NO852161L - PARTICULAR, CONSTRUCTED, NON-IONIC SYNTHETIC DETERGENT AND PROCEDURE FOR PREPARING THIS. - Google Patents

Description

The invention relates to a particulate, built, non-ionic, synthetic, organic detergent. It concerns more particularly such a detergent which contains a building proportion, in combination, of polyacetal carboxylate and carbonate, bicarbonate and zeolite builders for the non-ionic surfactant. The invention also relates to methods for the production of such products.

Particulate, non-ionic detergent products are known where base pearls which are mainly made up of inorganic building salt or salts, e.g. carbonates and bicarbonates, obtained by spray-drying an aqueous slurry from a kneader, have absorbed normally solid non-ionic surfactant in the liquid state for the production of free-flowing, particulate detergents. Polyacetal carboxylate builder salts suitable for use as builders with various organic surfactants, primarily anionic organic surfactants, have been described in the literature and in various US and other patents. Prior to the present invention, however, particulate, structured, non-ionic, synthetic, organic detergents containing carbonate-, bicarbonate-:. and zeolite building salts and polyacetal carboxylate in a total building proportion, not been described,

and the advantages of such detergents and of methods for their production, where the polyacetal carboxylate and the non-ionic surfactant are applied to basic beads of carbonate, bicarbonate and zeolite building salts, have not been known.

Particulate nonionic detergents in which the nonionic surfactant is applied in liquid form to porous base beads containing carbonate and bicarbonate builder salts are described in US Patent 4,269,722, and such detergents have been marketed under the trademark "Fre'sh Start" . They are particularly useful as detergents that are free of phosphate or that have a limited phosphate content, in areas where detergents with a high phosphate content are prohibited. Polyacetal carboxylates are described in US patents 4144226 and 4315092. In US patents 4146495 and 4219437 detergents are claimed which contain the polyacetal carboxylate builder

(US patent 4146495), and similar detergents containing

ketodicarboxylates (US patent 4219437) which can often be used as a substitute for the polyacetal carboxylates. Various other patents on similar constructions include US patents 4141676, 4169934, 4201858, 4204852, 4224420, 4225685,

4226960, 4233422, 4233423, 4302564 and 4303777. Also the European patent applications 0015024, 0021491 and 0063399 are relevant. Although such patents and/or patent applications contain a broad teaching that polyacetal carboxylates can be incorporated into various types of detergents and although some of such polyacetal carboxylates are described as components for detergents containing non-ionic surfactants and cationic softeners, in none of these references or in combinations thereof are such polyacetal carboxylates described or proposed as components for the nonionic detergents according to the invention, and in none of the counterclaims is any teaching regarding obtaining the described improved washing power for the detergents according to the invention and the free-flowing property of the manufactured products. Furthermore, the present manufacturing processes have not been described or suggested in any of these references or in any combination of these references.

The invention relates to a particulate, structured, non-ionic, synthetic, organic detergent comprising a cleaning portion of a non-ionic, synthetic, organic surfactant,

and the detergent is distinctive in that it comprises a building portion', in combination, of a polyacetal carboxylate builder for the non-ionic surfactant and carbonate, bicarbonate and zeolite builders for the non-ionic surfactant.

Preferably, certain non-ionic surfactants, poly-acetal carboxylate builders, carbonate, bicarbonate and zeolite builders are used in certain relative amounts, and the product obtained is a free-flowing, particulate, built detergent with improved washing power (or ability to remove dirt). The invention also relates to methods for producing such particulate detergents.

The polyacetal carboxylate can be considered to be

which is described in US patent 4144226, and it can be produced by the method described therein. Such a typical

product will have the formula

wherein M is selected from the group consisting of alkali metal, ammonium, alkyl groups of 1-4 carbon atoms, tetraalkylammonium groups, and alkanolamine groups, both having 1-4 carbon atoms in their alkyl groups, n averages at least 4, and and R 2 are any chemically stable groups which stabilizes the polymer against rapid depolymerisation in alkaline solution. The polyacetal carboxylate is preferably a carboxylate in which M denotes an alkali metal, e.g. sodium, n is 50-200, is or a mixture thereof, R is

and n is on average 20-100, more preferably 30-80. The calculated weight average molecular weights for the polymers will normally lie within the range 2000-20,000, preferably 3500-10,000, and more preferably 5000-9000, e.g. about. 8000.

Although the preferred polyacetal carboxylates have been described above, it will be understood that they can be completely or partially replaced with other such polyacetal carboxylates or related organic building salts which are described in the above-mentioned patents on such compounds, methods for their preparation and mixtures in which they are used. Moreover, the chain-terminating groups described in the various patents, especially in US patent 4144226, can be used, provided that they have the desired stabilizing properties that allow the aforementioned builders to be depolymerized in acidic media, facilitating their biochemical degradation in wastewater streams , but maintain' their stability in alkaline media, such as in washing solutions.

The carbonate and bicarbonate builders are strongly preferred sodium salts, but other water-soluble alkali metal carbonates and bicarbonates may also be used, at least in part, such as e.g. the potassium carbonates and bicarbonates. These can be in an anhydrous, hydrated or partially hydrated state. Sodium sesquicarbonate can be used as a full or partial replacement for the carbonate and bicarbonate. One of the advantages of the present invention is that the sodium carbonate occurring in "Builder U", i.e. the available polyacetal carboxylate, is usable as a builder in the manufactured detergents.

The zeolite component will usually have the formula (Na2O)x.(Al2O3) .(Si02).w H20, where x is 1, y is 0.8-1.2, preferably approx. 1, z is 1.5-3.5, preferably 2-3 or approx. 2, and w is 0-9, preferably 2.5-6. Such zeolites are cation exchange and have an exchange capacity for calcium ions of 200-400 or more milligram equivalents of calcium carbonate hardness per gram. They will preferably be hydrated to a degree of 5-30%, preferably 10-25%, moisture, e.g.

about. 20% of it. Zeolite A is preferred (X and Y are also applicable), and of such zeolite 4A is most preferred. The zeolites or zeolites' particle sizes will generally lie within the range 149-37 µm, preferably 105 µm or 74-44 µm, but their final sizes will be below 1 µm.

The fifth component in the present detergents

is a nonionic, synthetic, organic surfactant or a mixture of such surfactants. Although various suitable nonionic surfactants have the desired cleaning properties and physical characteristics (normally solid at room temperature, but can be transferred to liquid form so that they are 'applied to base beads in liquid form), can be used, at least as part of the surfactant content in the available detergents

funds. It is strongly preferred that the nonionic surfactant is a condensation product of ethylene oxide and a higher fatty alcohol. The ethylene oxide content in such surfactants will lie within the range 3-20, preferably 3-12, and more preferably 6-8, e.g. about. 6.5 or 7, moles of ethylene oxide per

moles of fatty alcohol, and the fatty alcohol will usually have 10-18, preferably an average of 12-15, e.g. about. 13 or 14, carbon atoms. Among the other non-ionic surfactants that can also be used are the ethylene oxide condensation products of alkylphenols with 5-12 carbon atoms in the alkyl group, such as nonylphenol, in which the ethylene oxide content is 3-30 mol per molecule, and condensation products of ethylene oxide and propylene oxide sold under the trade name Pluronic^.

Although essentially anhydrous products can be produced and are useful, as a rule moisture will be present in the detergent either in free form or as a hydrate, e.g.

a hydrated carbonate. The presence of such a hydrate helps to make the detergent particles stronger and sometimes makes it easier to dissolve such particles in the wash water. For these reasons and to facilitate manufacture, moisture is preferably present in the product.

In addition to the components mentioned, other materials, such as a supplementary builder (sodium silicate) and auxiliary additives, can be used. In some cases, condensation products of higher fatty alcohol and ethylene oxide with a higher ethylene oxide content than 20 mol per molecule is used as a replacement for part of the condensation products with a lower ethylene oxide content. If it is thus desirable to further improve the flowability of a preferred product, a harder non-ionic component, such as a component with 21-50 ethylene oxide groups per molecule, is used as a partial replacement, and in this case it will preferably amount to 1-50, as a rule more preferably 5-25%

of the total content of non-ionic surfactant. Moreover, sodium silicate, which exerts a supplementary building effect and helps to inhibit corrosion attack on aluminum objects in washing water containing the detergent, will have a ratio of Na20:SiO2 of 1:1.6-1:3, preferably -1*2-1:2 ,6, e.g. 1:2.35 or 1:2.4.

Among the various auxiliaries that can be used are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, antioxidants, fluorescent whitening agents, buffers, fungicides, germicides and fluidity-promoting agents. If desired, fillers such as sodium sulfate and/or sodium chloride can also be present. Among the "auxiliary additives" are also various fillers and impurities in other components of the detergents included, such as Na^CO^in the polyacetal carboxylate ("Builder U")

The amounts of the various components that will lead to the improved cleaning properties (mentioned above) will normally be 5-35% non-ionic surfactant and 30-95% of a combination of polyacetal carboxylate and carbonate, bicarbonate and zeolite builders. The ratio between the polyacetal carboxylate and the combination of carbonate, bicarbonate and zeolite will lie within the range 1:5-2:1, preferably 1:5-3:2, and more preferably 1:4-1:1, e.g. about. 1:2,4. Any residue in such mixtures will consist of filler or fillers, another builder or builders, an auxiliary additive or

- means and moisture. As a rule, the content of nonionic surfactant will be at least 5% of the product, and the content of carbonate plus bicarbonate plus zeolite builders will be at least 20, preferably at least 35,% of the product. The content of non-ionic surfactant will preferably be 10-30, more preferably 10-20, e.g. about. 16.%, the content of the polyacetal carboxylate will preferably be 10-40, more preferably 10-25, e.g. about. 18 or 22.%, and the total content of carbonate, bicarbonate and zeolite will preferably be 35-80, more preferably 50-70, e.g. about. 62.% of the detergent. The ratio between carbonate and bicarbonate will lie within the range 1:2-4:1, preferably 1:1-3:1, and more preferably 1:1-2:1, e.g. about. 1:1,4. The ratio between zeolite and the combination of carbonate and bicarbonate will normally lie within the range 3:1-1:3, preferably 1:2-2:1, e.g. about. 0.9.. Preferably the percentages of carbonate, bicarbonate and zeolite will lie within the ranges 5-25%, respectively. 3-20% and 8-35%, more preferably 10-20%, 5-15% and 10-25% respectively, e.g. he-

respectively approx. 14%, approx. 10% and. about. 21%. The product's moisture content will usually be 1^20, preferably 2-15, and more preferably 3-8, e.g. about. 4 or 5, %. Such a moisture content includes the moisture content that can be removed from the product in a standard drying oven (10 5°C for 2 hours). If sodium silicate is present, the sodium silicate content will be 1-18, preferably 5-15, and more preferably 5-10. e.g. about. 8.%. The total percentage of auxiliary additives can vary from 0 to 20%, but it will normally lie at the lower end of such a range, 1-10%, preferably 2-6%, e.g. about. 4 or 5%, as the percentage amounts for the individual auxiliary additives will as a rule lie within the range 0.1-5, preferably 0.2-3, %. In the above description and elsewhere in the description, the percentages for carbonate and bicarbonate have been given on an "anhydrous" basis and do not include moisture which can be removed by drying in an oven, as described above. The content of filler or fillers can be as high as 40% in some cases, but as a rule, if a filler is present, the amount of this will lie within the range of 5-30, often 10-25, %.

The particulate detergent product according to the invention can be produced using the method described in US patent 4269722. According to such a method, an aqueous slurry is produced which includes the particulate sodium carbonate, sodium carbonate and zeolite, sodium silicate, usually added in the form of an aqueous solution, water and any suitable fillers and auxiliary additives, such as e.g. fluorescent whitener and pigment, which are heat stable. Sodium sulfate has been shown to adversely affect the fluidity of the detergent when added to basic beads together with non-ionic surfactant, and its presence is therefore sometimes avoided. In some cases, the polyacetal carboxylate builder can be added in the kneading apparatus, but because it has occasionally been shown that this has limited stability when treated, at an elevated temperature, such a builder is often added afterwards. In general, the mixture in the kneader will have a solids content of 40-70% and is heated to a temperature of 40-70°C. Anhydrous or hydrated bicarbonate and carbonate or another suitable combined form of these, such as sodium sesquicarbonate, can be used. However, a major amount of the non-ionic surfactant component will not be present in the kneader. It will instead be added afterwards, and the amount of non-ionic surfactant in the kneader will preferably be limited to approx. 4%, preferably 2% or less (on a final product basis), and it is most preferred that no nonionic surfactant be present in the kneader to avoid loss of such surfactant during the spray drying operation. If it is difficult to stir for the slurry to become uniform, due to too strong gel formation or dilution of the mixture, viscosity-regulating agents, such as citric acid, magnesium sulfate and/or magnesium citrate, can be used. Such diluents will be considered as belonging to the group designated as "auxiliary additives". After careful mixing in the kneader, which can take from 10 minutes to an hour, the slurry is pumped into a conventional atomization drying tower in cocurrent or countercurrent, and in the tower it is dried using heated drying air at a temperature of 200-500°C preferably 200-350°C if the mixture contains polyacetal carboxylate, for the production of globular, spray-dried particles with sizes in the range from 2.38 mm to 149 µm. Such base pearls have a desired porosity so that they are able to

absorb nonionic surfactant, and this porosity is due at least in part to the splitting of bicarbonate to carbonate during the spray drying, which leads to the formation of "blowing" carbon dioxide. Normally 20-80% of the bicarbonate is converted to carbonate depending on the conditions in the atomization tower.

The obtained porous base beads are introduced into a suitable batch or continuous mixing apparatus, such as an inclined rotating drum (batch), in which they are post-sprayed at a suitable temperature at which no

ionic surfactants are liquid, usually in the range 45-60, preferably 45-50,°C. According to one embodiment of the present method, the entire amount of is non-ionic

surfactant in a liquid state and preferably at an elevated temperature within the described preferred range sprayed on the surface of the mass of base beads which are kept in motion, by means of an atomizing nozzle of the usual type, and during mixing it penetrates into the beads as part of it does not -ionic surfactants are kept close to the beads' surface. Without cooling until the surfactant's solidification point, the polyacetal carboxylate builder is then in finely divided powder form, e.g. with particle sizes in the range of 74-37 µm (although coarser particles as large as 149 µm can also be used), the dust on the base beads which are held in motion and which now contain absorbed nonionic surfactant. Some of the fin-

split polyacetal carboxylate particles are drawn into the interstices and voids of the beads by the still liquid nonionic surfactant, and other particles adhere to the surfactant near the surface of the beads and are retained on the beads gradually

as the surfactant is cooled to solidification. In such an operation, the polyacetal carboxylate held on the base beads inhibits the production of a sticky product. At the same time, the solid content of the surfactant in the beads prevents layer formation in the product in its end-use packaging during shipping and storage.

Various auxiliary additives of the types that would normally be added afterwards, such as enzyme powder and perfumes,

can be added together with the polyacetal carboxylate powder or before or after the powder addition. As a rule, as is the case with the nonionic surfactant, it is preferred

to spray liquid components on the surfaces of the intermediate detergent product particles, but in some cases, which is also the case when applying the non-ionic surfactant

in a liquid state on the base beads, spraying is unnecessary, and dripping the liquid also serves to distribute it satisfactorily and to promote absorption of it in the porous particles. Powdery materials that are added are preferably in finely divided powder form, as described above in connection with the polycarboxylate builder, but other particle size ranges can also be used (which they also can for the builder) even if the results in

such cases do not have to be as satisfactory. Instead of spraying the liquid material on spray-dried base beads for absorption, the liquid can also in some cases be applied to granular (not spray-dried or agglomerated) mixed carbonate, bicarbonate and zeolite particles, but this is usually not as satisfactory because such particles normally do not have the absorption capacity of spray-dried base beads, and they are less uniform.

Instead of causing post-applied powdery polyacetal carboxylate particles to adhere to liquid surfactant which has been applied to base beads, according to another and preferred method according to the invention, the builder is applied to the base beads in the form of a dispersion of the polyacetal carboxylate in the normally solid non-ionic surfactant at elevated temperature and in liquid state.

In such an application, part of the polyacetal carboxylate builder may be dissolved in the liquid, nonionic surfactant, but normally more of it will be dispersed therein, preferably in finely divided particles, such as particles smaller than 74 µm and preferably larger than 37 um. In such applications, the base beads may initially be heated to a temperature similar to that of the liquid surfactant being applied, but it has been found that although such an operation would theoretically be expected to promote stronger absorption of the surfactant and polyacetal carboxylate builder,

is it sufficient in practice for the base beads to be at room temperature at which satisfactory absorption and rapid cooling of the product is obtained. The dispersion of polyacetal carboxylate builder particles in nonionic surfactant in liquid state is preferably sprayed onto

a layer of base beads that is kept in motion, but occasionally spraying is unnecessary, and a mere dripping of the liquid medium onto the base beads is satisfactory, and in some cases it is sufficient simply to mix the base beads and the dispersion with each other without it is necessary to be concerned with the manner in which the liquid dispersion is applied to the base beads.

The temperature for the dispersion of polyacetal carboxylate particles in a non-ionic surfactant can be such a temperature that has been shown to be suitable for use in the described process. Normally, such a temperature will lie within the range 45-95°C, but preferably in order to better maintain the stability of the polyacetal carboxylate and to promote faster cooling after applying this to the base particles, the application temperature will lie within the range 45-60, most preferably 45-50 or 55, °C. However, this depends on the solidification point of the non-ionic surfactant, which will be the same as or lower than the lowest temperature within such a range. When using higher-melting non-ionic surfactants, the lower limit of the range will of course be correspondingly regulated and will, as a rule, be at least 2, preferably at least 5 or 10,°C higher than ■• the solidification point. The polyacetal carboxylate will preferably have such particle sizes that essentially all particles (generally over 90%, preferably over 95%, and more preferably over 98%) are no larger than they will pass through a sieve with a 74 µm sieve opening. However, particles of larger size can be used, but these will generally not be larger than 149 µm or 95 µm. The particles will preferably have sizes within the range from 74 µm to 37 µm, e.g. from 74 µm to 44 µm, to facilitate penetration into spaces in the base beads and to promote better adherence to the base bead surfaces.

In the aforementioned dispersions in which part of the polyacetal carboxylate can be present in a dissolved state, the ratio between polyacetal carboxylate and non-ionic surfactant will normally lie within the range 1:20t3:2, preferably 1:10-1:1, and more preferably 1:2- 1:1. Such conditions can, however, be regulated depending on the desired recipe conditions between the polyacetal carboxylate and non-ionic surfactant to be present in the final product. Normally no more than three parts polyacetal carboxylate will be present together with two parts nonionic surfactant, and such an upper limit will normally be 1:1. If more polyacetal carboxylate is desired in the product recipe, this can be added afterwards, as previously described, after absorption of part of the polyacetal carboxylate and the non-ionic surfactant in a liquid state. Although other materials, including particulate materials such as enzymes, may be subsequently added, these may occasionally be dissolved and/or dispersed in the nonionic surfactant together with the polyacetal carboxylate, and they may be applied to the base beads together with such a builder and a such surfactant. In addition, a small or large amount of the zeolite, e.g. 2-20% of the detergent is dispersed in the non-ionic surfactant together with the polyacetal carboxylate and/or it can be applied afterwards to improve the product's flow properties. The zeolite percentages include water of hydration because at least part of it cannot be easily removed by heating.

In some cases, a part (and sometimes the entire amount) of the polyacetal carboxylate can be spray-dried together with the carbonate, bicarbonate and zeolite builders, but in such cases it would be desirable to use mild conditions, as special care must be taken so that the product does not be accumulated on the inner walls of the spray tower where the poly-icetal carboxylate will be able to be split. As long as the spray tower conditions are such that the bead temperatures do not rise to a destabilizing temperature for the polyacetal carboxylate used, spray drying is possible, but as this cannot always be ensured in connection with spray drying processes on a technical scale, for practical reasons it is often preferable to subsequently add the polyacetal carboxylate.

The product of the stated recipes and prepared by any of the described methods is satisfactorily free-flowing, non-tacky and non-caking despite its nonionic surfactant and polyacetal carboxylate content. The product's particles are uniform in shape, approximately spherical, and the product has the desired bulk density (higher than the bulk density of common spray-dried products which tends to be in the range of 0.25-0.4 g/ml) normally within the range of 0.5-0.8, e.g. 0.6-0.7, g/ml. Thus, smaller packages can be used, and this provides more available shelf space in warehouses and facilitates storage for home washing. The manufactured detergent is an excellent detergent with improved cleaning ability against a number of dirt types. Its washing power is greater than the washing power of a control detergent without the polyacetal carboxylate. It is surprising that the washing power of the present detergents is better than the washing power of a control detergent despite the fact that the proportion of non-ionic surfactant in the control detergent is higher. It should be pointed out that the overall ratio of builders is greater in the "experimental" product, but on the other hand, the ratios of carbonate, bicarbonate, zeolite and silicate builders are lower.

The examples below serve to illustrate

the present invention. If nothing else is stated, all temperatures are in °C and all parts are based on weight in the examples, otherwise in the description and in the patent claims.

Example 1

^Condensation product of 6.5 mol ethylene oxide and 1 mol higher fatty alcohol with 12-13 carbon atoms sold under

trademark Neodol 2 3-6.5.

(2)

Calculated weight average molecular weight approx. 8000 and with approx. 80% active polymer content.

The particulate detergent with the above recipe is prepared by spray drying part of the recipe components, including the sodium carbonate, the sodium bicarbonate and the zeolite for the production of basic beads, after which other components according to the recipe, including the non-ionic surfactant, the polycarboxylate, the enzyme and the perfume, are mixed with the basic pearls. The kneader slurry is made by sequentially adding to a detergent kneader 32.5 parts water (preferably deionized water, but tap water with up to 150 ppm CaCO^ equivalent can be used), 7.9 parts natural sodium carbonate, 15.8 parts sodium bicarbonate of industrial grade, 24.2 parts of a 20% hydrated zeolite 4A (particle size approx. 44 µm), 2.1 parts of MgSO4.7 ^0, 0.4 part of sodium citrate, 15.6 parts of a 47, 5% aqueous solution of sodium silicate with a ratio Na~0:SiOa of approx. 1:2.4, 1.2 parts

(R)

fluorescent whitener (Tinopar^ 5 BM conc.) and 0.14

part ultramarine blue pigment, and the mixing is carried out at a temperature of 45°C during these additions

and for 20 minutes thereafter, after which the slurry, which has a solids content of approx. 45%, is dropped into a high-pressure pump that pumps the slurry through atomizing nozzles at the top of a counter-flow atomization drying tower in which heated drying air at a temperature of approx. 325°C dries the slurry to essentially globular, porous particles with sizes in the range of 2.0 mm to 149 µm and with a moisture content of approx. 6%. In some cases, a smaller proportion of recycled base beads (or final product) can be introduced into the mixing apparatus for renewed processing and then with the correct change to the recipe to make this possible.

The base beads obtained, which are usually approximately at room temperature, but which in some cases still have a temperature between the air temperature at the bottom of the tower and room temperature, closer to room temperature (occasionally 5--30°C above this), are introduced into a mixing device which in this case consists of an inclined rotating drum, into which 77.05 parts of the base beads, 20.72 parts of the ethoxylated nonionic alcohol surfactant, 30 parts of "Builder U", 1.98 parts of enzyme and 0.25 part of perfume are added in order. The ethoxylated alcohol is sprayed onto the layer of base beads which are kept in motion, at an elevated temperature of 503C at which it is in a liquid state, The used Builder U"

and proteolytic enzyme (mixtures of amylolytic and proteolytic enzymes, e.g. 1:1 mixtures, can also be used) are "dusted" onto the layer of base beads which are kept in motion, after these have absorbed the nonionic surfactant (which usually takes place within 2 - 10 minutes),

. after which the perfume is sprayed onto this intermediate product which is kept in motion. The manufactured particulate detergent has a particle size

within the range from 2.0 mm to 149 µm and has a bulk density of 0.65 g/ml. It is free-flowing, non-sticky and non-caking at room temperature. After cooling and sieving, should this be desired in order to achieve that all or essentially all of the particles have a size within the range from 2.0 mm to 149 µm,

the product is packed, crated, stored, and shipped. It turns out that it has a uniform composition throughout the pack and that the contents of the different packs are also uniform.

It also produces no bottom separation during shipping and storage.

A comparative product is prepared in the same manner as described above, except that the sodium polyacetal carboxylate ("Builder U") is omitted from it. Instead of 100.0 parts of product, 76.9 parts are thus produced, and the quantities of the various components in the product are .30% greater than the quantities stated in the above recipe. When the "trial" product is examined and compared to the "control" product to determine the washing power in a standard soil removal test using different soil types deposited on a variety of different cloth substrates, the product of the invention is found to be significantly superior in terms of soil removal -effect (or washing power) than the control product.

In the used washing power tests using an automatic washing machine with 6 7 liters of water at 49°C, 1.8 kg of clean laundry and three cloths of each of five different test substances are filled in the washing machine. The first and second of these test fabrics are available from the Test-Fabric Company.

The first is soiled with graphite, mineral oil and thickening mite on nylon, while the second is soiled with skin fat dirt, particulate matter and kaolin on cotton.

The third test fabric is cotton soiled with New Jersey clay, and the fourth fabric is a cotton-Dacron® blend soiled with such clay. The fifth test piece, designated as EMPA 101, is made of cotton

and is soiled with a mixture of skin grease dirt, soot and olive oil.

After the sets of sample cloths have been washed, one set being washed in an automatic washing machine in which the detergent according to the invention has been added to the wash water so that its concentration in the wash water is 0.07%, while the wash water has a hardness of approx. 150 ppm calcium carbonate equivalent (Ca:Mg of 3:2), and while the time for the washing part of the cycle is approx. 10 minutes, and as the second set is then washed in the same machine to which the control detergent has been added to the wash water, and after drying, the reflection from the cloths is measured and the average for each soiled test item calculated. Using various factors which have been shown by experience to be representative of people's assessment of the importance of a detergent's cleaning ability in relation to the different dirt types, the final dirt removal figures for the experimental detergent and the control detergent are obtained. The dirt removal figure for the product according to the invention is 26.5 points higher than for the control detergent, and this suggests a significant improvement in the detergent according to the invention in terms of washing power.

When other non-ionic surfactants are used in the recipe for the product according to the invention, such as Neodol 25.7, Alfonic^ 1618-65 or a suitable ethylene oxide-propylene oxide condensation product, such as those sold under the trade mark Pluronic, similarly improved washing power is obtained compared to a control detergent from which the polyacetal carboxylate has been looped. When, moreover, parts of the sodium carbonate and sodium bicarbonate are replaced with equivalent sesquicarbonate, e.g. 10-50%, comparable results are obtained. This is also the case when other zeolites, such as X and Y, used in an amount of up to 20% each of the zeolite content are used together with Zeolite 4A. This is also the case when the silicate used has a Na20:SiO2 ratio of approx. 1:2. Changes with regard to the auxiliary additives used, such as the omission of the enzyme or its replacement with amylolytic enzyme, or the addition of relatively small amounts of filler,

such as NaCl and Na2S04, or the presence of other builders, such as NTA or phosphates, will cause the products according to the invention to also exhibit the described type of improvement compared to the control detergent. This also applies when various polyacetal carboxylates, such as polyacetal carboxylates of potassium, ammonium, lower alkyl or alkanolamine with 1-4

carbon atoms in the alkyl groups, are present when the end capping groups used are other than those indicated in the above recipe, such others being those described in US patent 4144226, and when the calculated weight average molecular weights for the polyacetal carboxylate are 5000 or other weights within the be-

written preferred range of 3,500-10,000. When the less desirable components are used, of course the difference in washing power does not have to be as great.

Likewise, comparable results are obtained when the product is produced in other ways, under different conditions, as described above, and when the components are used in different relative amounts, as also described above.

When, for example, the detergent according to the recipe is varied by changing the proportions of components by -10, -20 and -30% while keeping them within the given ranges, similar results are obtained. Furthermore, when a part of the zeolite powder, such as 2-20% of the detergent, is subsequently added to the produced particles, further improved flowability is obtained.

Example 2

Ten parts Neodol 25-7 (a condensation product with

7 mol ethylene oxide and 1 mol higher fatty alcohol with 12-18 carbon atoms on average) and ten parts "Builder U" with a calculated weight average molecular weight of approx. 8000 is converted into a dispersion solution in a liquid state by first mixing these with each other and then heating the mixture to approx. 93 °C. The builder's powder with particle sizes in the range 4 4-3 7 µm does not dissolve in the hot non-ionic surfactant, but is well dispersed in it. The dispersion thus produced is mixed at an elevated temperature within the range 45-55°C, preferably 50°C, with 50 parts of base beads comprising 39% Zeolite 4A hydrate (20% hydration), 2.7% sodium carbonate, 14 % sodium bicarbonate, 4% clay, 1.3% magnesium sulfate, 2.2% fluorescent whitening agent, 0.1% synthetic material, 0.6% polymeric thickener and 11.8% moisture. The resulting product is free-flowing, non-caking and non-sticky and has an excellent appearance. When this is examined and compared with a control detergent from which "Builder U" has been omitted, it turns out to have significantly better washing power.

Similar results can be obtained when other carbonates, bicarbonates, non-ionic surfactants and polyacetal carboxylates are used, and in different relative amounts, within

for the purposes of the above description.

To improve the flowability and the non-sticky and non-caking properties further if this is desired, after the beads have absorbed the non-ionic surfactant and "Builder U", approx. 5 parts finely divided Zeolite 4A or another suitable zeolite is dusted on the beads, or the zeolite with similar particle sizes to the builder can also be dispersed in the non-ionic surfactant and applied to the base beads together with the surfactant and the builder. If such a zeolite is used, it will preferably be a Zeolite A

(4A is most preferred) with a particle size of 74-37 µm, preferably 44-37 µm (if it is dispersed in the non-ionic surfactant or is added afterwards), and the amount thereof will be 5-40 , preferably 10-20.%, and the ratio "between zeolite and non-ionic surfactant will be 1:20-1:1. The ratio of the sum of zeolite and polyacetal carboxylate to non-ionic surfactant (in such a suspension) will preferably lie within the range 1:10-1.1:1 or 1.2:1.

In another experiment where the proportion of base beads used is reduced and the dispersing temperature is lower, 30 parts of the spray-dried beads are mixed, preferably by spraying the dispersion on a layer of the beads kept in motion, with 20 parts of a 1:1 dispersion of the polyacetal carboxylate in the nonionic surfactant at 49°C. The product is free-flowing a few minutes after mixing begins. This product is also non-sticky, non-caking, non-separating and of excellent appearance. It is also a better detergent than a control detergent without the polyacetal carboxylate.

Example 3

The procedure according to example 2 is repeated, but the detergent is made by applying Neodol 25-7 in a liquid state at a temperature of 49°C to the base beads which are kept in motion, by dripping (or spraying) them, after which finely divided "Builder U" -powder (74-37 µm) is mixed with the intermediate product. Ten parts of the non-ionic surfactant are mixed with 30 parts of the basic beads, after which ten parts of "Builder u" powder are added while mixing. Before the addition of "Builder U", the beads are "lazy" (flow poorly), but after the addition of this, they become free-flowing. They have excellent appearance and are non-sticky, non-caking and non-separating and have better washing power than a control detergent without "Builder U".

Variations in the recipe according to the examples

2 and 3 can be carried out, e.g. by using various nonionic surfactants, such as those described previously,

and polyacetal carboxylates of other types, as mentioned earlier. Variations can also be made for the recipe of the base pearls, which has been described previously. in all such cases the product produced will be satisfactory and have improved detergency compared to a control detergent from which the polyacetal carboxylate component has been omitted. In some cases, such as when the proportion of "Builder U" and/or non-ionic surfactant used is sufficient

large enough that fluidity cannot be improved in the desired way,

flowability-improving agents (zeolite builders can fulfill this function) can be incorporated into the final product, preferably by mixing these with "Builder U" and applying this mixture to the base beads which already contain deposited non-ionic surfactant in a liquid state and are located at the pre-elevated temperature, or by applying the fluidity improving agent after the dispersion of nonionic surfactant polyacetal carboxylate has been absorbed by the base beads. Alternatively, endel zeolite, e.g. 10-20% of the product is also dispersed in the non-ionic surfactant.

The mixing methods and devices can also be changed. For example, instead of mixing for 20 minutes in a batch process using a tilting drum, the mixing time can be changed to from 5 to 40 minutes, and other devices can be used, such as V-mixers, fluidized bed mixers, Schugi mixers or Day mixers. The results of such changes will still be that an acceptable product is obtained with the desired characteristics and washing properties and with a desired bulk density of 0.6-0.8 g/ml, as in the present working examples.

Claims (12)

1. Particulate, built-up, non-ionic, synthetic, organic detergent comprising a cleansing part of a non-ionic, synthetic, organic surfactant, characterized in that it also comprises a building part, in combination, of polyacetal carboxylate, alkali metal carbonate, alkali metal bicarbonate and zeolite builders for the nonionic surfactant. 2. An essentially phosphate-free detergent according to claim 1, characterized in that the nonionic surfactant is a condensation product of ethylene oxide and a higher fatty alcohol, the polyacetal carboxylate builder has a calculated weight average molecular weight of 3,500-10,000, the alkali metal carbonate is sodium carbonate, the alkali metal bicarbonate is sodium bicarbonate, and the zeolite is Zeolite A, X and/or Y, and the amounts of the components are 5-35% nonionic surfactant and 30-95% of a combination of polyacetal carboxylate, sodium carbonate, sodium bicarbonate and zeolite builders, the ratio of polyacetal carboxylate and the combination of sodium carbonate, sodium bicarbonate and zeolite builders are within the range 1:5-2:1, while the ratio between sodium carbonate and sodium bicarbonate is within the range 1:2-4:1 and the ratio between zeolite and the combination of sodium carbonate and sodium bicarbonate is within the range 3:1-1: 3, and as any residue of the detergent consists of filler or fillers and/or another builder or builders and/or an auxiliary additive or agents and/or moisture. 3. Phosphate-free detergent according to claim 2, characterized in that the non-ionic surfactant is a condensation product of 3-20 mol of ethylene oxide and one mol of fatty alcohol with 10-18 carbon atoms, the polyacetal carboxylate builder has a calculated weight average molecular weight of 5000-9000, the zeolite is a type A zeolite, and the amounts of the components are 10-30% non-ionic surfactant, 10-40% polyacetal carboxylate, 5-25% sodium carbonate, 3-20% sodium bicarbonate and 8-35% zeolite. 4. Detergent according to claim 3, characterized in that the non-ionic surfactant is a condensation product of 3-12 moles of ethylene oxide and one mole of fatty alcohol with an average of 12-15 carbon atoms, the polyacetal carboxylate has sodium carboxylate as its carboxylate part, the zeolite is hydrated Zeolite A, and the amounts of the components are 10- 20% nonionic surfactant, 10-25% polyacetal carboxylate, 10-20% sodium carbonate, 5-15% sodium bicarbonate and 10-25% zeolite. 5. Detergent according to claim 4, characterized in that the non-ionic surfactant is a condensation product of 6-8 mol ethylene oxide per mol higher fatty alcohol, the polyacetal carboxylate has a calculated weight average molecular weight of approx. 8000, the zeolite is Zeolite 4A, and the quantities of the components are approx. 16% non-ionic surfactant, approx. 22% polyacetal carboxylate, approx. 14% sodium carbonate, approx. 10% sodium bicarbonate, approx. 21% Zeolite 4A with approx. 20% water content, approx. 8% sodium silicate with a ratio Na2 0:S102 of approx. 1:2.4, approx. 4% moisture and approx. 5% auxiliary additives. 6. Detergent according to claim 1, characterized in that it comprises zeolite builder in spray-dried base beads containing carbonate and bicarbonate builders, and subsequently added to such beads plus non-ionic surfactant and polyacetal carboxylate. 7. Detergent according to claim 3, characterized in that it comprises zeolite builder in spray-dried base beads containing carbonate and bicarbonate builders, and 2-20% of the detergent of zeolite which is subsequently added to such beads plus non-ionic surfactant and polyacetal carboxylate. 8. Method for producing a detergent according to claim 1, characterized in that an aqueous mixture from a kneading apparatus and consisting of alkali metal carbonate, alkali metal bicarbonate and zeolite is spray-dried and the obtained spray-dried beads are mixed with non-ionic surfactant in liquid form at an elevated temperature, whereby the surfactant is absorbed into the spray-dried carbonate-bicarbonate-zeolite beads, after which such beads containing the nonionic surfactant are mixed with a polyacetal carboxylate builder, whereby said builder is held firmly to such beads while forming a free-flowing, particulate detergent. 9. Method according to claim 8, characterized in that zeolite powder is mixed with the product according to claim 8 to further improve the flowability of the product. 10. Process for producing a detergent according to claim 1, characterized in that polyacetal carboxylate builder is dissolved and/or dispersed in non-ionic surfactant in liquid form at elevated temperature, an aqueous mixture from a kneader and consisting of alkali metal carbonate, alkali metal bicarbonate and zeolite is spray-dried, and the solution or dispersion of polyacetal carboxylate builder-non-ionic surfactant is applied to the obtained spray-dried beads during mixing, whereby the solution or dispersion is sorbed by the carbonate, bicarbonate-zeolite beads forming a free-flowing, particulate detergent. 11. Method according to claim 10, characterized in that zeolite powder is mixed with the product according to claim 10 to further improve its flowability. 12. Process according to claim 10, characterized in that finely divided zeolite particles are dispersed in the non-ionic surfactant together with the polyacetal carboxylate builder and are applied to the spray-dried beads with such a surfactant and builder.