FI61914C - TVAETTMEDELSKOMPOSITION INNEHAOLLANDE FOSFATBUILDERAEMNEN - Google Patents

Description

- —71 Γο, „KU ULUTUSJULATISU rac \ aa M (11> utlAggnincsskmft 61914 c (45) Patent ny, '', nne! Ly II 10 1982, Patent n-.edJelat V v (51) Kv.ik3 / iflc. ci.3 C 11 D 3/065 | __p | LAN D (21) Patent application - Patentantnnng 762hkÖ (22) Hakamitpiivi - Amöknlngtdag 25.08.76 (Fl) (23) Primary cloud — Giltlghattdag 25.08.76 (41) Tullut Julklsaktl - Bllvlt off March 1, 77

National Board of Patents and Registration (44) Date of issue * and date. - 30.06.82

Patent · och registerstyrelsen 'Ansttkan utlagd och utl.skrlft «n publkerad (32) (33) (31) Pyydetty atuolkaut— Begird prtorltet 28.08.75

England-England (GB) 355 ^ 5/75 Proven-Styrkt (71) Unilever N.V. , Burgemeester s'Jacobplein 1, Rotterdam, The Netherlands (NL) (72) David Ellis Clarke, Wirral, Merseyside, James Francis Davies, Wirral, Merseyside, John Barry Tune, Wirral, Merseyside, England-England (GB) (7) * 0 Leitzinger Oy (5M Detergent mixture containing phosphate builders - Tvättmedelskomposition innehallande fosfatbuilderämnen

The present invention relates to powder detergent compositions which are suitable for washing fabrics, and in particular to such compositions which contain synthetic detergent active compounds together with phosphate builders for detergency.

The most commonly used detergent builders are condensed phosphates, especially sodium tripolyphosphate, but it has been suggested that the use of detergent phosphate builders plays a role in water pollution problems. Many other alternative, mainly organic substances have been proposed for use as detergent builders instead of condensed phosphates, but most of these substances are unsatisfactory for one reason or another, for example they are less effective or biologically undesirable or may simply be too expensive.

It has also been suggested that water pollution problems be alleviated by the use of smaller amounts of condensable phosphate builders in combination with or without other detergent builders, but only a few of these proposals have come close to commercial acceptance. When sodium tripolyphosphate is used in smaller amounts of 2,61914 without complementary builders, considerable problems can occur when using mixtures in hard water if the amount of phosphate is not sufficient to sequester all the calcium ions present, as this causes precipitation of insoluble calcium phosphate salts. These salts can deposit on fabrics, in addition to reducing their washing ability because the water does not soften sufficiently, sometimes accompanied by the precipitation of insoluble calcium salts of anionic detergent compounds.

On the other hand, when a condensed phosphate builder is used in combination with a non-phosphate builder, the former may prevent the latter from working effectively, especially in the case of other detergent buffs which act by doping a calcium salt, for example sodium carbonate. In addition, there are only a relatively small number of other detergent builders that are fully environmentally acceptable and are so good that they are worth using even to partially replace the condensed phosphate filler.

To solve these problems, a lot of work and money has been spent in recent years and attempts have been made to synthesize and evaluate several new substances. However, the acceptance of any completely new substance for home use necessarily takes several years, and therefore very recently there has been a focus on known non-phosphate substances that act as builders by either sequestration, precipitation or ion exchange and are known to be environmentally safe.

The present invention consists in the surprising finding that certain blends can be selected from the well-known phosphate builders of detergent, which have good detergency of the fabrics and relatively low phosphate amounts. Since mixtures of such phosphates are well known in detergent products, especially in products not intended for washing fabrics, it is surprising that this advantage has not been previously observed and its importance understood. A preferred aspect of the invention is that the invention allows the formulation of good detergent products with relatively low phosphate levels without the use of complementary non-phosphate builders.

According to the present invention, a powdered alkaline fabric detergent composition comprises about 5 to about 30% synthetic anionic, nonionic, 6191 4 3 amphoteric or zwitterionic detergent compound or a mixture thereof and about 10 to about 30% combined sodium tripolyphosphate and alkali metal orthophosphate in a weight ratio of 1: 10: wherein the amount of sodium tripolyphosphate is at least about 5%, and the gastric amount of alkali metal pyrophosphate is not more than about 5%, all of which percentages are expressed as percentages by weight of the 0.1% aqueous solution of the total detergent mixture. 11.

The invention encompasses methods of making these detergent compositions. By appropriately selecting the amounts of sodium tripolyphosphate and alkali metal orthophosphate, it is possible to formulate effective detergent compositions containing lower amounts of phosphorus than comparable conventional sodium tripolyphosphate-based detergent compositions having similar detergency builders. Since these two essential detergent builders usually work differently, i. sodium tripolyphosphate acts as a sequestering detergent builder, and alkali metal orthophosphates act as precipitating builders, it is somewhat surprising that a mixture of these agents works so effectively. In particular, when alkali metal orthophosphates are used as the detergent builder, they normally tend to form an inorganic deposit that promotes soil deposition on the washed fabrics, but in the presence of sodium tripolyphosphate, soil re-deposition is significantly less, which would reduce the benefit of washing ability. In addition, compared to the use of sodium polyphosphate alone as the detergent builder, the same amount of combined sodium tripolyphosphate and alkali metal orthophosphate has better detergency build ability and lower dirt reprecipitation properties.

The alkali metal orthophosphate used is either potassium or, preferably, sodium orthophosphate, the latter being cheaper and more readily available. Tri-alkali metal salts are usually used, but orthophosphoric acid or di- or mono-alkali metal salts, for example disodium hydrogen orthophosphate or monosodium dihydrogen orthophosphate, can be used to form mixtures if desired. In the latter case, other temporal salts should also be present which would maintain a high pH in the final product upon neutralization to complete trialkali metal orthophosphate salts. It is particularly preferred to use a mixture of monosodium and disodium hydrogen orthophosphates 4 61914 in a ratio of about 1: 3 to 2: 3, especially about 1: 2, because such a mixture is prepared as a raw material for the preparation of sodium tripolyphosphate and is therefore readily available. Both alkali metal orthophosphate and sodium tripolyphosphate can initially be used as anhydrous or hydrated salts, for example, disodium orthophosphate dodecahydrate and pentasodium tripolyphosphate hexahydrate, but hydration is usually performed during the preparation of the detergent powder. However, the amounts of salts have been calculated in anhydrous form. Potassium tripolyphosphate could be used instead of sodium tripolyphosphate if desired, but this would be much more expensive and would not have a commercial advantage.

In the past, the use of combined detergent phosphate builders, for example mixtures of sodium pyrophosphate and sodium tripolyphosphate, has been proposed several times to provide better detergency deposition properties, or benefits other than a reduction in phosphorus content. In addition, it is well known that condensable phosphates, such as sodium tripolyphosphate, tend to decompose to form other phosphates under aqueous time conditions at the high temperatures commonly encountered during the manufacture of detergents. Sodium tripolyphosphate decomposes into a mixture consisting mainly of sodium pyrophosphate and a small amount of sodium orthophosphate, so spray-dried detergent products contain small amounts of all three of these substances.

However, to the best of the applicants' knowledge, it has not been proposed to date to use certain mixtures of sodium tripolyphosphate and alkali metal orthophosphate in the proportions set forth for the powdered fabric detergent compositions of the present invention. When mixtures of these substances have previously been proposed for use, the concentrations have not been suitable or in other types of mixtures, which often contain ingredients that are not suitable for use in fabric detergent compositions. For example, the pH of powdered dishwashing detergent compositions is generally too high for washing fabrics, and products that come into contact with the skin, such as soap bars, generally have a pH of about 7-8, which is too low for new systems with combined phosphate builders.

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Although the ratio of sodium tripolyphosphate to alkali metal orthophosphate can be varied from a weight ratio of 10: 1 to a weight ratio of 1: 5, it is preferred that the ratio be 8: 1 to 1: 2, especially using sodium tripolyphosphate in excess of alkali metal orthophosphate to a weight ratio of 1: 1 to 1: 1, e.g. - about 3: 2, and more specifically about 3: 1 to about 2: 1. These ratios of sodium tripolyphosphate to alkali metal orthophosphate are particularly suitable in detergent compositions used at relatively high feed concentrations, i. from about 0.3% to about 0.8% by weight, which is common practice in Europe, especially in front-loading automatic washing machines, and when relatively large amounts of phosphates are allowed in the products, i.e. corresponding to about 4 to about 7% phosphorus.

However, in detergent compositions intended for use at relatively low product concentrations, i. from about 0.1% to about 0.3%, which is common in North American washing conditions, especially in top-loading automatic washing machines, and when relatively low amounts of phosphate are selected in the products, i.e. always corresponding to about 4% phosphorus, it may be desirable to increase the proportion of alkali metal orthophosphate in the product. The ratio of sodium tripolyphosphate to alkali metal orthophosphate can then be expressed in parts by weight of 2: 1 to 1: 5, preferably 1: 1 to 1: 5, for example about 1: 1 to 1: 2 or 1: 3 by weight. Alternatively, when particularly low amounts of phosphate are required, it may be advantageous to add a complementary non-phosphate bulking agent, and still achieve optimal detergency formation from the phosphate bulking agents in the compositions of the present invention.

It is to be understood that the actual amounts of sodium tripolyphosphate and alkali metal orthophosphate are selected on the basis of the total content of detergent phosphate matrix desired in the detergent compositions or the maximum permissible phosphorus content. When the total amount of sodium tripolyphosphate and alkali metal orthophosphate is required to be from about 10% to about 30% by weight of the product, it is desirable that the sodium tripolyphosphate content be from about 10% to about 20% and the alkali metal orthophosphate content from about 3% to about 15%, especially from about 5% to about 10%. . The total amount of sodium tripolyphosphate and alkali metal orthophosphate is preferably at least about 15% and up to about 25% by weight of the mixture.

• i -1 6 61914

It should be noted that due to the detergency-forming properties of the combined detergent sodium tripolyphosphate and alkali metal orthophosphate builders, i. calcium binding capacity, corresponding to larger amounts of sodium tripolyphosphate used alone, it is possible to make detergent compositions either with higher detergency properties by using the same total amount of phosphate or with similar detergency properties with lower total phosphate. The latter choice leaves some extra "space" in the compositions, which can either be filled with fewer fillers or other useful ingredients, for example by using an additional amount of bleaching agents such as sodium perborate or percarbonate, fabric softeners or other detergents.

This new freedom for detergent manufacturers is a commercially significant advantage. When a low-cost filler, such as sodium sulfate, is used in combination with a lower total phosphate content than previously used with sodium tripolyphosphate as the sole bulking agent, significant cost savings are achieved that can be directed to the benefit of the consumer. The same lower phosphate content can also be used to meet the government-described restrictions described earlier, and if no cheap filler is used, some additional preferred ingredients can be used to enhance the overall performance of the compositions. Alternatively, the total amount of the same phosphate can be kept at the same level as using only the initial tripolyphosphate level, but in this case the washing capacity as a whole is enhanced. The cost-saving side of the mixtures according to the invention is particularly advantageous commercially, especially when this can be achieved by still meeting the requirements for a lower amount of phosphate, and it is significant that this has not been observed before.

It is preferred that the only detergent phosphate builders used in the preparation of the compositions of the invention are sodium tripolyphosphate and alkali metal orthophosphate. In particular, it is recommended that no alkali metal, i.e. sodium, or potassium, pyrophosphates because they tend to increase inorganic precipitation. In addition, the presence of significant amounts of alkali metal pyrophosphate instead of sodium tripolyphosphate or alkali metal orthophosphate results in lower detergent build-up capacities within the limited permitted amounts of phosphate. However, as mentioned above, some 6,41914 forms of sodium pyrophosphate as well as a smaller amount of sodium orthophosphate upon hydrolysis of sodium tripolyphosphate under hot time conditions during spray drying, so that spray-dried powders inevitably have low levels. i. up to about 5%, sodium pyrophosphate. The total amount of phosphate ingredients in the detergent compositions is preferably less than about 30% by weight of the compositions. It should be noted that the amounts of hydratable phosphate salts in the mixtures must be calculated anhydrous. It is necessary that the detergent compositions of the invention contain from about 5% to about 30%, most preferably from about 10% to about 25% by weight of the synthetic anion, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof. Several suitable detergent compounds are commercially available and have been described in detail in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, Schwartz, Perry and Berch.

Preferred useful detergent compounds are synthetic anionic or nonionic compounds. The foregoing are usually water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms. The term alkyl includes the alkyl moiety of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulfating higher (C8-C18) alcohols prepared, for example, from tallow or coconut oil; sodium and potassium alkyl (C 8 -C 20) benzene sulfonates, especially n Atrium linear secondary alkyl (C 1 -C 4) benzene sulfonates; sodium alkyl glyceryl ether sulphates, in particular ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (C 1 -C 6) fatty alcohol alkylene oxide, especially ethylene oxide, reaction products of fatty acids, such as coconut fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of methyltaurine fatty acid amides; alkane monosulfonates, such as compounds obtained by reacting alpha-olefins (C8-C2q) with sodium bisulfite, and compounds obtained by reacting paraffins with sulfur dioxide and C1-4, followed by hydrolysis of these to a basic "sulfate" sulfonate; ; and olefin sulfonates, designated 3,61914, from a substance prepared by reacting olefins, especially C10-C20 alpha-olefins, with sulfur trioxide and then neutralizing and hydrolyzing the reaction product. Preferred anionic detergent compounds are sodium (Cu-C15) alkyl benzene sulfonates and sodium alkyl sulfates.

Examples of useful nonionic detergent compounds are, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 8 -C 22) phenols, generally 5-25 EO units, i.e. 5-25 units of ethylene oxide per molecule; aliphatic (C 8 -C 22) condensation products of primary straight-chain or branched alcohols with ethylene oxide, usually 6 to 30 EO units, and products prepared by condensing ethylene oxide with the reaction products of propylene oxide and ethylenediamine. tertiary phosphine oxides and dialkyl sulfoxides.

Mixtures of detergent compounds, for example combined anionic compounds or combined anionic and non-ionic compounds, can be used in detergent mixtures, especially in the latter case, in order to obtain controlled low-foam properties. This is advantageous in compositions intended for use in foam-intolerable automatic washing machines. We have also found that the use of slightly non-ionic detergent compounds in the compositions can reduce the tendency of insoluble phosphate salts to deposit on the washed fabrics.

Amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention, but this is usually not desirable due to their relatively high cost. If an amphoteric or zwitterionic detergent compound is used, it is usually used in small amounts in mixtures based on the much more commonly used synthetic anionic and / or nonionic detergent compounds. For example, mixtures of amine oxides and ethoxylated nonionic detergent compounds can be used.

Certain soaps may also be used in the compositions of the invention, but H as the sole detergent compounds. They are particularly useful in low concentrations of 9 6191 4 in binary and ternary mixtures together with nonionic or combined synthetic anionic and nonionic detergent compounds which foam little. The soaps used are the sodium or less preferably potassium salts of cio - <'24 fat ^ aPP ° 3en. In particular, it is recommended that the soaps be based mainly on the longer chain fatty acids in this range, i.e. at least half of the soap has a carbon chain length of 16 or more. This is most conveniently done using soaps derived from natural sources such as tallow, palm or rapeseed oil, which can be cured if desired, along with smaller amounts of other shorter chain soaps made from nut oils such as coconut oil or palm kernel oil. The amount of such soaps may vary from about 0.5% to about 25% by weight, generally lower amounts of about 0.5% to about 5% will suffice to control the foam. Soap is best used from about 2% to about 20%, especially from about 5% to about 15%, to improve washing performance.

In addition to detergent compounds and detergent builders, the detergent compositions of the invention may contain any of the other conventional additives in amounts where such agents are commonly used in fabric detergent compositions. These additives are examples of suds enhancing agents, such as alkanolamides, particularly monoethanolamide obtained palmunydinrasvahapoista and coconut, foam control agents, such as alkyl phosphates and silicones, anti-redeposition agents such as sodium carboxymethylcellulose and polyvinylpyrrolidone, acid-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid valkaisuprekursorit, a chlorine-release bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softeners, inorganic salts such as sodium sulfate, sodium carbonate and magnesium silicate and - these are usually present in very small amounts - enzymes and enzymes, enzymes, perfumes, .

It is particularly advantageous to add an amount of sodium perborate to the detergent compositions, preferably about 10 to 40%, for example about 15 to about 30% by weight. The bleaching effect of sodium perborate has been found to be enhanced under higher temporal conditions, in which the washing-forming effect of alkali metal orthophosphate is also optimal. Thus, it is possible to obtain better bleaching properties by using sodium perborate in the same amounts as usual; or sodium perborate may be used in smaller amounts to give similar bleaching properties as conventional products with more perborate and sodium tripolyphosphate as the sole detergent builder. The latter choice can also be used to further reduce the raw material costs of the mixture if a cheap filler is used instead of some sodium perborate.

It is desirable to add one or more antifouling agents to the detergent compositions of the invention to reduce the potential tendency of inorganic deposits to precipitate on the washed fabrics. The amount of such an antifouling agent is usually about 0.1 to about 5 weight percent, most preferably about 0.2 to 2 weight percent of the mixture. Preferred antifouling agents include homo- and copolymers of acrylic acid or substituted acrylic acids, such as sodium polyacrylate, sodium salt of copolymethacrylamide / acrylic acid and sodium polyol alpha-ethylene, copyrene, maleic anhydride, maleic anhydride, and ethylene, anhydride, and ethylene. wherein the carboxyl groups are optionally partially esterified, especially in the case of styrene-maleic anhydride copolymers. Such copolymers preferably have relatively low molecular weights, for example between about 5,000 and 50,000. Other antifouling agents include, for example, sodium salts of polymaleic acid and polytaconic acid, phosphate esters of ethoxylated aliphatic alcohols, polyethylene glycol phosphate esters, and some and some phosphonates such as sodium ethane ethyl 2-tetraethylenethane triethylenethane triethylenethane triethylenethane. Mixtures with organic phosphonic acids or substituted acrylic acids or their salts and protective colloids, such as gelatin, can also be used, these are described in our Dutch application 7602082. The most preferred antifouling agent is sodium polyacrylate having a molecular weight of about 10,000 to 50,000, for example about 27,000.

It is also possible to add smaller amounts, preferably not more than about 20% by weight, of other non-phosphate builders of detergent which may be present in the detergent compositions of the present invention. h V * · '· ·, ·. ··' V *> - · ί n 6191 4 either so-called precipitating aggregates or sequestering aggregates.

This is particularly advantageous when it is desired to increase the detergency while using particularly low amounts of essential sodium tri-polyphosphate and alkali metal orthophosphate builders to achieve low phosphorus concentrations in the detergent compositions. Examples of such other detergent builders are amine carboxylates such as sodium nitrilotriacetate, sodium aluminum acetate, ion exchangers, sodium citrate and soap which can act as a detergent builder as discussed above. However, such other builders are not essential, and a particular advantage of the compositions of the invention is that good detergent build-up properties can only be achieved by using lower amounts of phosphate builders than have hitherto been considered necessary.

It is also desirable to add alkali metal silicate to the mixtures, especially sodium ortho-, meta- or preferably neutral alkali metal silicate. The presence of such alkali metal silicates in concentrations of at least about 1% and most preferably about 5-15% by weight of the compositions preferably reduces corrosion of the metal parts of the washing machines and is further advantageous for manufacture and generally improves the properties of the powder. More alkaline ortho- and metasilicates should normally only be used in smaller amounts in this range as a mixture with neutral or alkaline silicates.

The compositions according to the invention must be temporary, but not too strongly temporal, as this could damage the fabric and also be dangerous in home use. When used in aqueous aqueous solution, the mixtures should in practice be given a pH of 9-11. In household products in particular, it is recommended that the lowest pH be at least 9.25 and especially 9.5 or above, as the lowest pH tends to be less effective in creating optimal detergency, and the highest pH 10.5, as more alkaline products can be dangerous when misused. Our requirement is that the pH be measured at the lowest concentration normally used, 0,1% w / v product, in water with a hardness of 12 ° H (Ca), (French permanent hardness, calcium only), at 50 ° C, whereby satisfactory alkalinity can be obtained. guaranteed in use at all normal product concentrations. The pH is adjusted by the amounts of alkali metal orthophosphate and other alkaline salts such as alkali metal silicate, sodium perborate and sodium carbonate, the amount of the latter usually not exceeding 20% by weight of the mixture. The presence of other alkaline salts, especially alkali metal silicates, is particularly advantageous because the alkalinity of alkali metal orthophosphates decreases in hard water due to the precipitation of the calcium salt. In the alkaline detergent composition according to the invention, the other ingredients should, of course, be chosen so that they are stable under time conditions, in particular for pH-sensitive substances such as enzymes.

The detergent compositions of the invention should be in free-flowing powder form. They can be prepared by any of the methods commonly used in the preparation of detergent compositions for such fabrics, but preferably by slurry and spray-dry methods. In the slurry preparation step, it is advantageous to be able to form an alkali metal orthophosphate by neutralizing orthophosphoric acid or by using a so-called "bun feed", which is a crude mixture of mono- and disodium orthophosphates used in the preparation of sodium tripolyphosphate. More specifically, conventional sodium tripolyphosphate powders generally require about 50% sludge water, while the sludge content can be reduced to about 40% or even lower in the preparation of products of the invention based on combined sodium tripolyphosphate and sodium orthophosphate.

The invention is illustrated by the following examples in which parts and percentages are by weight and the amount of ingredients is indicated as anhydrous unless otherwise indicated.

Example 1

A spray-dried, low-foam detergent powder was prepared according to the following nominal formulation: 13,61914

Ingredient%

Sodium alkyl benzene sulfonate 7.0

Thallamide - 11 EO condensate 1.5

Sodium-cured tallow soap 3.0

Sodium tripolyphosphate 16.0

Sodium orthophosphate 6.0

Sodium alkali silicate 10.0

Sodium sulphate 23.4

Sodium perborate 25.0

Sodium carboxymethylcellulose 1.5

Fluorescent substances and preservatives

Water 6.1 This mixture was prepared by a standard slurry preparation method in a turbo mixer using a slurry temperature of 80 ° C and a final slurry moisture content of 38% (significantly lower than normal moisture content of about 50% in sodium tri-polyphosphate-based products) and then spray-counter as an inlet temperature of 300 ° C and an outlet temperature of 100 ° C. Under these conditions, the hydrolysis-induced phosphate degradation during the process was about 20%, with the finished product containing about 12.7% sodium tripolyphosphate, 6.9% sodium orthophosphate and 2.4% sodium pyrophosphate. The mixture had good powder properties and withstood storage in laminated cardboard boxes at temperatures up to 37 ° C.

The detergency of this product, which had a phosphorus content of about 5%, was compared with the detergency of a commercially available heavy-duty detergent composition (A). The nominal formulation of this detergent mixture (A) was otherwise similar, but contained about 35% sodium tripolyphosphate (corresponding to 9% phosphorus) instead of the combined sodium tripolyphosphate and alkali metal orthophosphate of the product of the invention and thus contained a small amount, 9%, of sodium sulphate. Washing experiments were performed using a 0.6% product concentration in 40 ° H water and an automatic Lavamat Regina washing machine with a 95 ° C washing program. Home-soiled garments were washed in 3.2 kg fillings containing various types of halved garments, including hand towels, tablecloths, and pillowcases.

14 6191 4

The appearance of garments washed with the mixture according to the invention was actually considered to be better than that of garments washed with a commercially available product containing more phosphorus. Similar results were obtained when the tests were repeated using 0.4% and 0.8% product concentrations in very hard water (40 ° H), and when the product was used in 0.6% softer water (25 ° H) when freezing under different practical washing conditions in continental Europe. In actual home washing experiments, similar results were still obtained for both products under these conditions and also at low washing temperatures (30-40 ° C) when washing mainly synthetic fabrics.

When 7.0% sodium alkyl benzene sulfonate and 1.5% thallamide-11 EO condensate were replaced with 8.5% sec-linear (C 1 -C 6) 11 Id alcohol-9 EO condensate (obtained as Tergitol 15-S -9), this was found to improve the washing results of the mixture according to the invention.

Experiments were also performed to determine the amounts of inorganic deposition on the cotton terry towel at a product concentration of 0.4 and 0.8% in 40 ° H water (Ca: Mg, 4: 1) under the same high temperature washing conditions. After ten consecutive wash cycles, the amounts of inorganic deposits were as follows:

Deposition,%

Product Concentration Example 1 Product A

0.4% 1.3 2.0 0.8% 2.6 0.2 These results show that the mixture according to the invention is better at a lower product concentration, but more inorganic deposition occurs at a higher product concentration under these harsh conditions. Other experiments showed generally similar properties for both products in terms of soil re-deposition and soil removal during washing, but significantly better talc properties with the products of the invention. It should be noted that the results are generally similar between the product of the invention and the reference mixture (A), despite the fact that a much lower total amount of phosphate was used in the former, whereby the cost of the substances is correspondingly lower.

is 61914

The experiments were further performed with a mixture similar to Example 1, but to which 1% ethane-1-hydroxy-1,1-diphosphonate and 1% sodium polyacrylate (molecular weight 27,000) obtained under the name Versicol E7) were separately added as antifouling agents. Both of these additives were found to reduce the amount of inorganic deposition on washed cotton terry towels to 1.1 and 1.2%, respectively, under the washing conditions described above (product concentration 0.8%, water hardness 40 ° H). Inorganic deposition was also found to be reduced by using 0.5% copolymers of ethylene and maleic anhydride and ethylene and vinyl methyl ether, especially when larger amounts of nonionic detergent compounds were used in the products.

In addition, a comparative experiment was performed with a product containing equal amounts of sodium tripolyphosphate and orthophosphate as in Example 1, but less, 6% alkylbenzenesulfonate and 2% nonionic detergent compound and only 18% sodium perborate (adjusting the amount of sodium sulfate accordingly). This product was compared to a conventional reference product containing the same detergent compounds and 35% sodium tripolyphosphate and 24% sodium perborate.

The results of the comparative home washing experiments showed that the washing capacities were similar under the experimental conditions using water at 45 ° C and 95 ° C with German hardness of 35 ° and 15 °. In particular, it was found that the bleaching efficiencies of both powders were similar despite the fact that the product of the present invention contained much less perborate. In a further experiment, when the amount of sodium perborate in the reference product was extended to 18%, the bleaching effect of the product of the invention was significantly better than that of the reference product based on sodium tripolyphosphate.

Yet another comparative experiment was performed using the formulation of Example 1 supplemented with 0.62% particles of the proteolytic enzyme "Alcalase" (activity 1 Anson unit). In the evaluation tests performed in the washing machine, the performance was generally similar to that of a commercially available product containing 35% sodium tripolyphosphate and the same amount of enzyme.

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Example 2 16 61914

A high-foam second detergent powder was prepared according to the following nominal formulation:

Ingredient

Sodium alkyl benzene sulfonate 20.0

Sodium tripolyphosphate 16.0

Sodium orthophosphate 5.0

Sodium alkali silicate 10.0

Sodium carbonate 10.0

Sodium sulphate 15.5

Borax (101 ^ 0) 14.0

Sodium carboxymethylcellulose 1.0

Fluorescent substances, moisture up to 100.0

The above detergent mixture was compared to a standard detergent (B) having a similar formulation except that 5% sodium orthophosphate was replaced by 16% sodium tripolyphosphate to give the latter in a conventional amount of 32%. At the same time, the amounts of borax and sodium carbonate were each reduced to 5%, respectively, and the amount of sodium sulfate was increased from 15.5% to 18.5% in the reference product (B). In laboratory washing experiments using soiled cotton vests, the light reflectance of the washed garments using the mixture of Example 2 and the reference product (B) was found to be 75% and 80% of the light reflectance of the original clean garments, respectively, which is not a significant difference. In the same test, the deposition of a fluorescent substance on the washed garments was also measured, and this was found to be marginally better in the product of the present invention. The products were also compared in home washing tests, where it was generally found that both products were acceptable to the user and neither product was significantly favored. This general uniformity in washing properties was achieved despite the much lower content of phosphate aggregate in the product according to the invention and thus its lower manufacturing cost.

Example 3

A powdered 17,61914 detergent composition was prepared according to the following nominal formulation:

Ingredient%

Sodium alkyl benzene sulphonate 4.0

Tallow Alcohol - 18 EO Condensate 4.0

Sodium tripolyphosphate 17.0

Sodium orthophosphate 8.0

Sodium silicate 10.0

Sodium tallow soap 5.0

Sodium hardened tallow soap 3.0 N sodium perborate 25.0

Sodium sulphate, water up to 100.0 This formulation was evaluated in washing machine tests on halved cotton garments and found to have overall washing performance similar to that of a commercially available product containing the same detergent compounds and sodium-cured tallow soap, but in a much larger amount, 35% sodium tripolyphosphate.

Examples 4 and 5

Two powder detergent mixtures were prepared according to the following nominal formulations:%

Ingredient Example 4 Example 5

Sodium alkylbenzenesulfonate 13.00 13.00

Sodium tripolyphosphate 23.65 9.50

Sodium orthophosphate 2.50 6.70

Sodium sulphate 23.60 33.55

Tallow ethanolamide 1.00 1.00

Sodium toluene sulphonate 0.50 0.50

Sodium carboxymethylcellulose

Sodium perborate 19.00 19.00

Fluorescent substances, perfume, moisture up to 100.00 up to 100.00 '. t- ’18 6191 4

Both powders were prepared by spray-drying, in which case sodium perborate was added to the spray-dried powders. The slurry temperature was about 70 ° C, the sludge water content was about 42%, the air inlet temperature was about 330 ° C and the air outlet temperature was about 110 ° C.

Both products of the invention containing combined phosphates were evaluated in home washing experiments compared to a commercially available product with a similar formulation except that it contained 32% sodium tripolyphosphate as the sole phosphate builder and that the amount of sodium sulfate was reduced accordingly. The overall result of the various attributes determined by the testers was that neither product was significantly popular at the expense of the other despite the lower phosphate contents of the products of the invention. Detailed analysis of the results showed that the detergency of the products of the invention is slightly worse in soft water, which could be improved by adding about 5% soap.

Examples 6-11

To ensure the compatibility of the various detergent compounds with the combined phosphate bulking system of the invention, a number of detergent formulations were prepared and tested on Terg-O-Tometer devices. The following amounts of ingredients were used:

Ingredient%

Detergent compound 10.0

Sodium tripolyphosphate 20.0

Potassium orthophosphate 8.0

Sodium alkali silicate 10.0

Sodium sulphate, water up to 100.0

The results obtained using the various detergent compounds are as follows (the experiment was washed for 15 minutes at 60 ° C, product concentration 0.6% in hard water (25 ° Ca, 5 ° Mg, French hardness)). The results show that all the detergent compounds tested fit well together.

19 6191 4

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Examples 12 and 13 61 91 4 20

Two detergent mixtures were prepared with the following nominal formulations:%

Ingredient Example 12 Example 13

Sodium alkyl (C, η-c15 ^ benzenesulfonate 8.0 8.0

Sodium tripolyphosphate

Sodium orthophosphate 6.0 6.0

Sodium sebum soap 10.0

Sodium nitrilotriacetate - 10.0

Sodium alkali silicate 10.0 10.0

Sodium sulphate, water up to 100.0 up to 100.0 The washability of these products was evaluated in a Terg-O-Tometer at a product concentration of 0.6% in soft water (5 ° H Ca) at 40 ° C. The results using artificially soiled test garments showed that both products had good washing performance under these conditions and could be compared to the washing performance of a conventional product containing much more phosphate (35% sodium tripolyphosphate) and significantly better than a similar product containing no added sodium. tallow soap or sodium nitrilotriacetate.

Example 14

Two detergent mixtures were prepared with the following nominal formulations:%

Ingredient

- A B

Sodium alkyl benzene sulphonate

Sodium tripolyphosphate 15.0 10.0

Sodium orthophosphate

Sodium pyrophosphate - 5.0

Sodium sulphate, water up to 100.0 up to 100.0 β S- / · "*% 21 6191 4

Pure cotton terry towel pieces were washed in 0.6% solutions of these products at 60 ° C in water having a hardness of 40 ° H Ca and then the garments were dried and this procedure was repeated until 20 complete wash cycles. The amounts of inorganic deposits on the fabrics were determined after 10 and 20 wash cycles by annealing the garments at 600 ° C and weighing the resulting ash. The results were as follows:

Ash 10% wash 20 wash

Product A 0.49 0.81

Product B 0.90 1.28 These results show that when 5% pyrophosphate replaces the 5% sodium tripolyphosphate used, more inorganic material is deposited on the fabric.

Example 15

A spray-dried detergent composition was prepared with the nominal formulation as follows:

Ingredient%

Sodium alkyl (C 1-4 -C 1-4) sulfate 8.0

Sodium tripolyphosphate 17.0

Sodium orthophosphate 8.0

Sodium-cured tallow soap 15.0

Sodium alkali silicate 10.0

Sodium perborate 27.0

Sodium sulphate, water up to 100.0 This mixture was compared to a product containing 31% sodium tripolyphosphate. Its washing performance was found to be superior in washing machine tests at a product concentration of 0.6% at both 60 and 90 ° C with water hardnesses of 15 °, 25 ° and 35 ° (French hardness) (Ca: Mg, 4: 1).

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Example 16 6191 4 22

The dry, combined and high-foam detergent powder was prepared according to the following nominal formulation:

Ingredient _%

Sodium linear sec-alkyl benzene sulfonate 16.0

Sodium tripolyphosphate 8.0

Sodium orthophosphate 10.0

Sodium alkali silicate 5.9

Sodium sulphate 39.0

Water up to 100.0 This product with a phosphorus content of 4% was compared with a reference product with a similar formulation except that n Atrium orthophosphate had been replaced by an additional 25% sodium tripolyphosphate to give a normal total amount of the latter detergent builder, 33 %, i.e. the amount of phosphorus in the reference product was about 8%, and the amount of sodium sulfate was reduced accordingly. Washing experiments were performed in automatic Whirlpool Supreme 80 washing machines using a product concentration of 0.1% at 48 ° C in water with a hardness of 8 ° H (6 ° Ca, 2 ° Mg). In this case, it was found that the performances of both products were similar overall, despite the fact that the amount of phosphate in the product according to the invention was much lower. When the experiments were repeated at a product concentration of 0.2%, the reference product, which contained much more detergent aggregate, was generally considered to be slightly superior.

Experiments were further performed in which the amounts of sodium tripolyphosphate and sodium orthophosphate were changed to 4% and 15%, respectively, i.e. the total phosphorus content was still only 4%. In comparative washing experiments performed under similar conditions, it was found that the product of the invention containing the combined aggregate was considered marginally but not significantly better at the product concentration of 0.1%, while at the product concentration of 0.2% the reference product was preferred.

6191 4

Examples 17 - 18 23

A biscuit detergent composition was prepared according to the following nominal formulation:%-° -S-a Example 17 Example 18

Sodium alkyl benzene sulfonate 10.0

Sec-linear (cn_c ^ 5) alkyl-9 EO condensate - 10.0

Sodium tripolyphosphate

Sodium orthophosphate

Sodium alkali silicate 10.0 10.0

Sodium sulphate, water up to 100.0 up to 100.0 These products were evaluated on a Terg-O-Tometer detergent tester at a concentration of 0.15% in water with a hardness of 6 ° H (French hardness: 5 ° Ca, 1 ° Mg) and 12 ° H (French hardness 10 ° Ca, 2 ° Mg), at 40 ° C compared to a reference product with a formulation similar to Example 17 but with 35% sodium tripolyphosphate as the sole phosphate backbone. The results using an artificially soiled cotton-polyesber test garment were generally acceptable for all three detergent products despite the much lower phosphate content of the products of the invention. However, under soft water conditions, the reference product was slightly preferred. In hard water, essentially similar washing results were achieved with all three products.

Additional experiments were performed using the same formulations as in Examples 17 and 18, but using different detergent compounds, i. hydroxyalkylmethyltaurine, sodium olefin sulfonate, sodium (C 1 -C 4) alkyl-9 EO sulfate, sodium C 1 -C 4 alkyl sulfate and lauryl dimethyl ammonium propanesulfonate. The results of experiments using artificially soiled test garments under the same conditions as before except for the use of hard water (25 ° H Ca and 5 ° H Mg, French hardness) showed that all detergent compounds were compatible with the combined phosphate bulking system. The best overall results were obtained using sodium alkyl 9 EO sulfate.

f.

Example 19 24 61 91 4

Spray-dried detergent powder was prepared according to the following nominal formulation:

Ingredient

Sodium alkyl benzene sulphonate 16.0

Sodium tripolyphosphate 14.0

Sodium orthophosphate 14.5

Sodium alkali silicate 8.0

Sodium sulphate, water up to 100.0 This formulation had good physical properties and good washing properties at low dosages compared to a conventional sodium tripolyphosphate-based product with a higher total phosphate content.

't Λ

Claims (19)

61914 25 A powdered alkaline fabric detergent composition comprising a synthetic detergent compound and combined detergent phosphate builders, characterized in that it contains from about 5% to about 30% of a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or a mixture thereof and from about 10% to about 10%. 30% of combined sodium tripolyphosphate and alkali metal orthophosphate in a weight ratio of 10: 1 to 1: 5, the amount of sodium tripolyphosphate being at least about 5%, and the amount of any alkali metal pyrophosphate not more than about 5%, all these percentages by weight of the total detergent composition, The pH of a 0.1% aqueous solution is 9-11. Detergent composition according to Claim 1, characterized in that the alkali metal orthophosphate is trisodium orthophosphate. Detergent mixture according to Claim 1 or 2, characterized in that the weight ratio of sodium tripolyphosphate to alkali metal orthophosphate is from 5: 1 to 1: 1. Detergent composition according to claim 3, characterized in that the weight ratio of sodium tripolyphosphate to alkali metal orthometallic phosphate is from about 4: 1 to about 3: 2, preferably from about 3: 1 to about 2: 1. Detergent composition according to one of the preceding claims, characterized in that the total amount of sodium tripolyphosphate and alkali metal orthophosphate is from about 15% to about 25% by weight of the mixture. Detergent composition 2 according to one of the preceding claims, characterized in that the amount of sodium tripolyphosphate 3 is from about 10 to about 20% by weight of the composition. 61 91 4 26 Detergent composition according to one of the preceding claims, characterized in that the amount of alkali metal orthophosphate is from about 3 to about 15% by weight, preferably from about 5 to about 10% by weight of the mixture. Detergent composition according to one of the preceding claims, characterized in that it contains soap. Detergent composition according to claim 8, characterized in that it contains from about 0.5% to about 25% by weight of soap of C 10 -C 24 fatty acids, at least half of which have a carbon chain length of 16 or more. Detergent composition according to claim 9, characterized in that it contains from about 2 to about 20% by weight of soap, preferably from about 5 to about 15% by weight of soap. Detergent composition according to one of the preceding claims, characterized in that it contains an antifouling agent. Detergent composition according to Claim 11, characterized in that the amount of antifouling agent is from 0.1 to 5% by weight of the composition. Detergent mixture according to one of the preceding claims, characterized in that it contains an alkali metal silicate. Detergent composition according to Claim 13, characterized in that it contains from about 5 to about 15% by weight of neutral or alkaline sodium silicate. Detergent mixture according to one of the preceding claims, characterized in that the pH of a 0.1% aqueous solution of the mixture is from 9 to 10.5, preferably from 9.5 to 10.5. 27 61914 Detergent composition according to one of the preceding claims, characterized in that the detergent compound contains a nonionic detergent compound. Detergent composition according to one of the preceding claims, characterized in that it contains from about 10 to about 25% by weight of detergent active substance. Detergent composition according to one of the preceding claims, characterized in that it contains from about 10 to about 40% by weight of sodium perborate. Detergent composition according to one of the preceding claims, characterized in that it does not contain added alkali metal pyrophosphate. Detergent composition according to one of the preceding claims, characterized in that it does not contain more than 20% by weight of alkali metal carbonate. 61 91 4 28