NL8500957A - Non-cohesive bleaching detergent composition containing sodium perborate hydrate. - Google Patents

Description

VO 7104

Non-cohesive bleaching detergent composition containing sodium perborate hydrate.

This invention relates to bleaching detergent compositions. More particularly, it relates to non-cohesive detergent compositions which contain a low hydrate of sodium perborate as the bleaching agent.

Sodium perborate in its tetrahydrate form is widely used in the formulation of bleaching detergent compositions, some of which also contain nonionic detergents and a "builder". When such compositions are added to washing water at a higher temperature (near the boiling point), the perborate releases oxygen in an active form, causing bleaching of the laundry during washing.

For washing operations, which are performed at lower temperatures, substantially below the boiling point of water and sometimes close to ambient temperature, the composition may also contain an activator to release active oxygen from the perborate during the wash operation to ease.

Although perborate-containing detergent compositions, in which the perborate is present in the form of its conventional hydrate, the tetrahydrate, may be able to flow sufficiently when poured from normal detergent composition containers and packages, it has been found that, when such compositions also contain a nonionic detergent and a "builder" and are held at an elevated temperature in a sealed container, which is water vapor-tight, for an appreciable time, for example a month, these compositions serious baking.

Detergent compositions containing a nonionic detergent such as ethylene oxide condensation products of lipophilic moieties, a "builder" such as sodium tripolyphosphate, sodium silicate, sodium carbonate or a cation-exchanging sodium aluminum silicate (zeolite), or mixtures thereof, and sodium perborate tetrahydrate thus bake together in an inconvenient manner and can still be tacky and flow poorly even after breaking up the baked composition. Such unpleasant features of these compositions are noted when detergent compositions of the type described are packaged 8500957 1 (> 2- in distribution bottles, which are closed with a screw cap or similar closure upon storage. In such containers, which are usually hollow having handles that communicate with the main body of the detergent composition contained therein, it is more difficult to break up the baked material so that it is pourable than if the material were packed in the normal or paper board of the liquid-tight and / or gastight-type cartons manufactured The relatively narrow neck, the substantial rigidity of the bottle and the presence of the hollow handle all add to the difficulty of administering a baked-on detergent composition from such bottles, while their customary transparency makes consumers more aware of the annoying conglomeration surprisingly found that by replacing the sodium perborate tetrahydrate in such detergent composition formulations with a sodium perborate hydrate, in which the degree of hydration is lower and usually not higher than that of the monohydrate, it can be baked together can be reduced and even completely prevented, in particular when the degree of hydration of the sodium perborate hydrate corresponds to that which is not higher than 18% water in the hydrate and preferably equals 12 to 15% thereof.

In accordance with the present invention, a non-cohesive, discrete, very small-particle bleaching detergent composition contains a thirty-second amount of a synthetic, organic, nonionic detergent, a detergent-building amount of a Builder for such a detergent and a bleaching amount of sodium perborate hydrate having a degree of hydration corresponding to at most 18% water in the hydrate. Such detergent compositions will usually contain from 5 to 28% synthetic non-ionic derterative, such as a high fat alcohol polyethoxylate, from 10 to 89% inorganic builder, such as sodium tripolyphosphate, sodium silicate, sodium carbonate, a cation-exchanging zeolite or mixtures thereof, 5 to 50% sodium perborate hydrate with a moisture content of up to 15% and 1 to 15% moisture (including the moisture from the sodium perborate hydrate and any other present hydratable salts). Also included in the invention is a detergent composition, such as that described, in a sealed and resealable capped and necked bottle, which composition is stored for at least four times Soak non-baking for weeks at a temperature of 43 ° C and can be poured out easily when the bottle is opened.

In addition, the invention includes a method which takes advantage of the fact that the sodium perborate hydrate used in this invention can absorb significant amounts of nonionic detergent when that detergent is in a liquid state. According to such a method, at least part of the nonionic detergent is absorbed into the sodium perborate hydrate during the production of the bleaching detergent compositions herein. Therefore, more nonionic detergent can be used in the present compositions without this having a deleterious effect on the flowability of the product. Also, because the sodium perborate hydrate used according to the invention has a greater bleaching effect than the tetrahydrate, a smaller amount of it can be used, leaving room in the composition for other components. Thus, larger amounts of adjuvants 20 can be used to impart particular effects to the composition, while obtaining its desired detersive and bleaching properties.

The invention will be readily understood from this description, in conjunction with the drawings, in which: Fig. 1 represents a vertical view of a packaged bleaching detergent composition of the invention poured from its container after storage at elevated temperature ; FIG. 2 is a side view of a comparative composition such as that of FIG. 1, except that sodium perborate tetrahydrate is used as the bleaching component, which composition cannot be poured from its bottle after storage at elevated temperature; and FIG. 3 is a flow chart of a method of the present invention.

Fig. 1 shows a transparent plastic bottle 11, which is made of polymethyl methacrylate, polyvinyl chloride, polyethylene or polypropylene and which contains a non-cohesive, non-8500957

· »V

"-4- tacky, free-flowing, bleaching, very small discrete detergent composition 13 of this invention is seen to flow from the threaded neck 15 of the container to form a stream 5 17 of particles of the detergent composition. It is noted that the particles of the detergent composition flow freely through the neck 15 despite the fact that the bottle is only allowed to slope about 20 ° at a relatively small angle. It is also noted that the flow of the detergent composition through the relatively narrow hollow handle portion 19 of the bottle proceeds easily, and it is further seen that the composition leaves the head wall 21 and bottom 23 free of particles when the detergent composition is administered, which proves the non-sticky nature of the product. The shown pouring out of the detergent composition takes place after the contents of the bottle, after storage of the closed bottle (airtight and water-vapor-tight with a screw cap made of plastic, not shown) after four weeks of storage, at a temperature of 43 ° C, had cooled to ambient temperature. After some of the contents had been used for washing purposes, the bottle was resealed and then reopened for further use. The content still did not bake and was free-flowing.

In Fig. 2, the bottle 11 ', which is identical to that of Fig. 1, contains a comparative detergent composition 25 which is exactly the same as the composition of Fig. 1, except that instead of the sodium perborate hydrate used in the present invention is now incorporated with sodium perborate tetrahydrate. Such a bottle, which was sealed with the contents contained therein, was subjected to the elevated temperature treatment as stated for the product shown in Figure 1, after which composition 25 was baked together in the bottle. In some cases, liquefaction of the comparative composition was noted. The contents could not easily be discharged from bottle 11 'after cooling to ambient temperature, even when the bottle was held with the discharge opening facing the ground, as shown. When the bottle was shaken vigorously, a little material could be added, but most of it remained baked together, poorly flowing and tacky.

It should be remembered that the particles of the composition have a solid mass of 8500957 β * -5- formed, the bottom of which is located at the surface 26, and that volume 28 below that surface is empty.

In Fig. 3, detergent grade Is containing "builder" *, adjuvants and a relatively small percentage of moisture are produced by "crutching" a water-containing "crutcher" mixture of such components in "crutcher". 33 and feeding the crutcher mixture to spray dryer 35, from which the desired base grains are obtained and fed to mixer 37, in which they are mixed with sodium perborate hydrate particles according to this invention, in which particles do not ionic detergent is absorbed.

Such perborate and nonionic detergent-containing particles are prepared by feeding nonionic detergent in a liquid state from a nonionic detergent storage tank 27 to a spraying and mixing device 29 in which the nonionic detergent 15 is sprayed on moving surfaces of the sodium perborate hydrate, which was fed to such an apparatus from tray 31. Several other detergent composition components may also be included in the composition in the spray and mixer 29, the crutcher 33 or the mixer 37, such as fragrances, enzymes, soil release promoters, stabilizers, activators, colorants, fabric softeners and flow promoters. The desired product is removed, preferably continuously, from the mixer through a drain, which is represented by line 39, and then leads to packaging, storage in warehouse 25 and forwarding.

The nonionic detergent component of the compositions of the invention may be any suitable nonionic detergent with satisfactory cleaning and physical characteristics, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-containing bases such as alkylphenols oxo-type alcohols and high fatty alcohols, such as the high linear alcohols. It is preferred that the nonionic detergents are usually solid at ambient temperature, but melt at temperatures still close to ambient, for example 45 ° to 50 tot, so that they are in a liquid state when fed to the base granules or of the sodium perborate hydrate used according to the present invention, but can be solidified thereafter, although nonionic compounds which are already liquid at ambient temperature may also be absorbed . Suitable nonionic detergents include the polyepoxylated alkyl phenols, wherein the alkyl group is a linear or substantially linear alkyl group having 7 to 12 carbon atoms, preferably 8 or 9 carbon atoms, and which is 3 to 30 moles, preferably 3 to 15 moles, for example 9 moles of ethylene oxide per mole of phenol. The most preferred nonionic detergents are the condensation products of 3 to 20 moles of ethylene oxide with a mole of high fatty alcohol, preferably a linear alkanol of 10 to 18 or 20 carbon atoms. Preferably, 6 to 15 and in particular 6 to 9 or 11 moles of ethylene oxide are present per mole of higher alcohol. The alcohol has an average of 12 to 15 carbon atoms per mole. Particular preference is given to the presence of 6, 6.5, 7 or 11 moles of ethylene oxide per mole of higher alcohol with 12 to 15 carbon atoms per mole. Suitable nonionic detergents include those representatives commercially available under the trademark names Alfoni® 1214-60C, which are sold by the Conoco division of E.I. Dupont de Nemours, Ine., And Neodoleur® 23-6.5 and 25-7, which are available from Shell Chemical Company, or equivalent types.

Mixtures of various nonionic detergents or a single product of that type can be used. Although it is preferred that only a nonionic detergent be used, the use of one or more anionic detergents together with one or more nonionic detergents is also within the scope of the invention, provided that it the properties of the composition are not adversely affected. The anionic detergents that can be used include the water-soluble high linear alkyl benzene sulfonates, for example linear sodium dodecyl benzene sulfonate, olefin sulfonates, alkane sulfonates, monoglyceride sulfates, high fatty alcohol sulfates, for example sodium lauryl sulfate, and high fatty alcohol. polyethoxylate sulfates. In such compounds, the high fat groups will usually contain from 8 to 20, preferably from 10 to 18, and especially from 12 to 16, carbon atoms. The number of moles of ethylene oxide per mole of detergent, if such a detergent is present, will usually range from 1 to 20, preferably 3 to 10. If an anionic detergent is present, the amount thereof will usually be less than that of the nonionic detergent and sometimes 10 to 50% thereof. Although amphoteric and cationic detergents and surfactants may also be present, any levels thereof will usually be small. It may sometimes be desirable to use quaternary ammonium compounds as fabric softening agents, such as the quaternary ammonium halides with two lower alkyl groups and two high alkyl groups, for example dimethyl distearyl ammonium chloride or diethyl dipalmityl ammonium bromide, but these compounds are considered adjuvants rather than detergents. Several "builders" and combinations thereof, which are effective in increasing the cleaning performance of the nonionic detergent and detergent composition and in improving the general wash properties of such composition, include both water-soluble and water-insoluble "builders". Of the water-soluble "builders", the inorganic salts are preferred, but various organic "builders" can sometimes also be used, such as sodium citrate, trisodium nitrilotriacetate, organic phosphates, gluconates and polyelectrolytes. Preferred water-insoluble "builders" include the naturally occurring zeolites and zeolite-like materials and other ion-exchange insoluble compounds that act as detergent "builders". Of the various zeolites, Zeolites A, X and Y are preferred, with zeolite 4A being most preferred. In general, such a zeolite satisfies the formula: CNa20) x · <Al2 ° 3) y · CSiO2) z-w H2 O, where x equals 1, y equals 0.8 to 1.2, z equals 1.5 to 3.5 and w equals 0 to 9, preferably 2.5 to 6. Such zeolites are characterized in that they have a high ion exchange capacity for calcium ions, which power is generally About 200 to 400 or more milligrams equivalents of calcium carbonate hardness per gram of the aluminum silicate, based on anhydrous zeolite. The zeolite usually has a moisture content of 5 to 30%, preferably 15 to 25%, for example about 20%.

The preferred soluble inorganic builder salts of this invention include polyphosphates, carbonates and silicates, usually in the form of the alkali metal salts and preferably in the form of the sodium salts. Although pyrophosphates may be present, the preferred polyphosphate is sodium tripolyphosphate and usually a hydrated or water-treated form thereof will be used. Instead of sodium carbonate, sodium sesqui-carbonate may be present or a mixture of sodium carbonate and sodium hydrogen carbonate may be used depending on the desired product characteristics. The sodium silicate will usually be added to the crutcher mixture in liquid form, but according to this description the amount added thereto is in an anhydrous state, which also applies to the other components (except perborate and optionally used hydrated polyphosphate). The sodium silicate usually has a Na 2 O 2 SiO 2 ratio in the range 1: 1.6 to 3.0, preferably 1: 1.6 to 2.4, e.g. 1: 2.0, 1: 2.4. Several other suitable builder salts and various mixtures thereof can be used. However, it is most preferred that the major "builder" salt is sodium tripolyphosphate and that it also contains (is) sodium silicate and / or zeolite. In those cases where phosphate is to be avoided due to eutrophication problems, zeolite (s), mixtures of carbonate and zeolite, carbonate and hydrogen carbonate, and carbonate, hydrogen carbonate and zeolite may also be present in solid compositions. or other "builder" combination, which is not based on phosphate.

The sodium perborate hydrate 30 used according to the invention is one, the hydration of which corresponds to considerably less moisture than that of the perborate tetrahydrate. Where sodium perborate tetrahydrate contains about 47% moisture and about 10.4% active oxygen, the monohydrate contains about 18% moisture and about 16% active oxygen. The active oxygen content is about the same in a range of moisture contents of about 12 to 18%, but the lower amounts of this range, 12 to 15% or 12 to 14%, for example, 8500957 +. % -9- Image 13% have been found to be more suitable because it is such that the detergent composition characteristic is non-cohesive than best maintained and untimely, rapid release of oxygen from the composition into the wash water does not occur, which has been observed when the perborate of such compositions contained less than 12% water of hydration. The suitable perborate hydrates can be prepared by heating sodium perborate tetrahydrate, expelling the desired amount of moisture. Although it is possible to mix perborate hydrates of different moisture contents together to obtain the desired average moisture content, such a method is considered less good than dehydrate the perborate tetrahydrate in a controlled manner to the desired moisture content, so that the perborate particles are very similar in terms of their moisture contents.

In addition to the three major components (and water) of the present compositions, various adjuvants may also be present.

These include compounds that promote loosening of dirt, tissue softeners, enzymes, stabilizers, perborate activators, anti-gelling agents and anti-binding agents (anti-20 setting agents), anti-oxidants, clay agents, fragrances, fluorescent brighteners, dispersants, sequestrants, flow promoters, fillers, beads strength enhancers, defoamers, bactericides, fungicides, and grain density modifiers.

Preferred compounds which promote soil loosening are the copolymers of polyethylene terephthalate and polyoxyethylene terephthalate with molecular weights in the range of about 15,000 to 50,000, preferably 19,000 to 43,000, especially 19,000 to 25,000, for example about 22,000. In such polymers, the polyoxyethylene has a molecular weight in the range of 1,000 to 10,000, preferably 3,000 to 4,000, for example, about 3,400, and the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units is in the range of 2: 1 to 6: 1 , preferably 3: 1 to 4: 1, for example about 3: 1. In such copolymers, the ratio of ethylene oxide to the phthalic acid portion in the polymer is at least 10: 1 and usually 20: 1 or more, while it is preferably in the range of 20: 1 8500957 4 * -10-: 1 to 30: 1, for example, about 22: 1. Such materials are available under the trademarks Alkaril QCJ and Alkaril QCF from Alkaril Chemicals, Ine. Other copolymers of this type, but with different molecular weights and component ratios may also be used, but are not considered to be as effective. Suitable fabric softeners include, in addition to the aforementioned quaternary ammonium halides, sodium bentonites, such as Wyoming or "western" bentonites, which often have good gelling ability and good cation exchange capacity (greater than 50 milliequivalents of calcium ion per hundred grams). ) to own. Suitable enzymes include proteolytic and amylolytic enzymes, for example Maxatase and Esperase 4T. Such enzymes referred to herein are commercial formulations containing a carrier containing the active ingredient (the weights given herein refer to the formulations as supplied).

Enzyme stabilizers, including sodium formate and formaldehyde, may be present, as well as stabilizers for other components of the composition. Perborate activators include N-acetyl caprolactam and acetamides, and those known as TAED, TAGU 20 and PAG, as well as other acetyl group-containing chemicals, which can form peracetic acid. Among the anti-gelling agents and anti-binders, mention may be made of citric acid, sodium citrate and magnesium sulfate, the citric acid based compounds usually being used previously in small adjuvant amounts, in larger amounts of builder. Antioxidants, colorants, fragrances, bactericides and fungicides are known in the art and are minor components of the products of the invention, so that they will not be discussed further. Fluorescent whiteners are usually of the stilbene type, such as Tinopal CBS-X and Tinopal 5BM. Suitable dispersants include the polyacrylates, which also contribute to grain strength and allow control of grain density. Sequestrants, such as NTA, EDTA and citric acid-based substances (in small amounts) may be present. Of the flow promoters, magnesium silicates are preferred. In the present formulation, there is usually little room for fillers, but a suitable 8500957-11 filler, which also acts as an enhancer for the crutchern mixture, is sodium sulfate and it is sometimes possible to include it in the formulation because of the "hole" / which is left by replacing a larger amount of sodium perborate tetrahydrate with a smaller amount of the lower hydrate. Suitable anti-foaming agents include the known dimethyl silicone and soaps, such as sodium tallow soaps / sodium soaps of hydrogenated tallow and sodium stearate. Such soaps are also used in greater amounts in view of their contribution as a detergent, replacing an anionic detergent when it was present in the compositions.

Although in the broadest sense, amounts are not critical in the present invention, there are certain amounts which are highly desirable for the proper functioning of the invention. For example, the synthetic, nonionic, organic detergent content will usually be in the range of 5 to 28% of the composition. Below 5%, an insufficient detersive effect is noted, and it appears that about 28% is the upper limit of the nonionic detergent content in the present product, without resulting in tackiness and susceptibility to the product baking. Especially when the synthetic nonionic detergent is an ethylene oxide condensation product of a high fatty alcohol or an alkyl phenol and no other detergent is present, the amount thereof is preferably 10 to 25%, more preferred to 14 to 22%, in particular to about 18 to 20%. The amount of inorganic builder is usually in the range of from 10 to 89%, preferably from 30 to 55%, especially from 35 to 50%, for example, 39% and 45%. For those compositions containing sodium tripolyphosphate as the major builder, the amount thereof is usually from 30 to 55%, preferably from 35 to 50%, for example, 37% and 43%. As a rule, sodium silicate is present with the polyphosphate and the amount thereof is 1 to 10%, preferably 1 to 8% and in particular 2 to 4%, for example about 2 or 3%. In some cases, however, larger amounts of silicate can be used, usually when zeolite, carbonate and / or hydrogencarbonate are present in formulations containing no phosphate instead of poly-phosphate.

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In such cases, the silicate content can be 2 to 10%, preferably 3 to 5%. The levels of carbonate, hydrogen carbonate and zeolite vary according to the formulations. When zeolite is used together with tripolyphosphate, it will generally be present in an amount of about 1/5 to 1/2 of that of the tripolyphosphate, but sometimes the amount of zeolite used can be equal. In compositions which do not contain phosphate, the zeolite percentages are usually 5 to 25%, preferably 10 to 20%. In compositions containing no phosphate, the carbonate amounts can be from 5 to 30%, preferably from 10 to 25%, as well as the amounts of hydrogen carbonate.

The sodium perborate hydrate component of this invention is generally present in an amount ranging from 5 to 50% of the composition, preferably 10 to 30% thereof, and especially 15 to 25% thereof. When a nonionic detergent is absorbed by the perborate hydrate, micrographs show that it fills the roughnesses on the surfaces of the perborate particles, resulting in a grain with a substantially smooth surface, which grain flows better than the grains with a rough surface of the same composition. Although the hydrate at a moisture content below 12% may release oxygen in the wash water too easily, in some cases such rapid release may be desirable and therefore the moisture content may be as low as 1% and therefore the range of such levels may be between 1 and 15 % or 25 between 1 and 14%. The hydrates with the low moisture contents within such a range may have a greater absorbency for non-ionic derivatives than those with a higher moisture content.

The amount of moisture in the present compositions is usually in the range of 1 to 15%, although it is contemplated that in the presence of certain components, such as zeolite and / or bentonite, a higher moisture content limit may be applicable, for example 18% . Such amounts of moisture include the moisture contained in the sodium perborate hydrate and also other easily removable moisture from other hydrates, which may also be present. A preferred moisture range is between 5 and 15%, while a more preferred range is from 10 to 13 or 14%. It is desirable to limit the amounts of adjuvants present to a range from 1 to 15%, with individual adjuvants generally being present in an amount of not more than 10%, e.g., 0.1 to 8%. Of course, the amounts of the adjuvants depend on their nature and function, so that regions are indicated here for only a few components. As a rule, the amount of compound that promotes soil loosening is from 1 to 10%, preferably from 3 to 8%, which range is also suitable for a fabric softener such as bentonite. Fabric softeners based on quaternary ammonium halide 10 can be present in an amount of 0.5 to 4%, while the enzyme content is usually 0.2 to 2%. Perborate activators can be present in an amount of 0.1 to 4%, while the amount of anti-gelling agent and anti-binder may be 0.2 to 3%. As a rule, the content of perfumes and colorants is 0.1 to 1% and of the flow promoters 0.5 to 5%. Anti-redeposition agents, such as CMC, can be present in an amount from 0.5 to 3%, while the amount of polyacrylates can be from 0.05 to 1%. Fillers, such as sodium sulfate, which also serves to improve the properties and flow of the particles while desirably affecting the mixing of the crutcher slurry when it contains sodium tripolyphosphate may be present in a amount from 0.5 to 8 or 10%.

In an important embodiment of this invention, the disclosed compositions are packaged in hermetically sealed bottles, similar to blow molded bottles, which are commonly used to package liquid detergents. However, it is highly preferred that the bottles herein be translucent so that the attractive particles of the product can be seen by the consumer. Often the particles of the detergent composition are colored, sometimes they have more than one color and it is desirable to be able to see them. It can also be observed how the product flows, while it can be seen that it does not adhere to the container walls. Materials for the container have been previously described and the present discussion is limited to descriptions of some of the salient features of the bottles and their dimensions. The bottles can reasonably be characterized as narrow neck bottles, where, in general, the neck is generally round and has an open cross section with a surface in the range of 2 to 40. cm.

The hollow handle has a cross-sectional area for the opening therein of 1 to 10 cm.

The compositions of this invention are free-flowing, often flowing through a suitable narrow opening at a rate of about 70% or more of that of dry sand. The flow rate is at least comparable to that of other free-flowing detergent powders. The bottles are therefore easily filled by means of an automatic filling equipment and the particles of the detergent composition easily fill the hollow handle portion. Of course, bottles without such handles, which contain the composition of the invention, also fall within the product aspect of this invention. After the previously described test on heat storage and after cooling, the compositions of the invention flow easily through the handle and out of the bottle when tilted only slightly, with flow occurring at a rate, which is approximately equal to the original flow rate. Even after the bottle is resealed with a cap, stored again at elevated temperature, opened and placed in a pouring position, as shown in Fig. 1 of the drawing, the product flows easily, does not bake together and it is not sticky.

The preparation of the compositions of the invention is essentially without complications and does not require the use of equipment which is not usually used in the detergent industry. Of course, there are several ways in which the perborate hydrate can be combined with the components of the bleaching detergent composition. It can be mixed with the other 30 individual components, mixing the dry powders and spraying or dripping the liquid components on the surfaces of the moving powders. This is not preferred because it is desired that the composition be in a non-dusting form, such as in the form of granules of the type obtained in spray drying operations. Because sodium perborate decomposes 8500957-15- (200 to 500 ° C) at elevated temperatures, such as those in a spray drying tower, the perborate is not included in the "crutcher" mixture and is subsequently added to any substances which are spray dried. have been subject. However, the perborate hydrate according to the invention can be mixed with spray granules, which contain all or almost all other components of the detergent composition, after which the mixture is fluidized in a tumbling drum, a coating pan. , a V-mixer, a zig-zag mixer or similar equipment, the non-ionic detergent is applied to the mixture.

Preferably, the perborate hydrate is "charged" with nonionic detergent in the liquid state at elevated temperature, usually in the range of 50 to 65 ° C, eg 55 ° C, 60 ° C, where the "charge" exists from 20 to 30% non-ionic compound, after which this product is mixed at ambient temperature with base granules, to which the possibly desired additional amount of non-ionic detergent has previously been added. It has been found that up to 30% nonionic detergent can be satisfactorily absorbed into the perborate hydrate particles and, as discussed previously, the solidified detergent covers dimples on the surface of the particles, thereby facilitating release of the particle. is smoothed. Better absorption can be obtained when the moisture content of the perborate hydrate is less than the theoretical amount of about 18%, with the range from 12 to 15%, especially 12 to 14% being preferred and most preferred goes to 13%.

In another embodiment of the invention, the perborate hydrate may have absorbed nonionic detergent, while spray-dried particles of sodium tripolyphosphate, either hydrated or anhydrous, may also have absorbed nonionic detergent. limit of absorption for the tripolyphosphate is about 20% and a reasonable range for nonionic detergent contents of such a product is between about 5 and 20%. Then, these two components can be mixed with various other components of the composition, which may be in an agglomerated form, so that their particle sizes are improved, it being desired that all or substantially all particles have dimensions in the range of 2. .38 to 0.105 mm (wherein 8500957-16 is more than 90 wt%, and preferably more than 95 wt%, of the particles in such range). If more than the allowable limit of the particles is outside such a range, they are removed by screening. Specifications are set for purchased materials 5 so that the particles are in the desired particle size range.

The advantages of the invention have already been referred to. In the first place, a problem in the baking process, which could seriously interfere with the promotion of bleaching action of nonionic detergent compositions in sealed bottles, has been overcome. By replacing sodium perborate tetrahydrate with the lower hydrates of the present invention, stability of the product with respect to such firing and prevention of the development of poor flow properties and tackiness are achieved.

In addition, because the lower hydrate of perborate absorbs more nonionic detergent, larger amounts of such detergent can be included in the composition without causing caking, poor flow and tackiness. Since the lower hydrate of perborate contains about 50% more active oxygen than the perborate-20 tetrahydrate, less of it can be used and other components can be included in the product to further improve its properties. The end result is thus an improved and stable product, which has the desired bleaching properties of the corresponding sodium perborate tetrahydrate based compositions and has excellent detergent similar to that of the perborate tetrahydrate compositions, while the product does not baking, free-flowing and non-tacky, while the absorbance for nonionic detergent is greater and the product is better able to provide formulation flexibility due to the "hole" left in the formulation by eliminating the hydration water of the tetrahydrate.

The invention is further illustrated by the following examples without limiting it. Unless otherwise indicated, all parts are by weight and all temperatures are in degrees Celsius.

8500957.

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EXAMPLE I

Component Share

Water15 54.3 2)

Sodium Silicate (Na2O: SiO2 = 1: 2.0) 6.8

Sodium tripolyphosphate (NTPF) (hexahydrate) ^) 42, /

Sodium carboxymethyl cellulose (detergent grade) '

Magnesium silicate (flow improver) 0.5 4)

Fluorescent whiteners 0.3

Colorant (blue dye and pigment) 0.04 106.14 1) Tap water with hardness of less than 150 ppm (as CaCO3) or deionized water 2) 44.1% solution in water 3) Alternatively, another NTPF may be used applied

4) Mixtures of 0.24 part stilbene whitener No. 4 (designation of Colgate-Palmolive Co.) and 0.06 part Tinopal CBS-X

A "crutscher" mixture of the above formulation is prepared by adding the various components to its water which has been placed in a standard detergent "crutcher", after which the mixture is heated to a temperature of about 50 ° C. It is then spray dried in a conventional countercurrent spray tower, the tower temperature being about 350 ° C. Sufficient water is removed from the product during drying so that its final moisture content is about 16%.

The granules obtained by spray-drying are free-flowing particles, substantially all of which have particle sizes in the range from 2.38 to 0.105 mm, with more than 75% of the particles having dimensions in the range from 0, 84 to 0.177 mm.

To 56.9 parts of the spray-dried granules, 17 parts of sodium perborate hydrate with a moisture content of about 13%, 1 part of a phosphoric acid ester of a mixture of about equal parts of cetyl alcohol and stearyl alcohol and 0.8 part of enzyme (Esperase 4.0 T). To this mixture are added 16 parts of an 8500957-18 condensation product of ethylene oxide and a high fatty alcohol (7 moles of ethylene oxide per mole of high linear fatty alcohol with 12 to 15 carbon atoms), the temperature of which is about 60 ° C, the addition is effected by spraying or dripping the non-ionic compound onto the tumbling particles of the other components. The composition is mixed until the fatty alcohol has been satisfactorily distributed and absorbed by the various particles. 0.4 part of perfume is added during mixing. When mixing is complete, which takes about 10 to 10 minutes, the product is removed from the mixer (sieved in some cases) and filled with distressed polyacrylate bottles with hollow handles and relatively narrow necks, which bottles are then are closed, packed in cardboard boxes, stored in a warehouse and shipped.

The prepared bleaching detergent composition has particles within the size range previously mentioned for the spray drying components (the perborate starting material also had such a size). The composition has a density of 0.7 g / ml and is free-flowing. The product contains about 17% of the non-ionic detergent, 46% sodium tripolyphosphate, 17% sodium perborate hydrate, 3% sodium silicate, 1% phosphoric acid ester, 1% sodium carboxymethyl cellulose, 0.9% enzyme, 0, 5% flow promoter, 0.4% fragrance, appropriately smaller percentages of other adjuvants and about 13% moisture (including the moisture of any hydrates, from which it can be removed at 105 ° C) .

When the hermetically sealed container of the bleaching detergent composition of this invention is subjected to a stability test by keeping it at a temperature of 43 ° C for four weeks, the product meets the test requirements. In such an experiment, the bottle and contents are allowed to cool to ambient temperature before opening the bottle, after which the contents are poured from the bottle. It is noted that the contents can be poured relatively easily, do not bake together and do not stick to the walls of the bottle. Using a standard flow rate test, the content flows through a narrow opening at a rate of about 70% that of dry sand. Even when the heated materials are poured from the open bottle while still warm, 8500957-19 flow well. Chemical analyzes show that the active oxygen content of the perborate has not decreased during storage, nor has the P20 content of the polyphosphate decreased. The product is an attractive free-flowing detergent composition that can satisfactorily withstand elevated temperatures, which can be presumed to exist during normal warehouse, shipping and pre-use storage. When tested in a laboratory, in commercial washing machines and household washing machines, where washing is carried out at an elevated temperature, for example 75-90 ° C, it is found that the composition has excellent washing and bleaching properties compared to washing normally soiled and in relation to various stains. Such properties are retained during normal use of the product, which entails the repeated opening and closing of the polyacrylate bottle, while during such repeated applications, the product is non-cohesive, non-tacky and easy to flow. remains.

When sodium perborate hydrate with 13% moisture is replaced by other such hydrates, such as those with moisture contents of 12, 14 and 15%, essentially the same results are obtained and the product does not bake together when stored at elevated temperature in sealed containers . Similar results can be obtained when instead of the sodium tripolyphosphate a mixture of approximately equal parts of sodium carbonate and sodium hydrogen carbonate is used or when half of the tripolyphosphate is replaced by hydrated zeolite 4A (20% water of hydration). However, the flow of the phosphate-free product is not as good as that of the first product of this example.

Results such as those according to the first example described herein can also be obtained when no flow improver is used, but the flow rates are then somewhat slower. Even when the only components are perborate hydrate, tripolyphosphate, nonionic detergent and sodium silicate in the proportions described in this example, an excellent detergent is obtained, but the various desirable properties of the adjuvants are missed.

85 0 0 S 5 7 ---- i -20-

When the 17 parts of the perborate hydrate of this example are replaced with enough sodium perborate tetrahydrate to obtain the same active oxygen content, and the resulting product is heat-tested by the method described previously herein, it then appears that such a product coalesces severely and that in some cases liquid can be observed between the particles of this "comparative" composition. Thus, the comparative composition is considered unacceptable for commercial use in sealed containers, such as the mentioned bottles. Also, the comparative composition is considered unacceptable for use in cardboard packaging material which is moisture proof.

EXAMPLE II

Sodium perborate tetrahydrate parts of sizes from 2.38 to 0.105 mm are partially dehydrated to moisture contents of 12 to 15% by controlled heating, such as by heating in fluidized bed or by the particles at a controlled flow rate through a heated pipe. During such heating operations, the particles swell slightly, but at the end they are within the desired size range (from 2.38 to 0.105 mm) and have the desired density (about 0.5 or 0.6 g / ml ), so that the final product can have a density of about 0.7 g / ml. Particles so prepared are used as sorbents for a nonionic detergent as described herein.

A nonionic detergent, such as that described in Example 1, is heated to 60 ° C and coated and absorbed into the perborate hydrate particles by being sprayed on such particles while being granulated in a pan 30 or the coating device are kept in motion. In place of the described equipment, various other types of injectors, including inclined drums, Day mixers, and V and zig zag mixers, may be used. Mixing can be carried out continuously or batchwise. The type of mixer or mixer used is one which tends not to cause disintegration or agglomeration of the particles. It has been found that the 8500957-21 nonionic detergent and perborate hydrate particles obtained are free-flowing, have the desired particle size (2.38 to 0.105 mm) and have a smoother appearance than the perborate particles initially If the moisture content of the perborate is less than 12% and such an experiment is repeated, good absorption of the nonionic compound can also be obtained, but when the moisture content is higher than about 18%, the sorption greatly reduced. For example, sodium perborate tetrahydrate is not a good absorbent for a nonionic detergent.

The sodium perborate hydrate, which contains about 30% nonionic detergent (total base), is mixed with spray drying detergent base granules, such as those of Example 1, after such base granules are mixed with the remainder of the formulation, with the exception of fragrance, the formulation 15 taking into account the nonionic detergent previously mixed with the perborate. Fragrance is then mixed in and after five or more minutes of mixing at ambient temperature, the product is ready for packaging, which is carried out in the manner described in Example I.

The product is prepared from the same composition as that of Example 1, but because of the preliminary absorption of non-ionic detergent by the perborate hydrate particles, absorption of the rest of the non-ionic detergent during production is easier . The product of this example is resistant to decomposition and deterioration at elevated temperatures by the previously described test method. After such an experiment, it does not bake together and is free-flowing, while being an excellent bleaching detergent.

In variations of this example, the percentage of perborate hydrate in the final product is increased to 25%, the contents of the other components being reduced accordingly. A product with a greater bleaching effect is obtained when 25% sodium perborate monohydrate is used in the same type of formulation. Also, the levels of active oxygen and P 2 O 2 of the product are substantially retained, while that of the comparative product containing perborate tetrahydrate decreases after storage at elevated temperature.

_ i 8500957 -22-

In another variation of this example, the perborate of this invention, which contains a nonionic detergent, can be mixed with the spray pellets base granules, followed by mixing with other components, including the remainder of the non- ionic detergent. The resulting product is a satisfactory bleaching detergent and well withstands the elevated temperature test. In a further variation, the nonionic detergent is separately absorbed by the base grain portion and the perborate hydrate portion of the composition, after which the two portions are mixed together. At each absorption step, the amounts of nonionic compound used will be the maximum amount absorbable for absorption by perborate hydrate, with the remainder of the nonionic compound being absorbed by the base granules (basically by the sodium 15 tripolyphosphate ). The product is resistant to storage in sealed bottles at elevated temperatures without caking.

Another modification of the techniques described is dry mixing of the various components of the composition after the nonionic detergent is first absorbed on the perborate hydrate particles and the sodium tripolyphosphate particles. However, dry mixtures are generally not preferred and if prepared, certain liquids such as fragrances and sodium silicate solution must still be mixed into the composition and satisfactorily distributed throughout.

EXAMPLE III

A composition containing: 18% nonionic detergent (approximately equal parts of ethoxylated fatty alcohols with 16 to 18 carbon atoms and 3 and 12 moles of ethylene oxide per mole of fatty alcohol), 35% sodium tripolyphosphate, 11% hydrated zeolite 4A (water content 20 %), 8% sodium silicate with a Na 2 O: SiO 2 ratio of about 1: 2, 6% sodium perborate hydrate (14% moisture), 3% tetraacetyl ethylenediamine (TAED; perborate activator), 1 % sodium carboxymethyl cellulose, 0.2% stilbene fluorescent whitening agent, 2% sodium formate, 1% proteolytic enzyme, 14% moisture and the remainder minor adjuvants, is prepared according to the main method of Example II and vol. satisfactorily satisfies the requirements of test 8500957 -23- described previously concerning heat storage. When the tetrahydrate is used instead of the lower hydrate of the perborate, the product bakes severely together. This example shows that instead of using larger amounts of perborate, smaller amounts can be used in conjunction with a perborate activator, such as TAED. The products prepared according to this example, when tested at low wash temperatures, such as 40 to 50 ° C, are good detergents which effectively stain due to the release of active oxygen by the perborate in the presence of the activator.

Similar results can be obtained when the compositions of this example are prepared by the other techniques mentioned in the previous example and elsewhere in the description.

EXAMPLE IV

The main recipe of Example I is modified by adding each of the following components: 5% loosening soil promoting copolymer of polyethylene terephthalate and polyoxyethylene terephthalate; 8% tissue-softening bentonite; 1% dimethyl-20 distearyl ammonium chloride; 1% polyvinylpyrrolidone? and / or 0.1% dimethyl silicone. Such components can be added to the "crutcher" mixture or added afterwards after the production of the base granules to suit their stabilities. The amounts of the other components can be reduced accordingly. One or more of the above five additional components may be used in the base formulation, while the base formulation may also be varied. For example, instead of the condensation product of ethylene oxide with a high fatty alcohol, the nonionic detergent may be a condensation product of ethylene oxide with iso-octylphenol or nonylphenol, of the type previously described, or it may be another fatty alcohol ethoxylate or mixture thereof within this patent specification. The enzymes used can be either amylolytic or proteolytic or a mixture of both. The polyvinylpyrrolidone can be used with the CMC or in part to replace it. Although the copolymer described in the specification is preferably used for promoting soil release, other materials can also be used.

85 0 0 9 5 7 -4 -24-

The products of this example are good bleaching detergents under suitable conditions of use and do not bake together when stored at elevated temperatures in hermetically sealed containers.

In addition to the above modifications, the various amounts of components listed in the main formulations of the examples can be varied to make up about 10% and about 25%, provided they are still within the scope of the invention as described. are located, wherein the products are bleaching detergents having good storage characteristics at elevated temperature.

This invention has been described with respect to several examples and explanations thereof, but not limited thereto, since equivalents and substitutions may be used without departing from the invention.

8500957

Claims (22)

A non-cohesive, discrete, particulate bleaching detergent composition containing: a detergent acting amount of a synthetic organic nonionic detergent, a detergent builder amount of a builder 5 for such a detergent and a bleaching amount of sodium perborate hydrate having a degree of hydration corresponding to at most 18% water in the hydrate. A free-flowing detergent composition according to claim 1, suitable for being packaged in a moisture-tight container and stored at an elevated temperature without baking or slowly flowing, the synthetic, organic, nonionic detergent having a condensation product of ethylene oxide and a lipophilic part, the "builder" is an inorganic compound and the sodium perborate hydrate has a moisture content of at most 15%. A detergent composition according to claim 2, containing: 5 to 28% of the synthetic, nonionic, organic detergent, 10 to 89% of the inorganic builder, 5 to 50% of the sodium perborate hydrate and 1 to 15% moisture, including the moisture from the sodium perborate hydrate. A detergent composition according to claim 3, wherein the nonionic detergent is selected from the group consisting of condensation products of ethylene oxide with a high fatty alcohol and of ethylene oxide with alkyl phenol, the builder being selected from the group, consisting of sodium polyphosphate, sodium silicate, sodium carbonate and cation exchange zeolite and mixtures of two or more of these components, the sodium perborate hydrate has a moisture content of 12 to 15% and the composition has a moisture content of 5 to 15% . A detergent composition according to claim 4, wherein the nonionic detergent is a condensation product of 3 to 20 moles of ethylene oxide per mole of high linear alcohol of 10 to 18 carbon atoms, the "builder" includes sodium tripolyphosphate, the sodium -perborate hydrate has a moisture content of 12 to 14%, the composition has a moisture content of 10 to 14%, the composition contains 0.1 to 20% of __Λ 8500957 -26- adjuvant (s) and the particle sizes in most of the cases are all are in the range from 2.38 to 0.105 mm. A detergent composition according to claim 5, wherein the nonionic detergent is a condensation product of an average of about 7 moles of ethylene oxide per mole of high alcohol, which high alcohol contains an average of 12 to 15 carbon atoms per mole, the "builder" -drated sodium tripolyphosphate and the sodium silicate has a Na 2 OS SiO 2 ratio in the range of about 1: 1.6 to 1: 2.4, the sodium perborate hydrate has a moisture content of about 13 % and the levels of nonionic detergent, sodium tripolyphosphate, sodium silicate, sodium perborate hydrate and adjuvants are in the ranges 14 to 22%, 30 to 55%, 1 to 8%, 10 to 30% and 1, respectively. up to 15%. A detergent composition according to claim 6, wherein the sodium tripolyphosphate and at least some amount of adjuvant (s) are in the form of spray-dried base granules, at least some amount of the nonionic detergent is absorbed into such granules and the sodium perborate hydrate is present in mutually different particles, which are in a mixture with the base granules. A detergent composition according to claim 6, wherein at least some amount of the nonionic detergent is absorbed into the sodium perborate hydrate particles, the sodium tripolyphosphate and at least some amount of the adjuvant (s) in the form base granules obtained by spray drying and the particles of sodium perborate hydrate and nonionic detergents are present in a mixture with the basic granules. A detergent composition according to claim 1, wherein at least some amount of the "builder" in the form of spray granules, is at least some amount of the nonionic detergent in the sodium perborate hydrate. particles is absorbed and the sodium perborate hydrate and nonionic detergent particles are present in a mixture with the base granules. A dertergens composition according to claim 9, wherein the sodium perborate hydrate and nonionic detergent particles are 5 to 30% nonionic detergent. 8500957 -27- A detergent composition contained in a hermetically sealed container or package according to claim 1, wherein the composition remains non-cohesive after storage at elevated temperature and can be easily poured from the container or package after opening it. 12. A detergent composition contained in a capped, resealable and necked bottle, the composition remaining non-cohesive after storage for at least four weeks at a temperature of 43 ° C and out of the bottle after 10 opening thereof can be poured easily. A detergent composition according to claim 10, which is contained in a capped and resealable narrow-necked urt transparent polymeric plastic or glass bottle with a hollow handle which connects to the interior of the bottle 15, with the neck opening having a cross-sectional area 2 from 2 to 40 cm and the handle opening having a cross-sectional area 2 from 1 to 10 cm, the composition after four weeks of storage at 43 ° C non-cohesive and free. remains fluid and after removal of the cap, after cooling of the contents, can be easily poured through the handle opening and out of the bottle. 14. A process for the preparation of a non-cohesive, discrete, particulate bleaching detergent composition, which process comprises: absorbing a synthetic, organic, nonionic detergent, in a liquid state, in a small individual particles of sodium perborate hydrate, the hydration of which corresponds to at most 18% water in the hydrate, and the mixing of particles of said sodium perborate hydrate and nonionic detergent composition with small individual particles existing detergent builder. The method of claim 14, wherein the hydration of the sodium perborate hydrate corresponds to 12 to 15% water in the hydrate and the amount of nonionic detergent absorbed by the sodium perborate hydrate is 5 to 30% of the sodium perborate hydrate and nonionic detergent existing particles. The method of claim 14, wherein the "builder" is sodium tripolyphosphate, the nonionic liquid detergent is absorbed into the sodium tripolyphosphate particles, such that 5 to 20% of the sodium content of tripolyphosphate and nonionic detergent particles are nonionic detergent and the sodium perborate hydrate and nonionic detergent particles are mixed with the sodium tripolyphosphate and nonionic detergent particles. The method of claim 16, wherein the amounts of synthetic, organic, nonionic detergent, builder and sodium perborate hydrate are detersive, detergent build and bleaching amounts, respectively. A method for the preparation of a non-cohesive, discrete, particulate bleaching detergent composition, which method comprises: absorbing a synthetic, organic, nonionic detergent, in a liquid state, in a mixture of small individual particles of sodium perborate-15 hydrate and small individual particles of sodium tripolyphosphate hydrate, with mixing, the amounts of the nonionic detergent, the sodium tripolyphosphate hydrate and the sodium perborate hydrate are detersive detergent-building and bleaching acting amounts, respectively, and the particle sizes of the discrete bleaching detergent are in the range of 2.38 to 0.105 mm. 19. The method of claim 18, wherein the produced small-particle detergent composition comprises 5 to 28% synthetic nonionic organic detergent, 10 to 89% sodium tripolyphosphate, 5 to 50% sodium perborate hydrate, and 1 to 15% moisture, including the moisture from the sodium perborate hydrate and the sodium tripolyphosphate hydrate. A detergent composition according to claim 4, comprising: a soil release promoter amount of a soil release agent copolymer of polyethylene terephthalate and polyoxyethylene terephthalate. A composition according to claim 4, comprising: a fabric softening amount of a fabric softening bentonite. A composition according to claim 4, containing: sodium 35 tripolyphosphate as the "builder", which polyphosphate is in the form of spray-dried granules, with sodium silicate 8500957-29 and sodium sulfate being present in such granules, the sodium being perborate hydrate and the nonionic detergent are present in various particles which are mixed with the builder granules, and wherein the detergent composition contains 1 to 10% sodium sulfate, which improves the processability of the crutcher - mixture from which the granules obtained by spray drying are obtained and improves the flow of the composition. j 8500957