limited to a total of 10%, and preferably they are maintained at less than 5%, at least. when such detergents are used. The main detergents used according to the present invention are anionic and / or nonionic. Among the anionic detergents, the sulfated and / or sulfonated lipophilic materials generally having an alkyl chain of 8 to 20 carbon atoms, preferably from 10 to 18, and better still from 12 to 16, are chosen. Although various cations forming water-soluble salts can be used to form the desired sulfated and sulfonated detergents, e 4 t: including ammonium and a lower alkanolamine (eg triethanolamine) and magnesium, an alkali metal such as sodium is generally used or potassium, and very particularly such a cation is sodium.

5. Among the various anionic detergents which are useful in the practice of the present invention, mention may be made of (linear upper alkyl) benzene sulfonates, monoglyceride sulfates, sulfates of higher fatty alcohols, paraffin sulfonates and olefin sulfonates.

In all of these compounds, the alkyl group (or aryl for monoglyceride sulfates) present has 10 or 12 carbon atoms. Although some of these alkyl groups may have branching, they still have a carbon chain length in the range described. Although the anionic detergents mentioned are useful in the practice of the invention, the one which is considered to be the most useful and effective, in combination with the detergency builder of the polyacetal-carboxylate type, is a detergent anion which has an ethoxy group. Among them, particularly preferred are the polyethoxylated, sulfated higher alkanols in which these alkanols can be synthetic or natural, and which contain 3 to 20 or 30 ethoxy groups per mole. Preferably, these detergents are alkali metal salts, for example sodium salts, their higher fatty alcohols have 12 to 18 carbon atoms, and the detergents contain 3 to 12, preferably 3 to 7, for example 3 or 5 molar proportions of ethoxy groups per .mol e.

Nonionic detergents, which can be used as main detergents in place of anionic detergents, or can be used with anionic detergents, are preferably normally solid materials (especially when incorporated into solid products compact or particulate) and are preferably condensation products of ethylene oxide and higher fatty alcohol, higher fatty alcohol generally having 10 S 18 carbon atoms, to prefer “- m-yen - 5 ne of 12 to 15 carbon atoms, for example about 12 or 13 carbon atoms, and the content of ethylene oxide being from 3 to 20 moles, preferably from 3 to 12 moles, and better still from 5 to 9 moles, for example from about 6.5 to 7 moles of ethylene oxide per mole of fatty alcohol. Among the other nonionic detergents which are also useful, mention may be made of the condensation products of ethylene oxide and of alkylphenol s having 5 to 12 carbon atoms in the alkyl groups, for example nonylphenol, in which the ethylene oxide content "* 0 is 3 to 30 moles. In addition, it is possible to use condensation products of ethylene oxide and propylene oxide, such as those sold under the trademark of ® manufactures Pluronic , as well as various others belonging to the well known group of nonionic detergents in which a pop 1 hil group such as a higher alkyl, alkyl phenyl, polyoxy (lower alkylene) group, for example polyoxypro-pylene, is linked to a polyoxyethylene-ethanol by reaction with ethylene oxide.

The polyacetal carboxylate can be considered to be of the type described in the U.S. Patent. No. 4,144,226 and it can be manufactured by the process mentioned therein.

This type of product corresponds to the formula: R, - (CH0) n - R2 -

25 COMM

in which M is chosen from the class consisting of alkali metals, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraal kyl ammonium groups and alkanolami groups, both having 1 to 4 carbon atoms 30 in their alkyl portion; n is on average equal to 6; and R.j and F * 2 represent all chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. Preferably, the polyacetal -carboxyl ate is one of those in which M is an alkali metal, for example sodium, R-j is represented by 6 ch3ch2o mooc HÇO- or H3C-CO-

H3C MOOC

5 or their mixture, is represented by och2ch3

-CH

ch3 10 and n is on average between 15 and 120, preferably between 40 and 70. The calculated weight average molecular weights of the polymers are normally in the range from 3000 to 6000, preferably from 4000 to 6000, and better 15 again from 4500 to 5500, for example around 5250.

Although the preferred polyacetal carboxylates have. have been described above, it is obvious that they can be replaced totally or partially, at least in part, by other polyacetal carboxylates of this type or by related organic detergency builder salts described in various Monsanto patents. Co. concerning such compounds, processes for their manufacture and compositions, if they have the same molecular weights. The various chain termination groups described in the various patents, in particular US Pat. No. 4,144,226, can be used, provided that they have the required stabilizing properties, which allow the mentioned detergency builders to be used. be depolymerized in acidic media, to facilitate their biodegradation in waste streams, but which retain their stability in alkaline media, such as washing solutions.

In the compositions of the invention, detergency builders other than the polyacetal carboxylate may also be present although they are not essential. It is often desirable to avoid the presence of 7 phosphorus in the detergent compositions, so that the polyphosphates, which have been the detergency builders of choice in the detergent technique for many years (in particular tripolyphosphate penta-5 sodium) will preferably be omitted in these formulations. In certain cases also, they may be present, at least in relatively small proportions, for example reaching 5 or 10%. Among the detergency adjuvants other than polyphosphates such as sodium polyphosphate and tetqasodium pyrophosphate, those which can advantageously be incorporated into the present compositions to complement the reinforcing action of po-lyacetal-carboxyla include sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, zeolites, e.g. Zeolite A, NTA, sodium citrate, sodium gluconate, borax, other borates , and other detergency builders known in the art of detergents. Inert fillers may be present, such as sodium sulfate and sodium chloride, to give volume to the product when considered desirable. In liquid compositions, which are generally to be used soon after manufacture, diluents such as solvents, dispersants, extenders and antifreezes, may be present, as well as additives such as buffers, thickeners and stabilizers. Typical diluents include water, ethanol, isopropanol, and propylene glycol, and additives include gums, clays, polymers, and salts.

Among the various other additives which may be used in the particulate compositions (some of which may also be used in liquids) are dyes, such as soluble dyes and pigments, perfumes, enzymes, stabilizers, activators (in particular, activators causing the release of active oxygen from the perborate possibly present), fluorescent brightening agents, fungicides, germicides and flow promoting agents. Additives also include, unless mentioned in other classes previously mentioned, various other components or impurities which may be present with other ingredients. For example, it is known that sodium carbonate and water are often present with polyacetal-carboxylate in "Builder U", the product which is the present source of polyacetal-carboxyl ate.

The solid (including particulate) compositions of the invention generally contain moisture, either in the form of free moisture, or in the form of one or more hydrates. Although moisture is not an essential component of these improved detergent compositions, = it is normally present as a result of the use of water in manufacturing, and it can help dissolve and bind the other components of the composition together, as is generally desired.

The proportion of total synthetic organic detergent may be a proportion with detergent effect up to 40 2 of the present compositions, but normally it is from 5 to 30 2, preferably from 5 to 25 2, and better still from 10 to 20 2, for example approximately 15 2. These proportions normally apply either for the anionic detergent of the type (polyethoxylated higher fatty alcohol) sodium sulfa, or for the nonionic detergent which is a condensation product of 'higher fatty alcohol and ethylene oxide, or for a combination of the two. When combinations of these two detergents are used, their proportions are generally in the ratio range of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, and more preferably 1: 2 â 2: 1, for example 1: 1. In such compositions, the proportion of polyethylenated higher fatty alcohol sulphate is generally from 2.5 to 27.5 2, preferably from 3 to 12 2, 35 and better still from 5 to 10 2. The percentages of this product condensation of higher fatty alcohol and this polyoxyethylene in these compositions are the complements of the percentages of such an anionic detergent, these percentages of nonionic detergent being included in the same ranges as previously indicated for the anionic detergent, the ratio 5 (ju anionic detergent to nonionic detergent being located in the ranges of ratios mentioned, and the total of anionic and nonionic detergents being proportions with detersive effect included in the ranges indicated above.

1® The proportion of detergency builder of the polyacetal-carboxylate type is a proportion with reinforcing effect (or is such a proportion by association with any other detergency builders which may be present). The detergency builder of the polyacetal-carboxylate type can constitute 5 to 95% of the composition, preferably 10 to 50%> and better still 15 to 40%, and in particular approximately 20 to 30%, for example approximately 25 %. This concentration is based on the active polymer, which normally constitutes approximately 80 to 87% of the available sources of detergency builders of the polyacetal-carboxylate type, 83% for Lot No 2547312 of "Builder U" (supplied by Monsanto Company) which has a calculated weight average molecular weight of 5250 and which contains 3.9% sodium carbonate, the remainder being mainly water.

The ratio of synthetic organic detergent to polyacetal carboxylate is normally in the range of 1:10 to 2: 1, preferably 1: 5 to 1: 1, more preferably 1: 3 to 4: 5, for example 5: 8. These reports take into account detergents other than those containing at least one ethoxy group per molecule but which, when present, constitute only a minor proportion, preferably less than 1/5, and better still less than 1 / 10 total detergent.

The other components of the present compositions, in addition to the synthetic organic detergent (s) and the polyacetal carboxylate (s), consist of one or more other detergency builders, and / or one or more inert fillers and / or a or more solvents and / or one or more diluents and / or one or more dispersants -and / or one or more other additives. Although technically only the detergent and the polyacetal carboxylate are the necessary components of the invention in its broadest aspects, other materials are normally also present for their complementary properties. Any additional detergency builder materials which may be present are normally limited to 50%, preferably 2 to 3 or 40 to 40%, and more preferably 5 to 30%. Among the preferred additional detergency builders are sodium carbonate, sodium bicarbonate, Zeolite A (but other zeolites can also be used), sodium silicate with Na20: SiO2 ratio from 1: 1.6 to 1: 3.0, preferably from 1: 2.0 to 1: 2.6, and in some cases (although not preferred), polyphosphates such as tripolyphosphate sodium and tetra-sodium pyrophosphate. The proportions of these individual components are generally limited to 30% t and preferably do not exceed 20%. The proportion of sodium carbonate which can be used is preferably from 5 to 15%, and the amount of sodium silicate is preferably from 3 to 12%. If phosphates are present, their proportions are preferably limited to 10% or less.

The inert filler content of the present formulations is generally not more than 70 2, and is preferably 10 and 60 2, more preferably 10 to 40 2. Although this inert filler is generally sodium sulfate , it can also include a minor proportion, 50 less than half, of other inert fillers such as sodium chloride.

The other additives of the compositions of the invention normally constitute a total not greater than 20 2 and preferably do not exceed 10 2 (except that if a bleaching material is used, such as sodium perborate, it may constitute up to approximately 30 2 of the product), η and preferably the total content of other additives is less than 5%, the contents of individual additives generally not exceeding 3% or 5%, and preferably being less than 1 or 2 %. Thus, if a sodium soap of a higher fatty acid (10 to 18 carbon atoms) is present (for its foaming reduction property), it could be advantageous to use 1 to 4% and if the the sodium salt of carboxymethylcellulose (as anti-redeposition agent) is used, its proportion can be from 0.3 to 3%, preferably about 1%. In liquid preparations, very porous silica such as those sold under the trademark Cab-0- © can be used.

If 1 in proportions of 0.5 to 5% to help keep the polyacetal carboxylate in suspension, and 1 to 5% of one or more hydrotropes, such as sodium xylene sulfonate, may be present to promote physical stability and uniformity of the product. The moisture content of the products of the invention is generally from 3 to 20%, preferably from 5 to 15%, and better still from 5 to 12%, for solid particulate products, and for liquids, can increase the proportions in the range from 20 to 90%, preferably from 25 to 70%, and more preferably from 30 to 60%. Some of the water in liquid (or paste) preparations can be replaced by other solvents, the percentages of such other solvents, if any, (such as ethanol) in the final product are normally from 2 to 30. %, preferably from 5 to 20%. These complementary solvents can help the solubilization of the components of the composition and they can be used to adjust the viscosity of the product.

The manufacture of the compositions of the invention can be carried out in any suitable conventional manner, whether solid or liquid products are produced. For the liquid products, the diluent (solvent or dispersant) can be added with the various components, preferably normally with a hydrotrope or other dispersant, for the polyacetal carboxylate and all other insoluble materials, which is found in the liquid medium when the various components are added to it and mixed. The addition can be sequential or simultaneous, sequential addition being the usual practice. The order of additions normally followed 5 is not of great importance but in general, all dyes and fragrances are added towards the end of the process. Often, the viscosity adjusting materials are added after the other components. In some cases it may be desirable to keep some of the solvent for final addition, so that a final dilution of the mixture can be obtained, when desired. Various types of mixers can be used and, in some cases, it is preferred to use mixers; homogenizers. Instead of the liquid form, with viscosities in the range allowing easy flow, which can be; Being distributed by a bottle with a narrow neck in a practical way, it is possible to produce pastes which cannot flow which normally comprise higher proportions of a thickener and often of less proportions of solvent or diluent.

To make the preferred particulate solid compositions, which have particle sizes of 0.125 to 2.38 or 0.149 to 2.00 mm, it is often preferable to spray-dry the formulation as much as possible so as to obtain particles. globulars of substantially uniform shape. Since the polyacetal carboxylate of the present compositions can be adversely affected by heat, it may be desirable to add it after the fact to the other components of the product which have been spray-dried beforehand to form the so-called "base" beads. If the polyacetal carboxylate is to be added after the fact, it is preferable that it has essentially the same shape, particle size and approximate density as the rest of the composition, so as to avoid separation during transport and storage. storage. However, even if a more finely divided polyacetal carboxylate-powder is used, for example with particle sizes ranging from 0.044 or 0.074 mm to 0.094 or 0.149 mm, it has been found that these particles often adhere to the larger pearls, main-5 held the product within the desired range of dimensions and essentially did not separate (although, of course, the results were not as good in this respect as when the various components of the composition were all of the same dimension, same shape and have the same apparent density).

If the polyacetal carboxylate is spray dried with the detergent composition, care should be taken to prevent its decomposition due to its exposure to the high temperatures of the drying air of the spray tower. When spray drying is not used or when costs are to be minimized, the various components of the compositions of the invention can be mixed together, in the form of powders, and can be agglomerated to the desired size from 0.149 to cv 2.00 mm, or they can be mixed together in the form of fine powders, generally ranging in size from 0.044 to 0.074, 0.094 or 0.149 mm. When the product must contain a non-ionic detergent in a significant proportion, its main proportion can be atomized after the fact on the beads spray-dried previously or on the particles of the other components of the composition. Normally, a spray dried product will not contain more than about 4% of non-ionic detergent, based on the final product, unless it is added after spray drying, due to the decomposition of the non-ionic detergent. ionic which can appear at the high temperatures prevailing in the tower when there is more than a relatively small proportion in the suspension of the mixer after spray drying. The very temperature-sensitive components of the product can also be added quickly so as to avoid (14) undesirable exposures to high temperatures. Thus, if the formulation is to contain a bleaching agent such as sodium perborate, it will be added afterwards, as well as the powdered enzyme, perfume and others = 5 heat sensitive components. In addition, materials such as mineral detergency builders, for example carbonate sodium, sodium bicarbonate, sodium silicate and zeolites, and inert fillers such as sodium sulfate, favor the production of spray-dried pearls, free flowing, resistant and interesting and are preferably incorporated in the mixer suspensions must be spray-dried to take advantage of their physical characteristics, as well as their reinforcing and filling role.

In carrying out the washing method of the present invention, in which soiled (and stained) fibrous materials such as conventional clothing and "linen" of cotton, polyester-cotton blends, polyesters, acrylic materials , in "nylon", in acetates, in rayon and their various mixtures, are washed in an aqueous washing medium, this medium contains a suitable detergent, as described, and a polyacetal-carboxylate having the desired calculated average molecular weight . Preferably, these components are part of a detergent composition, but the invention contemplates introducing these materials separately into the wash water. Although the effects of washing can be improved with the compositions described based on the aforementioned preferred nonionic detergent and this at intermediate or medium water hardnesses and also at higher hardnesses, during washing in both cold and hot water, the greatest improvements are achieved when the wash water has medium hardness. Also, when the detergent is the preferred anionic detergent, the greatest improvement is obtained for washing in cold water with water of medium hardness, washing in cold water with water of higher hardness being also improved, but not to a great extent. Thus, the preferred conditions for washing with the compositions of the invention, whether anionic, nonionic or anionic and nonionic and nonionic detergents are used, involve cold water (10 to 30 ° C.) medium hardness (50 to 150 ppm equivalent calcium carbonate). These preferences also apply when the active components are used and are added separately to the wash water of an automatic washing machine. However, in many cases, the wash water can have a higher hardness, for example 150 or 200 to 300 or 400 ppm, and can be at a higher temperature, often reaching 70 DC.

Preferably, the washing will be carried out with a detergent composition of the present invention and 0.05 to 0.5%, preferably 0.1 to 0.3%, and more preferably about 0.15% will be used. The wash water used will normally contain 0.0025 to 0.15% of the synthetic organic detergent (s) and 0.0025 to 0.475% of the polyacetal-carboxylate. Preferred ranges of these materials are 0.005 to 0.075% and 0.01 to 0.15% respectively, and, in the concentration of 0.15% of the composition, the preferred proportions of the detergent and the detergency builder polyacetal-carboxylate type will be approximately 0.0225% and 9 25 approximately 0.0375% respectively. The water used will advantageously have a hardness of 50 to 150 ppm and will be at a temperature of 10 to 70 ° C, preferably 10 to 30 ° C, for example 21 ° C. The hardness of the water will preferably be approximately 100 ppm of equivalent calcium carbonate (the ratio of the hardnesses of calcium to magnesium generally being from 1: 1 to 10: 1, for example from 3: 2 to 4: 1 ).

Under the conditions described, better cleaning is obtained using the preferred anionic and / or nonionic detergents of the present invention with the described low molecular weight polyacetal carboxylate. When, in such compositions, the polyacetal-carboxyla te * 16 of low molecular weight is replaced by a similar material, but of higher molecular weight (8034), the cleaning is considerably less good, in particular during washing in cold water in medium hard water. When using other detergents than those which have been recommended here with the polyacetal carboxylate described in the present invention, the results obtained are clearly lower than those obtained when the preferred detergents are used with the polyacetal- carboxylate. Also, with such other detergents, it was noted that the higher molecular weight polyacetalcarboxyl ate appeared to be slightly more effective than the lower molecular weight carboxylate, which is the opposite of the results obtained with relates to the compositions of the invention. Also, when the detergency builder of the present invention is replaced by the conventional and preferred detergency builder of the prior art, sodium tripolyphosphate, the washing results are much lower than those obtained in the present invention.

‘20 The following examples illustrate the invention without limiting it. Unless otherwise specified, all parts are expressed by weight and all temperatures are in ° C.

EXAMPLE 1 25 parts of Neodol ^ 25-3S, which is the sodium salt of an acid (polyethoxylated higher fatty alcohol (3 ethoxy groups) having on average 12 to 15 carbon atoms) -sul-furic, than l available from Shell Chemical Company, 30 parts of Builder U (Lot 2547313 containing 83% sodium polyacetal carboxylate of molecular weight 5250, 3.9% sodium carbonate, the remainder consisting primarily of water) and 55 parts of anhydrous sodium sulfate, are dissolved at a concentration of 0.15% in washing water (0.0225% of the detergent, 0.045% of the detergency adjuvant and 0.0825% of the inert filler being in water) At a temperature of 21 ° C. and a hardness of 17,100 ppm in equivalent calcium carbonate (the ratio. Ca: Mg in water being approximately 3: 2) , and the wash water is used to wash test batches showing various soils and stains on various fabrics serving as a substrate in a typical laboratory washing machine e Tergotome-ter, using a ten-minute wash cycle. The batches are dried and their reflectances to light are measured and, from these reflectances of all the stains and stains remaining on the different materials, the indices of removal of stains (and stains) are calculated. The higher the index, the whiter the test batch after washing and the more efficient the washing operation. This test is repeated with a conventional control detergent composition in which sodium tripolyphosphate replaces sodium polyacetaicarboxylate. We obtain a very significant improvement (plus 21) compared to the control. When this test is repeated except that anodic Neodol 25-3S is replaced by nonionic Neodol 25-7 (condensation product of seven moles of ethylene oxide with one mole 20 of higher fatty alcohol having on average 12 to 15 atoms carbon, which can be obtained from Shell Chemical Company), an even greater improvement (plus 23) is obtained. When sodium dodecylbenzenesulfonate with a linear dodecyl group is used as an anionic detergent in place of Neodol 25-3S, a decrease in washing efficiency is observed compared to the control. However, when the linear sodium dodecylbenzene sulphonate constitutes only a minor proportion, for example 1/10, of the anionic detergent present, the other detergent being Neodol 25-3S, a significant improvement in the detergent power is obtained by report to witness.

In the tests described above, when using a polyacetal carboxylate of higher molecular weight, Builder U Lot N ° 2538422, of molecular weight of 35 8034, S instead of the lower molecular weight material previously described, we still obtain 18 improvements over the witness, both with 1 es. fortnulations comprising Neodol 25-3S than with those comprising Neodol 25-7. However, the improvements are not as pronounced and it is evident that the washing methods using the lower molecular weight polyacetal carboxylate are markedly more efficient than those using the higher molecular weight carboxylate. , when the previous test, in which the linear sodium dodecylbenzene sulfonate is used, is repeated, but the higher molecular weight Builder U is used, the cleaning is lower compared to the control.

In the above experiments, when instead of adding the components separately to the wash water, they are first mixed together to form detergent compositions, either by mixing finely divided powders (particle sizes included between 0.074 and 0.149 mm) or by spray drying of the anionic detergent and the inert filler from mixtures of aqueous mixers to particle sizes of 0.149 to 2.00 mm, then mixing with the polyacetal carboxylate likewise particle size (and non-ionic detergent when used), ie by agglomeration of the finely divided powders of the components into particles of 0.149 and 2.00 mm, the cleaning results by the tests described are the same. Similarly, when the compositions are produced in liquid products, such as those in which water is substituted for the sodium sulphate constituting the inert filler, and when they are used at the same concentration in the washing water ( 0.15 ï), the same results are obtained.

Instead of using the "stripped" formulations previously indicated, it is also possible to obtain products which are aesthetically, functionally and commercially more acceptable, according to the methods previously described herein. Thus, a composition comprising 15 X of Neodol 25-7, 30% of Builder U (Lot 2547312), 10% ♦ 19 of carbonate. sodium, 10% sodium silicate (Na ^ O: Si = 1: 2.4), 1% sodium salt of carboxymethyl cellulose, 0.5% perfume, 10% humidity, the rest being sulfate sodium, is made by spray drying base beads made of all materials except non-ionic detergent and Builder U, spraying the molten non-ionic detergent on the base beads and mixing with the product Builder U in powder form to obtain particles of size between 0.149 and 2.00 mm. This product also has a higher cleaning power compared to a control of the type previously mentioned, and compared to similar products in which the batch of Builder U of higher molecular weight (8034) is used in place of the material of weight 15. lower molecular (5250). Similarly, when liquid compositions are produced in which part of the water is replaced by 10% ethanol, 3% xy-1ene sodium sulfonate (hydrotropic) and 0.5% perfume, which leaves 41.5% of water (preferably deionized), all these percentages being expressed on the basis of the composition, the same results can be obtained.

EXAMPLE 2

When the experiments with Neodol 25-7 of Example 1 are repeated, the only change being that the temperature of the washing water is 49 ° C., an even greater improvement in washing power is obtained compared to the witness. When the polyacetal-carboxylate of lower molecular weight from this experiment is replaced by the material of higher molecular weight (Lot N ° 30 2538422), it is found that the washing process with the poly- acetal-carboxylate of lower molecular weight is clearly better, as evidenced by the fact that its SRI value (soil removal index [and stains]) is significantly higher. This is also the case when the compositions of the invention, whether in the form of particles, solids, paste or liquid, are manufactured and tested in the same way.

EXAMPLE 3

When the experiments of Examples 1 and 2 are repeated using water temperatures of 10 to 30-30 eC, for example 15 ° and 25 ° C, and water hardnesses of 50 to 150 ppm, for example from 75 to 125 ppm, for the experiments of Example 1, and using temperatures from 40 to 60 ° C, for example from 45 ° to 55 ° C, and water hardnesses from 50 to 150 ppm, for example from 75 to 125 ppm, for the experiments of Example 2, the same significant improvements in washing power are obtained compared with the control and the same improvements in the effects of washing are noted when the lower molecular weight polyacetal carboxylates in place of higher molecular weight polymers.

EXAMPLE 4

Wash water with a hardness of 100 ppm, in equivalent calcium carbonate, which is at a temperature of 21 ° C., containing 0.0113% of Neodol 25-7 and 0.0113% of Neodol is prepared. 25-3S, 0.045% Builder U (molecular weight = 5250) and 0.0825% sodium sulfate. When the various soiled fabrics are washed in this washing water as described in Example 1, they are very well cleaned and their SRI values are higher than those provided by a control composition in which the Builder U is replaced by sodium tripolyphosphate. Also, these indices are higher than those obtained for similar washing waters in which the Builder U used has a molecular weight of 8034.

30 Similar results can be obtained when the -

Neodol 25-7 is replaced by Neodol 23-6.5 (a condensation product of one mole of higher fatty alcohol having 12 to 15 carbon atoms and 6.5 moles of ethylene oxide),

PIuronics (condensation products of ethylene oxide and pnopylene oxide), and condensation products of nonylphenol and polyoxyethylene-ethanol, and when 30 Z

* 21 of the sodium sulphate are replaced by 10% of sodium carbonate, 10% of sodium silicate and 10% of humidity.

EXAMPLE 5

When in the experiments of the preceding examples-_5 teeth, the proportions of the components are varied by ± 10% and ± 25% and when the concentrations in the washing water of such components vary by ± 10% or ± 25%, all remaining still within the ranges of proportions and in the percentages indicated in the present specification, the detergent compositions and the washing waters thus obtained have satisfactory washing properties, are superior to washing waters and similar compositions in which uses sodium tripolyphosphate in place of the lower molecular weight polyacetal carboxylate, and are superior to compositions in which the lower molecular weight material is replaced by higher molecular weight polyacetal carboxylate. This is also the case when various other detergency builders, including sodium bicarbonate, Zeolite 20 4A, sodium sesquisilicate and sodium citrate, are used in a total proportion with reinforcing effect, and when additives such as brighteners, enzymes, bleaches, clays, flow improvers and fabric softeners are also present in functional proportions.

It goes without saying that the invention is not limited to the embodiments described and that it is capable of various variants without departing from its scope.

Claims (17)

1. Synthetic organic detergent composition reinforced with detergency additives, useful in particular for washing laundry in cold water with a hardness of 50 * 150 to 150 ppm, expressed as equivalent calcium carbonate, characterized in that '' it comprises 5 to 30% of a synthetic organic detergent chosen from anionic and nonionic synthetic organic detergents and their mixtures, which detergents contain at least 10 ethoxy groups per molecule, and 5 to 95% of detergency builder polyacetal-carboxylate type having a weight-average molecular weight calculated from 3000 to 6000, the optional residue of this composition consisting of one or more additives, and / or one or more inert fillers and / or one or more detergency builders and / or one or more diluents. 2. A detergent composition according to claim 1, characterized in that the synthetic anionic organic detergent is a higher fatty alcohol sulfated ethoxylate and the synthetic nonionic organic detergent is a condensation product of ethylene oxide and a donor compound lipophilic groups chosen from higher fatty alcohols, alkylphenols and polyoxypropylenes. 3. Particulate detergent composition without phos-25 phate “according to claim 1, characterized in that the anionic detergent is an alkali metal salt of a sulfuric acid (polyethoxylated higher fatty alcohol) in which the fatty alcohol greater than 10 to 18 carbon atoms, and which contains 1 to 30 moles of ethylene oxide per mole, and in that the nonionic detergent is a condensation product of 3 to 20 moles of ethylene oxide and a mole of higher fatty alcohol having 10 to 18 carbon atoms and / or of a mole of alkylphenol having 6 to 12 carbon atoms in the alkyl group. 35 4 - Detergent composition according to claim 3, "* 23 f characterized in that it comprises 5 to 25% of polyethoxylated higher fatty alcohol sulfate and / or the condensation product of ethylene oxide and fatty alcohol higher, and 10 to 50% of detergency builder of the polyacetal-5 carboxylate type. 5. Detergent composition according to claim 4, characterized in that it comprises 10 to 20% of (polyethoxylated higher fatty alcohol) sodium sulfate which contains 1 to 5 moles of ethylene oxide per mole and in which 1 * a1 -10 cool higher fatty acids have on average 12 to 15 carbon atoms, and / or a condensation product of 5 to 9 moles of ethylene oxide with one mole of higher fatty alcohol having on average 12 to 15 atoms of carbon, and from 15 to 40% of polyacetal-carboxylate of molecular weight from 4500 to 5500. 15 6 - Detergent composition according to claim 5, characterized in that it comprises approximately 15% of (al- '* cool higher polyethoxylated fatty) sodium sulphate which contains approximately 3 moles of ethylene oxide per mole, and about 25% polyacetal carboxylate of molecular weight about 5250. 7. Detergent composition according to claim 5, characterized in that it comprises approximately 15% of a condensation product of ethylene oxide and higher fatty alcohol which contains approximately 7 moles of ethylene oxide. 25 per mole, and about 25% of polyacetal carboxylate of molecular weight of about 5250. 8. A detergent composition according to claim 5, characterized in that it comprises a (polyethoxylated higher fatty alcohol) sodium sulfate and a condensation product of ethylene oxide and higher fatty alcohol in a proportion of 1: 3 to 3: 1. 9. Detergent composition according to claim 8, characterized in that it comprises approximately 5 to 10% of (polyethoxylated higher fatty alcohol) sodium sulphate which contains approximately 3 moles of ethylene oxide per mole, approximately 5 to 10 % of a condensation product of approximately 7 moles * 24 of ethylene oxide and of a mole of higher fatty alcohol, and approximately 25% of polyacetal-carboxylate of molecular weight of approximately 5250. 10. A method of washing a soiled fibrous material 5. in order to remove the dirt, characterized in that it consists in washing this soiled fibrous material in washing water with a hardness of 50 to 150 ppm, expressed as equivalent calcium carbonate, at a temperature of 10 to 70 ° C, with a detergent composition reinforced by detergency builders 10 comprising 5 to 30% of a synthetic organic detergent chosen from anionic synthetic organic detergents and nonionic and their mixtures, which detergents contain at least one ethoxy group per molecule, 5 to 95% of a detergency builder of the poly-15 acetal-carboxylate type with a weight average molecular weight calculated from 3000 to 6000, the rest, if any of this composition consisting of one or more additives and / or one or more inert fillers and / or one or more detergency builders and / or one or more diluents, to a concentration of this detergent composition in water lava ge between 0.05 to 0.5%. 11. Method according to claim 10, characterized in that the detergent composition comprises 5 to 25% of a sulfated (polyethoxylated higher fatty alcohol) and / or of a condensation product of ethylene oxide and of alcohol higher fat, and 10 to 50% of detergency builder of the polyacetal-carboxylate type, the concentration of the detergent in the washing water being from 0.1 to 0.3% t and the temperature of the washing water being from 10 to 30 ° C. 30 12 - Process according to claim 11, characterized in that the detergent is a (polyethoxylated higher fatty alcohol) -sulphate of which the fatty alcohol greater than 10 S 18 carbon atoms and about 3 moles of ethylene oxide per mole, the proportion of such a detergent in the detergent composition is approximately 15 £, the polyacetal carboxylate has a molecular weight of approximately 5250, its proportion in the detergent composition is approximately 25%, the temperature of the washing water is about 21 ° C, the concentration of detergent composition in the washing water is about 0.15% and the washing water has a hardness -5 d '' about 100 ppm, expressed as equivalent calcium carbonate. 13. Method according to claim 1, characterized in that the synthetic organic detergent is a condensation product of 5 to 9 moles of ethylene oxide and of a 10 mole of higher fatty alcohol having on average 12 to 15 atoms of carbon. 14. The method as claimed in claim 13, characterized in that the non-ionic synthetic organic detergent has approximately 7 moles of ethylene oxide per mole, r the proportion of this detergent in the detergent composition is approximately 15%, the polyacetal carboxylate has a molecular weight of approximately 5250 and its proportion in the detergent composition is approximately 25%, the concentration of detergent composition in the washing water is 0.1 20 g 0.3%, and the wash water has a hardness of about 100 ppm to about 300 ppm expressed as equivalent calcium carbonate. 15. Method for washing soiled fibrous materials in order to remove the dirt, characterized in that it consists in washing such a soiled fibrous material in washing water with a hardness of 50 to 150 ppm, expressed as equivalent calcium carbonate, at a temperature of 10 to 70 ° C. with a synthetic organic detergent chosen from anionic and nonionic synthetic organic detergents and their mixtures, which detergents contain at least one ethoxy group per molecule, and an adjuvant detergency of the polyacetal-carboxylate type having a weight-average molecular weight calculated from 3000 to 6000, at concentrations of these components in the washing water from 0.0025 to 0.15% of the synthetic organic detergent (s) and 0 0.0025 to 0.475% of the polyacetal carboxylate. *; 26 16. Method according to claim 15, characterized in that the temperature of the washing water is 10 to 30 ° C, the anionic detergent is a polyethoxylated higher fatty alcohol) sulfate, the nonionic detergent is a pro-5 product of ethylene oxide and higher fatty alcohol and the proportions of the synthetic organic detergent (s) and the polyacetal carboxylate are in the ranges of 0.005 to 0.075% and 0.01 to 0.15%, respectively , in the wash water. 10 17 - Process according to claim 16, characterized in that the synthetic organic detergent is a non-ionic synthetic organic detergent which is a condensation product of a higher fatty alcohol having on average 12 to 15 carbon atoms and of approximately 7 moles of ethylene oxide per mole, the polyacetal carboxylate has a molecular weight of about 5250 and the concentrations of these components in the wash water are about 0.0225% and in about 0.0375%, respectively.