CH666694A5 - PARTICULATE DETERGENT PRODUCT. - Google Patents

Description

DESCRIPTION

The invention relates to a particulate detergent product containing builder and nonionic surfactant. The product contains a builder-effective amount of a combination of polyacetal carboxylate and carbonate, bicarbonate and zeolite builders. The invention also relates to methods for producing such products.

Particulate detergent products containing nonionic surfactant are known, in which to obtain free-flowing products, base beads, usually made of inorganic builder salt or builder salts, e.g. B. car bonates, bicarbonates and zeolites, which were formed by spray drying an aqueous Crutcher mixture or a pulp, normally contain solid, non-ionic, liquid-applied surfactant absorbed. In the literature and in various patents, polyacetal carboxylate salts are considered to be used with various

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suitable builders are described, in particular anionic surfactants. To date, however, particulate detergent products based on builder (s) and nonionic surfactant containing carbonate, bicarbonate and zeolite builders salts and polyacetal carboxylate within a total amount of builder are not known, nor are the advantages offered by such products and processes for producing the same by applying polyacetal carboxylate and nonionic surfactant to base beads made of carbonate, bicarbonate and zeolite builder salts.

The particulate detergent products containing nonionic surfactant, in which the nonionic surfactant is applied in liquid form to base beads containing porous carbonate, bicarbonate and zeolite builder salts, are described in U.S. Patent 4,269,722. Products of this type were also sold under the Fresh Start trade name. They are particularly valuable as phosphate-free detergents or detergents with a limited phosphate content in areas where detergents with a high phosphate content are prohibited. Polyacetal car-boxylates are described in U.S. Patents 4,144,226 and 4,315,092. U.S. Patent Nos. 4,146,495 and 4,219,437 claim detergent products containing polyacetal carboxylate builders (4,146,495) and similar products containing ketodicarboxylates (4,219,437), which can often serve as a replacement for polyacetal carboxylate. Various other patents deal with similar builders such as e.g. See, for example, U.S. Patent 4,141,676; 4,169,934; 4,201,858; 4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,422; 4,233,423; 4,302,564 and 4,303,777 or European patent applications 0 015 024; 0 021 491 and 0 063 399.

The object of the invention is to make free-flowing detergent products containing nonionic surfactants and improved detergency available.

To achieve this object, a detergent product is proposed according to the invention, which contains a cleaning amount of a nonionic surfactant and a builder effect amount of a combination of a polyacetal carboxylate builder and carbonate, bicarbonate and zeolite builder for the nonionic surfactant. Certain nonionic surfactants, polyacetal carboxylate builders, carbonate, bicarbonate and zeolite builders are preferably used in certain proportions, to obtain a free-flowing, particulate builder-containing detergent product with improved washing power or improved ability to remove dirt. According to the invention, processes for the production of such particulate detergent products are also proposed.

The polyacetal carboxylate used can be that described in US Pat. No. 4,144,226 and can also be prepared by the process mentioned therein. A typical such compound has the formula

RX - (CHO) n - R2 COOM

wherein M is from the group consisting of alkali metal, ammonium, alkyl groups with 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups each with 1 to 4 carbon atoms in the alkylene thereof, wherein n is on average at least 4 and R 1 and R 2 are chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. Preferred is a polyacetal carboxylate in which M is an alkali metal, e.g. B. is sodium, n means 50 to 200, Ri for ch3ch2o mooc

HCO- or H-.C-CO- • J 1

h3c mooc or a mixture thereof, R2 for och2ch3

-CH

stands and n is on average 20 to 100, particularly preferably 30 to 80. The weight-average molecular weights of the polymers are usually in the range from 2000 to 20,000, preferably 3500 to 10,000 and particularly preferably 5000 to 9000, e.g. B. at about 8000.

Although the preferred polyacetal carboxylates have been described above, they can of course be replaced in whole or in part by other polyacetal carboxylates or similar organic builder salts as described in the previously mentioned patents, including processes for their preparation and mixtures in which they are used. Also, the chain end groups specified in the various patents, particularly in U.S. Patent No. 4,144,226, can be used, provided that they have the desired stabilizing properties that allow the builders mentioned to be depolymerized in acidic medium, which will biodegrade them Relieved in waste water, but maintain its stability in alkaline media such as washing solutions.

Particularly preferred carbonate and bicarbonate builders are the sodium salts thereof, but other water-soluble alkali metal carbonates and bicarbonates can also be used, at least in part, such as e.g. B. the potassium salts.

These can be anhydrous, hydrated or partially hydrated. Sodium sesquicarbonate can partially or completely replace the carbonate and the bicarbonate. One of the advantages of the invention is that the sodium carbonate present in Builder U, the commercially available polyacetal carboxylate, is valuable as a builder for making the detergent products of the invention.

The zeolite component generally has the formula (Na20) x. (AhChjy. (SÌO2). W H2O, where x is 1, y is 0.8 to 1.2, preferably about 1, where z is 1.5 to 3.5, preferably 2 to 3 or about 2 and w 0 to 8, preferably 2.5 to 6. Such zeolites are cation exchangers and have an exchange capacity for calcium anen of about 200 to 400 or more mg equivalent calcium carbonate hardness per g. They are preferably up to 5 to 30% hydrated all up to a moisture content of 10 to 25%, for example about 20% thereof. Zeolite A is preferred (X and Y are also useful) and zeolite 4A is most preferred. The particle sizes of the zeolite or zeolites are usually 0.194 to 0.037 mm, preferably 0.105 or 0.074 to 0.044 mm, but their extreme sizes are in the submicron range.

The fifth component of the detergents or detergent products according to the invention is a nonionic surfactant or a mixture of such surfactants. Although various suitable nonionic surfactants can be used, provided they have the desired cleaning and physical properties (i.e., normally solid at room temperature but are liquefiable to be applied to the base beads in liquid form),

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it is very preferred that at least some of the nonionic surfactants used in the products according to the invention are a condensation product of ethylene oxide and a higher fatty alcohol. The ethylene oxide content of such surfactants should be in the range from 3 to 20 moles, preferably 3 to 12 and particularly preferably 6 to 8, e.g. B. are about 6.5 or 7 moles of ethylene oxide per mole of fatty alcohol. The fatty alcohol is usually said to have 10 to 18 carbon atoms, preferably an average of 12 to 15, e.g. have about 13 or 14. Other nonionic surfactants that can also be used are the ethylene oxide condensation products of alkylphenols having 5 to 12 carbon atoms in the alkyl group such as nonylphenol in which the ethylene oxide content is 3 to 30 moles per mole, and condensation products of ethylene oxide and propylene oxide sold under the trade name Pluro-nic are sold.

Although substantially anhydrous products can be made and are useful, the detergent product of the invention generally contains moisture, either in free form or as a hydrate, e.g. as hydrated carbonate and hydrated zeolite. The presence of such hydrates can solidify the particles of the detergent product and sometimes facilitates the dissolution of these particles in the wash water. Therefore, and to facilitate manufacturing, moisture is preferably present in the product.

In addition to the ingredients mentioned, other substances such as supplementary builders (sodium silicate) and auxiliary substances can be used. In some cases, condensation products of higher fatty alcohol and ethylene oxide with ethylene oxide contents above 20 moles per mole can also be used instead of a part of the condensation products with a lower ethylene oxide content. Therefore, if it is advantageous to further improve the flowability of a preferred product, a harder or higher melting (harder) nonionic component, such as e.g. B. one with 21 to 50 ethylene oxide groups per mole, with weight amounts of 1 to 50% preferred, mostly 5 to 25% of the total content of nonionic surfactant are particularly preferred. The sodium silicate, which complements the builder action and helps prevent the corrosion of aluminum objects in the water containing the detergent product, has a NaîO: Si02 weight ratio in the range of about 1: 1.6 to 1: 3, preferably 1: 2 up to 1: 2.6, e.g. B. 1: 2.35 or 1: 2.4.

Among the various auxiliaries that can be used are coloring substances such as dyes and pigments, fragrances, enzymes, stabilizers, antioxidants, fluorescent brighteners, buffers, fungicides, ger-micides and flow-promoting substances. If necessary, fillers such as sodium sulfate and / or sodium chloride can also be present. The "auxiliaries" also include various fillers and impurities in other components of the product, such as Na2CÜ3 in the polyacetal carboxylate (Builder U).

The amounts by weight of the various ingredients which result in the above-mentioned improved washing performance are normally 5 to 35% nonionic surfactant and 30 to 95% of a combination of polyacetal carboxylate and carbonate, bicarbonate and zeolite builders. The weight ratio of polyacetal carboxycat to the combination of carbonate, bicarbonate and zeolite is usually in the range from 1: 5 to 2: 1, preferably 1: 5 to 3: 2 and particularly preferably from 1: 4 to 1: 1, e.g. at about 1: 2.4. A possible balance in such product compositions are filler (s), other builders, auxiliaries) and moisture. The content of nonionic surfactant is usually bicarbonate plus zeolite builder at least 20%, preferably

35% of the same. The content of nonionic surfactant is preferably 10 to 30%, particularly preferably 10 to 20%, e.g. about 16%, that of the polyacetal carboxylate preferably 10 to 40%, particularly preferably 10 to 25%, e.g. 18 or 22%, and the total content of carbonate, bicarbonate and zeolite is preferably 35 to 80%, particularly preferably 50 to 70%, e.g. about 62% of the detergent. The weight ratio of carbonate to bicarbonate is in the range of 1: 2 to 4: 1, preferably 1: 1 to 3: 1 and particularly preferably 1: 1 to 2: 1, e.g. at about 1: 1.4. The weight ratio of zeolite to the combination of carbonate and bicarbonate is normally in the range of 3: 1 to 1: 3, preferably 1: 2 to 2: 1, e.g. about 0.9. The weight percentages of carbonate or bicarbonate or zeolite are preferably in the ranges from 5 to 25% or 3 to 20% or 8 to 35%, particularly preferably from 10 to 20% or 5 to 15% or. 10 to 25%, e.g. at about 14%, 10% and about 21%. The moisture content of the product is usually 1 to 20%, preferably 2 to 15% and particularly preferably 3 to 8%, e.g. B. about 4 or 5%. This moisture content includes that which can be removed from the product when dried in the oven under standard conditions (105 ° C, 2 hours). The content of optionally present sodium silicate is 1 to 8%, preferably 5 to 15% and particularly preferably 5 to 10%, e.g. about 8%. The total percentage of excipients is usually in the range of 0 to 20%, but is normally 1 to 10%, preferably 2 to 6%, e.g. about 4 or 5%, the percentages of the individual auxiliaries usually being about 0.1 to 5%, preferably 0.2 to 3%. The percentages of carbonate and bicarbonate given above and overall in the description are on an anhydrous basis and do not include the moisture which can be removed by oven drying. The percentages of zeolite include the water of hydration, however, since at least part of it cannot be easily removed by heating. The filler content) can be as high as 40% in some cases. If fillers are present, however, they are usually present in an amount of 5 to 30%, often 10 to 25%.

The processes for producing the detergent products according to the invention are defined in the patent claims.

The detergent product according to the invention can also be produced by the process described in US Pat. No. 4,269,722. Reference is expressly made to this patent as well as to US Pat. No. 4,144,226. Such a process produces an aqueous slurry of particulate sodium carbonate, sodium bicarbonate and zeolite, sodium silicate, which is usually added as an aqueous solution, and water, and suitable and heat-stable fillers and auxiliaries such as fluorescent brighteners and pigment may be present. Sodium sulfate has been shown to adversely affect the fluidity of the detergent product when added to the base beads with nonionic surfactant so that its presence is sometimes avoided. In certain cases, the polyacetal carboxylate builder can be added to the crutcher, but this builder is often added afterwards, since it has been shown that it is sometimes only of limited stability when working at elevated temperatures. The Crutcherge mixture generally has a solids content of 40 to 70% and is heated to a temperature of 40 to 70 ° C. Anhydrous or hydrated bicarbonate and carbonate or other suitable combinations thereof such as sodium sesquicarbonate can be used. However, the majority of the nonionic surfactant is not present in the crutcher, but is instead added subsequently. The amount of nonionic surfactant in the crutcher is preferably limited to approximately 4%, particularly preferred

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to 2% or less (based on the end product) and most preferably there is no surfactant in the crutcher so that there is no loss of surfactant during spray drying. If it becomes difficult to stir to obtain a uniform mixture because of excessive gelation or thickening, viscosity control agents such as citric acid, magnesium sulfate and / or magnesium citrate can be used. These diluents are said to fall under the group known as "auxiliaries". After thorough mixing in the crutcher, which may take 10 minutes to 1 hour, the crutcher slurry is pumped to a conventional spray drying tower operating with cocurrent or countercurrent methods, in which it is preferred by heated drying air at a temperature of 200 to 500 ° C 200 to 350 ° C, if the mixture contains polyacetal carboxylate, is dried. Round spray-dried particles with sizes in the range from 2.38 mm to 0.149 mm are formed. Such base beads are desirably porous so that they can absorb nonionic surfactant. This porosity is at least partly due to the decomposition of bicarbonate in carbonate during spray drying, which leads to the emission of carbon dioxide. Typically, depending on the conditions in the spray tower, 20 to 80% bicarbonate changes to carbonate.

The resulting porous base beads are usually placed in a suitable batch or continuous mixer, e.g. into an inclined rotary drum (discontinuously), and then sprayed at a suitable temperature at which the nonionic surfactant is liquid, usually in the range from 45 to 60 ° C., preferably 45 to 50 ° C. In one embodiment of the process according to the invention, the entire nonionic surfactant, which is in the liquid state and preferably at an elevated temperature in the preferred range, is sprayed onto the moving base beads by means of a spray nozzle of the usual type and penetrates into the interior of the beads during mixing, a portion of the nonionic surfactant remains near the surface thereof. Then, without cooling to the solidification point of the surfactant, the polyacetal carboxylate builder in finely divided powdered form, for example with particle sizes in the range from 0.074 to 0.037 mm (although coarser particles with sizes of 0.149 mm can also be used), is dusted on the moving base beads that already contain absorbed nonionic surfactant. Some of the finely divided polyacetal carboxylate particles are drawn into the spaces or gaps and hollows or depressions of the beads by the still liquid nonionic surfactant, while others adhere to this surfactant close to the bead surfaces and are held on the beads when the surfactant is cooled to solidify. In this process, the polyacetal carboxylate held on the base beads prevents a sticky product from forming and the product packaged for sale forms layers during shipping and storage.

Various auxiliaries that would normally be added afterwards, such as powdery enzymes and fragrances, can be added with the polyacetal carboxylate powder or before or after the powder addition. As with the nonionic surfactant, it is generally preferred to spray liquid ingredients onto the surfaces of the particles of the detergent composition (intermediate). In some circumstances, however, as with the application of the nonionic surfactant in liquid form to the base beads, spraying is unnecessary and it is sufficient to drip the liquid on to distribute and promote its absorption in the porous particles. The powdered materials are preferably added in finely divided powder form as described above for the polyacetal carboxylate builder, but other particle size ranges are also possible (as for the Buil-5 of), although the products obtained may not be so advantageous. Also, instead of spraying the liquid material for absorption onto spray-dried base particles, in some cases the liquid can be applied onto the granulated (not spray-dried) carbonate, bicarbonate and zeolite particles, but this is usually not as satisfactory as these particles usually do not have the absorption capacity of spray dried base beads and are not as uniform.

Instead of subsequently applying the powdered polyacetal carboxylate particles 15 adhering to liquid surfactant applied to the base beads, according to another and preferred method of the invention, the builder is applied to the base beads as a dispersion of the polyacetal carboxylate in the normally solid nonionic surfactant at elevated temperature and in liquid Condition upset. Here, part of the polyacetal carboxylate builder can be dissolved in the liquid nonionic surfactant, normally it is largely dispersed therein, preferably in fine particles, for example less than 0.074 mm and preferably greater than 0.037 mm. In such application methods, the base beads can first be heated to a temperature equal to that of the surfactant to be applied in the liquid state. However, although such a measure seems theoretically suitable to promote a stronger absorption of the surfactant and the polyacetal carboxylate builder, it has been shown in practice that it is sufficient if the base cakes are at room temperature, whereby a satisfactory absorption takes place and the product cools down quickly. The dispersion of the polyacetal carboxylate builder particles in the nonionic surfactant, which is in the liquid state, is preferably sprayed onto a moving bed or fluid bed with base beads. However, sometimes spraying is not necessary and it is sufficient to simply drop the liquid medium onto the base beads. Under certain circumstances, it is even sufficient to simply mix the base beads and the dispersion with one another without the manner in which the liquid dispersion is applied to the base beads being important.

The dispersion of the polyacetal carboxylate particles in a 45 nonionic surfactant should have a temperature suitable for application, which is normally in the range from 45 to 95 ° C. In order to be able to keep the polyacetal carboxylate more stable and to cool it more quickly after it has been applied to the base particles, an application temperature in the range from 45 to 60 ° C. is preferred, most preferably from about 45 to 50 or 55 ° C. However, this depends on the freezing point of the nonionic surfactant, which is said to be equal to or lower than the lowest temperature of such a range. Of course, with 55 higher melting nonionic surfactants, the lower limit is set accordingly and is normally at least 2 and preferably at least 5 or 10 ° C. higher than the solidification point. The particle sizes of the polyacetal carboxylate are preferably essentially all 60 (usually more than 90 percent, preferably more than 95 percent and particularly preferably more than 98 percent) not greater than 0.074 mm. However, larger particles can be used, but generally not larger than 0.149 mm or 0.094 mm. Preferably the particles have 65 sizes in the range 0.074 to 0.037 mm, e.g. B. 0.074 to 0.044 mm to promote the penetration of the gaps or the gaps between the or the base beads and better adhesion to the surface thereof.

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In the dispersions mentioned, in which part of the polyacetal carboxylate can be in solution, the weight ratio of polyacetal carboxylate to nonionic surfactant is usually in the range from 1:20 to 3: 2, preferably 1:10 to 1: 1 and particularly preferably 1: 2 to 1: 1. These weight ratios can, however, be adjusted depending on the desired formulation ratios of polyacetal carboxylate and nonionic surfactant in the end product. Usually, however, no more than 3 parts of polyacetal carboxylate per 2 parts of nonionic surfactant are present, preferably this upper limit is 1: 1. If more polyacetal carboxylate is desired in the formulation of the final product, it can be applied subsequently, as previously described, after absorption of some of the polyacetal carboxylate and the nonionic surfactant in the liquid state. Although other materials including particulate substances such as enzymes can be added afterwards, they can sometimes also be dissolved and / or dispersed in the nonionic surfactant with the polyacetal carboxylate and applied to the base beads together with this builder and surfactant. Part or all of the zeolite, e.g. B. 2 to 20 percent of the composition in which the nonionic surfactant is dispersed with the polyacetal carboxylate, and / or applied later to improve the flow behavior of the product.

In some cases, part (sometimes all) of the polyacetal carboxylate can be spray dried with the carbonate, bicarbonate and zeolite builder, however mild conditions are desirable and particular care must be taken to avoid product build up on the interior walls of the spray tower , which could decompose the polyacetal carboxylate. If the conditions in the spray tower are such that the bead temperatures do not reach the destabilization temperature for the polyacetal carboxylate used, spray drying can be carried out, but this is not always guaranteed in spray drying processes customary in industry, which is why, for practical reasons, the subsequent application of the polyacetal carboxylate is often preferable is.

The product according to the formulations specified, which is produced by one of the processes described, is sufficiently free-flowing, not sticky and does not cake, despite its content of nonionic surfactant and of polyacetal carboxylate. The product particles have an approximately round, regular shape. The product has a desired bulk density (higher than the bulk density of the known spray-dried products, which is often in the range of 0.25 to 0.4 g / ml), which is usually about 0.5 to 0.8 g / ml, for example Is 0.6 to 0.7 g / ml. This means that smaller packs can be used, making more control room available in the supermarket and also making it easier to keep supplies in the household. The detergent product is an excellent detergent with improved cleaning power against a wide range of soiling. Its cleaning power is greater than that of a comparison product without polyacetal carboxylate.

Surprisingly, the detergency of the products of the invention is better than that of a comparison product, although the proportion of nonionic surfactant in the comparison product is greater. It is noteworthy here that the total builder content in the product of the invention is greater, but at the same time the amounts of carbonate, bicarbonate, zeolite and silicate builders are lower.

The following examples are intended to illustrate the invention. The temperatures are given in ° C, the parts in the examples and the description and in the claims relate to the weight.

example 1

Part of parts

Sodium carbonate (anhydrous) 13.6

Sodium bicarbonate 9.7

Sodium zeolite (Zeolite 4A, 20% hydrate) 20.7

Polyethoxylated higher fatty alcohol than 15.9 non-ionic surfactant1

Sodium polyacetal carboxylate (Builder U) 23.1

Sodium silicate, solid (NA2O: Si02 = 1: 2.4) 8.2

Magnesium sulfate (anhydrous) 1.17

Sodium citrate (viscosity regulator) 0.45

Moisture 4.0 enzyme, powder (proteolytic enzyme,

0.074 mm corresponding to 200 meshes) 1.52 fluorescent brightener (Rinopal 5BM Conc.) 1.32

Blue pigment (ultramarine blue) 0.15

Perfume 0.19

100.0

1 condensation product of 6.5 moles of ethylene oxide and one mole of higher fatty alcohol having 12 to 13 carbon atoms, sold as Neodol 23-6.5 by Shell Chemical Company.

2 Supplied by Monsanto Company (as Builder U), with an average molecular weight (weight average) of approximately 8000 and a content of approximately 80% active polymers.

The particulate detergent product according to the above formulation was prepared by spray drying part of the formulation including sodium carbonate, sodium bicarbonate and zeolite to form base beads and then subsequently mixing the other components of the formulation including nonionic surfactant, polyacetal carboxylate, enzyme and fragrance with these base beads. To make the crutcher mixture or slurry, 32.5 parts of water (preferably demineralized water, although tap water with up to 150 ppm CACO3 equivalent hardness can be used), 7.9 parts of natural soda ash, 15.8 parts were added to a soap crutcher Sodium bicarbonate (industrial grade), 24.2 parts of a hydrated 4A zeolite (particle size about 0.044 mm), 2.1 parts of MgSO-t. 7 H2O, 0.4 parts of sodium citrate, 15.6 parts of a 47.5% aqueous solution of sodium silicate with a Na20: Si02 ratio of about 1: 2, 1.2 parts of fluorescent brightener (Tinopal 5PM conc.) And 0 , 14 parts of ultramarine blue pigment and mixed at a temperature of about 45 ° C during these additions and then for about 20 minutes. Then the crutcher pulp, which has a solids content of about 45%, was dripped into a high-pressure pump, which pumped it through spray nozzles at the top of a countercurrent spray drying tower, in which it was mixed with substantially spherical porous particles by drying air heated to about 325 ° C Sizes in the range of 2.00 to 0.149 mm and a moisture content of about 6% were dried. In certain cases, a small proportion of recycled base beads (or end product) can be incorporated into the crutcher mixture for reprocessing, the formulation having to be changed accordingly.

The base beads obtained, which are mostly around room temperature, but in some cases still at a temperature between the air temperature at the tower floor and room temperature, closer to room temperature (sometimes 5 to 30 ° C above), were placed in a mixer, especially in an inclined rotary drum, in which 77.05 parts of base beads, 20.72 parts are gradually placed

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ethoxylated alcohol (nonionic surfactant), 30 parts Builder U, 1.98 parts enzyme and 0.25 parts fragrance were added. The ethoxylated alcohol was sprayed onto the moving bed with base beads at a temperature raised to 50 ° C at which it was liquid. The builder U and the proteolytic enzyme (mixtures of amylolytic and proteolytic enzymes, e.g. I: 1 mixtures can also be used) were "dusted" with (besides) absorption of the nonionic surfactant on the moving bed with base beads (which is usually within about 2 up to 10 minutes). Then the fragrance was sprayed onto this moving intermediate. The particulate detergent product obtained has particle sizes in the range of 2.00 to 0.149 mm and a bulk density of 0.65 g / ml. It is free flowing at room temperature, not sticky and not caking. The product was cooled and optionally sieved to have all or substantially all of the particles in the desired range of 2.00 to 0.149 mm, then it was packaged, coated, stored and shipped. The product is consistent and uniform within the packaging, and the contents of different packs are also uniform. No settling takes place during shipping and storage.

A comparative product was prepared in the same manner as described above, except that the sodium polyacetal carboxylate (Builder U) was omitted. Instead of 100.0 parts of product, 76.9 parts were produced, the proportions of the various components in the product being 30% larger than those given in the above formula. When the product of the invention was tested against the comparative product for detergency in a standard soil removal test in which different soils are applied to different substances, the product of the invention was significantly better than the comparative product in terms of its soil removal effect or cleaning power.

In the tests for checking the washing power, an automatic washing machine containing 67 liters of water at 49 ° C. was used. machine with 1.81 kg of clean textiles and 3 test sections of 5 different test substances each. The first and second test fabrics were obtained from Test Fabric Company. The first was nylon contaminated with graphite, mineral oil and a thickener, the second with cotton contaminated with sebum, particulate matrial and kaolin. The third test fabric was cotton soiled with New Jersey clay and the fourth was a cotton-Dacrone blend soiled with this clay. The fifth test fabric, designated EMPA 101, consisted of cotton and was contaminated with a mixture of sebum oil, soot and olive oil.

The test substance samples were then put together in “sets” and washed. One set was washed in an automatic washing machine in the presence of the detergent product according to the invention in a concentration of 0.07%, the washing water having an approximately 150 ppm calcium carbonate equivalent hardness (Da: Mg ratio of 3: 2) and the washing time of the washing cycle was about 10 minutes. The other set was then washed with washing water in the presence of the comparison product in the same machine. After drying, the reflection values of the sample sections were measured and the average values for each soiled test substance were determined. With the help of various empirical factors, which are considered to be representative for the assessment of the washing power of a cleaning agent by people against various types of soiling, the dirt removal indices for the inventive and the comparative product were determined. The soil removal index for the product of the invention is 26.5 points higher than that of the comparative product, which means that the product according to the invention has a very significantly improved washing power.

If other nonionic surfactants are used in the formulation of the product of the invention, such as Neodol 25-7, Aflonic 1618-65, or a suitable ethylene oxide propylene oxide condensation product such as Pluro-nic, a similarly improved detergency is obtained compared to a product using this Omits polyacetal carboxylate. Even if sodium carbonate and sodium bicarbonate are partially replaced by equivalent sesquicarbonate, e.g. B. 10 to 50%, the results are corresponding. This is also the case when other zeolites, e.g. B. X and Y, up to 20% of the zeolite content, are used with the zeolite 4A or if the silicate used has a Na20: Si02 ratio of about 1: 2. Variants in the auxiliary materials used, such as. B. the omission of enzyme or the replacement of the same by amylolytic enzyme or the addition of relatively small amounts of fillers such as NaCl and Na2SÛ4 or the presence of other builders such as NTA or phosphates also result in products according to the invention with the improvements described compared to the comparison products. This also applies in the presence of various polyacetal carboxylates, such as. B. those of potassium, ammonium, lower alkyl and alkanolamine having 1 to 4 carbon atoms in their alkyl groups when the terminal groups are other than in the formulation above, such other groups being described in U.S. Patent No. 4,144,226, and when the weight average molecular weights of the polyacetal carboxylate are 5000 or other weights within the specified preferred range of 3500 to 10,000. Of course, if the less desirable ingredients are used, the improvement in detergency may not be as great.

Similarly, comparable results are obtained when the product is made differently, under different conditions as described above, and using the components in different proportions. If, for example, the composition of the formulation is changed by varying the proportions of the components by ± 10, +20 and ± 30%, but within the specified ranges, similar results are obtained. In addition, if part of the powdered zeolite, such as. B. 2 to 20% of the detergent product is subsequently applied to the particles produced, the flowability further improved.

Example 2

10 parts of Neodol 25-7 (a condensation product of 7 moles of ethylene oxide and 1 mole of higher fatty alcohol with 12 to 18 carbon atoms on average) and 10 parts of Builder U with a weight-average molecular weight of approximately 8000 were converted into a liquid dispersion / solution by first mixing and then heating to about 93 ° C. The builder powder, which has particle sizes in the range of 0.044 to 0.037 mm, does not dissolve in the hot nonionic surfactant, but does disperse well therein. The dispersion thus prepared was at an elevated temperature in the range from 45 to 55 ° C., preferably at about 50 ° C., with 50 parts of base beads (in a moving bed) made of 39% zeolite 4A hydrate (20% hydration), 27% sodium carbonate , 14% sodium bicarbonate, 4% clay, 1.3% magnesium sulfate, 2.2% fluorescent brightener, 0.1% dye, 0.6% polymeric thickener and 11.8% moisture mixed. The product obtained is free flowing, does not cake, is not sticky and looks good

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out. When tested against a comparative product that does not contain Builder U, it showed significantly better detergency.

Similar results are obtained if other carbonates, bicarbonates, nonionic surfactants and polyacetal carboxylates are used and if different proportions are used within the specified ranges.

In order to further improve the properties such as flowability, non-sticking and non-caking, about 5 parts of finely divided zeolite 4A or another suitable zeolite can be dusted after the absorption of nonionic surfactant and Builder U, or the zeolite with particle sizes similar to those can also be dusted disperse the builder in the nonionic surfactant and apply to the base beads with the nonionic surfactant and builder. If such zeolite is used, it is preferably a zeolite A (4A is most preferred) with a particle size of 0.074 to 0.037 mm, preferably 0.044 to 0.037 (if it is dispersed or subsequently applied in the nonionic surfactant) and the proportion thereof should be 5 to 40%, preferably 10 to 20%, and the ratio of zeolite to nonionic surfactant 1:20 to 1: 1. The ratio of the sum of zeolite and polyacetal carboxylate to nonionic surfactant (in such a suspension) is preferably in the range from 1:10 to 1.1: 1 or 1.2: 1.

In another embodiment, with a lower amount of base beads and a lower dispersion temperature, 30 parts of the spray-dried beads were mixed by spraying the dispersion onto a moving bed of beads, 20 parts of a 1: 1 dispersion of the polyacetal carboxylate in the non-ionic surfactant at 49 ° C. The product will flow freely a few minutes after mixing begins. It is also not sticky, does not cake, does not settle and looks great. It is also a better detergent than a comparison formulation without polyacetal carboxylate.

Example 3

The procedure of Example 2 was repeated, but the composition was made by leaving Neodol 25-7 in a liquid state at a temperature of

490 C was dropped (or sprayed) onto the moving base beads and then a finely divided Builder U powder (0.074 to 0.037 mm) was mixed with this intermediate. 10 parts of nonionic surfactant were mixed with s 30 parts of base beads, after which 10 parts of Builder U powder were added with mixing. Before Builder U was added, the particles were "lazy", i.e. poorly flowing, after the addition they were free flowing. The product looked excellent, was not sticky, did not cake, did not settle and had a better washing power than a comparison product without Builder U.

Deviations in the formulation of Examples 2 and 3 are possible, such as. B. Use of various non-ionic surfactants as described above and other polyacetal carboxylates also mentioned above. Modifications to the base bead formulations as previously indicated are also possible. In any case, a satisfactory product is obtained which has an improved detergency 20 compared to a comparative product without a polyacetal carboxy lat component. If necessary, e.g. B. the amount of Builder U and / or nonionic surfactant is so large that an improvement in the fluidity may be desired, the fluidity-improving substances 25 (zeolite builders can perform this function) can be incorporated into the end product, preferably by mixing them with the Builder U and applying this mixture to the base beads, to which nonionic surfactant has already been applied in the liquid state at elevated temperature 3o, or by applying the flowability-improving agent after absorption of the dispersion of nonionic surfactant and polyacetal carboxylate onto the base beads as indicated.

The methods and equipment 35 used for mixing can also be changed. For example, instead of 20 minutes of mixing in a batch process in an inclined drum, the mixing time can be changed to 5 to 40 minutes, and other devices can be used, such as V-mixers, fluid beds, 40 Schugi mixers and day mixers. Here too, a product of the desired properties and detergency is obtained with a bulk density in the range from 0.6 to 0.8 g / ml, as in the other examples.

Claims (12)

666 694 2nd PATENT CLAIMS 1. Particulate detergent product containing builder and nonionic surfactant, characterized in that it contains a cleaning amount of a nonionic surfactant and a builder effect amount of a builder combination of polyacetal carboxylate, carbonate, bicarbonate and zeolite for the nonionic surfactant. 2. Substantially phosphate-free detergent product according to claim 1, characterized in that the nonionic surfactant is a condensation product of ethylene oxide and a higher fatty alcohol, that the polyacetal car-boxylate builder has a weight-average molecular weight in the range from 3500 to 10,000 that the carbonate sodium carbonate is that the bicarbonate is sodium bicarbonate, and that the zeolite is zeolite A, X and / or Y, and that the ingredients are in amounts by weight of 5 to 35% nonionic surfactant and 30 to 95% of a combination of polyacetal carboxylate, sodium carbonate, sodium bicarbonate and zeolite builders, the weight ratio of polyacetal carboxylate to the combination of sodium carbonate, sodium bicarbonate and zeolite builder being in the range from 1: 5 to 2: 1, the weight ratio of sodium carbonate to sodium bicarbonate being in the range from 1: 2 to 4 : 1 and the weight ratio of zeolite to the combine ion of sodium carbonate and sodium bicarbonate is in the range of 3: 1 to 1: 3, and that the rest of the product may contain filler (s) and / or other builders and / or adjuvants) and / or moisture. 3. phosphate-free detergent product according to claim 2, characterized in that the nonionic surfactant is a condensation product of 3 to 20 moles of ethylene oxide and 1 mole of fatty alcohol with 10 to 18 carbon atoms, that the polyacetal carboxylate builder has a weight-average molecular weight in the range from 5000 to 9000, that the zeolite is type A and that the ingredients are present in amounts by weight of 10 to 30% nonionic surfactant, 10 to 40% polyacetal carboxylate, 5 to 25% sodium carbonate, 3 to 20% sodium bicarbonate and 8 to 35% zeolite. 4. Detergent product according to claim 3, characterized in that the nonionic surfactant is a condensation product of 3 to 12 moles of ethylene oxide and 1 mole of fatty alcohol with an average of 12 to 15 carbon atoms, that the polyacetal carboxylate, a sodium carbonate, that the zeolite is hydrated zeolite A. and that the components are present in amounts by weight of 10 to 20% nonionic surfactant, 10 to 25% polyacetal carboxylate, 10 to 20% sodium bicarbonate, 5 to 15% sodium bicarbonate and 10 to 20% zeolite. 5. Detergent product according to claim 4, characterized in that the nonionic surfactant is a condensation product of 6 to 8 moles of ethylene oxide per mole of higher fatty alcohol, that the polyacetal carboxylate has a weight-average molecular weight of about 8000, that the zeolite is 4A and that the components in Amounts by weight of about 16% nonionic surfactant, about 22% polyacetal carboxylate, about 14% sodium carbonate, about 10% sodium bicarbonate, about 21% zeolite 4A with a water content of about 20%, about 8% sodium silicate with a Na2: Si02 weight ratio of about 1: 2.4, about 4% moisture and about 5% auxiliaries are present. 6. Detergent product according to claim 1, characterized in that it contains zeolite builders in spray beads containing carbonate and bicarbonate builders and contains nonionic surfactant and polyacetal carboxylate on these beads. 7. Detergent product according to claim 3, characterized in that it contains zeolite builders in spray beads of base beads containing carbonate and bicarbonate builders and 2 to 20% by weight of the product on these beads together with nonionic surfactant and polyacetal carboxylate zeolite. 8. A method for producing a detergent product according to claim 1, characterized by Spray drying an aqueous crutcher mixture of carbonate, bicarbonate and zeolite, Mixing the spray-dried beads obtained with the nonionic surfactant in liquid form at elevated temperature, the surfactant being absorbed into the spray-dried carbonate-bicarbonate-zeolite beads, - Mixing these beads containing the nonionic surfactant with the polyacetal carboxylate builder, this builder being held on the beads and a free-flowing particulate detergent product being formed. 9. The method according to claim 8, characterized in that zeolite powder is subsequently mixed with the product obtained to further improve the flowability. 10. A method for producing a detergent product according to claim 1, characterized by Dissolving and / or dispersing the polyacetal carboxylate builder in the nonionic surfactant in liquid form at elevated temperature, - spray drying an aqueous crutcher mixture of carbonate, bicarbonate and zeolite, and - Applying the solution or dispersion of the polyacetal carboxylate builder in the nonionic surfactant to the spray-dried beads with mixing, this solution or dispersion being sorbed by the carbonate-bicarbonate-zeolite-IC beads to form a free-flowing particulate detergent product. 11. The method according to claim 10, characterized in that sodium carbonate and bicarbonate are used as sodium bicarbonate, and that zeolite powder is subsequently mixed with the product obtained to further improve the flowability. 12. The method according to claim 10, characterized in that sodium carbonate and bicarbonate are used as sodium bicarbonate, and that additionally finely divided zeolite particles are dispersed in the nonionic surfactant with the polyacetal carboxylate builder and applied to the spray-dried particles with this surfactant and builder.