CH631482A5 - Particulate detergent packed in a bottle - Google Patents

Description

The invention relates to a new particulate detergent packaged in bottles which can be dispensed like a liquid but does not have the numerous disadvantages of liquid detergents.

Particulate detergents based on surfactants and builder salts are known. The detergent particles preferably have a round or spherical shape or often consist of aggregates of a small number of spherical particles, such as are obtained when spray-drying a detergent mixture from the crutcher after subsequent screening according to size. Post-spraying the surfaces of the spray-dried beads with liquid, in particular heat-sensitive components is also known.

There are considerable difficulties in obtaining free-flowing products that contain significant amounts of liquid or sticky surfactants, e.g. liquid non-ionic surfactants and water-soluble organic builders. As a result, less tacky surfactants have been used, such as anionic surfactant salts, e.g. B. linear sodium tridecylbenzenesulfonate, which has an excellent washing activity.

Due to the easier handling, liquid detergents are often packed in plastic bottles, e.g. in bottles with a hollow handle. In the case of solid or particulate free-flowing detergents with a high bulk density, the packaging was in bottles from which the solid detergent could be dispensed as easily as a liquid,

not known.

The invention has set itself the task of proposing a packaged, particulate new detergent which does not have the above disadvantages, the detergent according to the invention not being separated into different phases which would otherwise require the presence of constituents which have no detergency, such as Hydrotrope.

To solve this problem, a detergent according to claim 1 is therefore proposed.

The detergent packaged in bottles according to the invention has the advantage, for example, that decomposition reactions in the aqueous or liquid phase do not occur between the individual detergent constituents, since the particulate detergent is essentially dry. Furthermore, the addition of special stabilizers or a modification of the formulation of the detergent to avoid reactions in an aqueous medium, for example, is not necessary. Furthermore, the detergents according to the invention do not, for example, have the disadvantages that would otherwise arise when pouring solid detergent mixtures containing builders, namely that the solid detergent particles are in gel form or bend together at the bottle neck. Overall, the detergent according to the invention therefore preferably combines the advantages of a solid detergent with the advantages of a liquid detergent in terms of packaging and handling.

The particulate new laundry detergent packaged in a bottle according to the invention is characterized in that the bottle has a neck with an outlet opening for dispensing the detergent from the bottle and the bottle is provided with a free-flowing, particulate new detergent mixture pourable through the outlet opening, the particles of which are an organic surfactant and contain a builder for this surfactant and have a particle size such that at least 90% by weight of the particles pass through an 8 mesh US standard sieve and are retained by a 200 mesh US standard sieve, a bulk density of at least 0 , 5 g / cm3 and have a fluidity that is at least 70% of the fluidity of pure dry sand.

In preferred embodiments of the invention, the cross section through the bottle neck region lies in a certain fluctuation range and is matched to the cross section of the bottle region; the bottle may consist of a hollow handle made uniformly with the bottle, which communicates with the main volume of the bottle and has a certain dimension; the bottle neck can be circular and closed by a screw cap of a certain size, which can serve as a measuring vessel for the detergent; the detergent particles can be dust free and the detergent composition can be modified in preferred ranges depending on the properties desired. The invention also relates to a simple method for filling the described bottle and the hollow handle.

In the following the invention is preferably explained in connection with the drawings; show it:

1 is a side view of the filled but unsealed detergent,

2 is a top view of the product,

3 is a side view of the product from the handle side,

4 shows a section along the plane 4-4 of FIG. 1, FIG. 5 shows a partial side view of the upper part of the product according to FIGS. 1 to 4 with a closure cap,

6 is a microphotograph of a larger proportion of a spray-dried builder bead or a particle before spraying with a surfactant to achieve a free-flowing detergent, magnification 200 times,

7 shows an enlarged detail of the bead according to FIG. 6 in a magnification of 2,000,

8 shows a schematic representation of the sequence of the filling operations and filling stages.

The bottle 11 shown in FIG. 1 made of transparent polyvinyl chloride plastic has a main body 13 with a blow-molded handle 15 and a neck part 17. The bottle can have various shapes. Essentially, an oval cross section is preferred, at least in the upper or lower region. The bottle neck and handle are located at the ends of the main or long horizontal axis. The bottle neck or pouring region is located at the top of the bottle, closer to one end of the main horizontal axis of the oval, with the handle located at or near the opposite end of said axis. The upper region 14 of the wall 12, namely the region which is closer to the bottle neck opening, preferably runs almost vertically, namely at an angle of 70 to 90 ° C. to the horizontal. The upper region 16, which is closer to the handle, can run less vertically, namely at an angle of 30 to 60 ° C. Inside the bottle 11 are the detergent particles 19, which can easily be poured through the opening 21 in the neck of the bottle while tilting the bottle. 4 is the area of the main volume 23 of the bottle

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and part of the passage 25 through the handle 15. Both volumes are filled with the detergent 19.

1 to 4, the bottle is shown unlocked. For normal closing and transport, a screw cap 27, shown in FIG. 5, is screwed onto the threaded bottle neck 17. The closure material is normally sufficiently elastic so that usually no sealing washers are required; sealing inserts are often sufficient.

6 and 7, the light areas are reflections of the framework area of the bead, the outer and inner parts of which contribute to its stability. The dark areas represent gaps in the bead into which liquid or dissolved surfactants can penetrate after being sprayed or otherwise applied to the substrate bead. In this way, substrate beads can be produced whose surface is free of detergents and which, for example, have less than 10% of detergents in the outer areas. The bead shown in Figures 6 and 7 was obtained by spray drying. It contains approximately 18.8 parts of pentasodium tripolyphosphate hexahydrate, 7.6 of sodium silicate (NazO: SiOz = 2.4), 28.3 parts of pentasodium tripolyphosphate (anhydrous) and 49.6 parts of water. Spray-dried, the moisture content is approximately 10%.

8 shows six stages of filling the bottle 11 with the detergent 19. The filling head 29 has an extendable filling pipe 31 with a control valve 33. The filling head is in the first filling stage above the empty bottle 11; in the next stage, the filling tube 31 is brought into position and is partially inside the bottle neck 17, the filling of the detergent not yet commencing at this stage. The next stage is the filling of the detergent 19 into the bottle 11. The filling height 35 is half the height at which the handle opens into the main volume of the bottle. The filling level 37 in the area of the handle 15 is lower at this time. In the fourth stage, the filling level has increased. The detergent is now already above the passage 25; the passage is filled with detergent up to fill level 39. In the fifth stage, the fill level of the particles 19 has now reached the final height 41. In the sixth stage, the filling pipe 31 is already drawn in. In a subsequent stage, the bottle is closed automatically or manually.

The bottle which is the container for the final product can be made from any suitable material, although synthetic organic polymeric plastics are preferred, such as polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyester and polyether, glass fiber reinforced plastics and polyamides. For example, it is also possible to use glass bottles. Transparent bottles are preferably used. However, it is also intended to use, for example, opaque and translucent plastics. An important advantage of the bottle materials mentioned is that they are generally conditional or completely water-resistant and that they also prevent the escape of volatile organic substances, e.g. of perfumes. This is usually prevented even with comparatively thin walls with a thickness of 1 to 3 mm.

The bottles can have various shapes. However, they differ from other containers in that they have a neck area that is relatively narrow and, based on the average cross-section of the bottle, is characterized by a narrow opening. In general, such cross sections will be less than 40% of the average bottle cross section; less than 30 or even 25% are preferred. In order to ensure that pouring out is as easy as possible and accurate delivery, the cross section of the bottle neck should be 2 to 40 cm 2, preferably 3 to 20 cm 2 and in particular 5 to 15 cm 2. The bottle neck is usually oriented so that the passageway and walls are parallel to the vertical axis of the bottle, but can also be inclined, usually not more than 30 °, to the vertical axis. Larger angles of inclination are generally also possible. The size of the neck is usually dependent on the bottle volume and on the other hand on the size of the cap, which also serves to measure the amount of detergent required. In the case of Va or 1 liter bottles, the neck height can be 1 to 5 cm. Usually, however, the height is 1.5 to 3 cm. With larger dimensions such as 2-liter and 4-liter bottles, the neck height can be 1 to 5 cm, but a height of 2 to 5 cm is preferred. Other bottle dimensions are expediently adapted to the bottle volume, provided that the bottle has the characteristics described here or a modified one.

The bottle can have different shapes and cross-sections; however, a cross section that is mainly oval is preferred, the bottles shown in the drawings being assigned to this category. Sometimes it is desirable to convert the round shapes that result from such an oval into slightly angular shapes. Such corrected forms are nevertheless understood in the following as oval in the sense of the word. Instead of oval cross sections, other curved shapes can also be used, such as circular, elliptical (which are considered oval bottles), regularly polygonal, for example rectangular, square and polygonal with rounded corners.

Although not an essential feature of the invention, the integrated hollow handle is generally an important feature of the bottle that is consistent with the present detergent composition. Integrated with the bottle neck and with the main area of the bottle, it is often blow molded or otherwise suitably shaped. The inside of the handle communicates with other inner areas of the bottle, so that the detergent can be filled into the handle mentioned and flow out of it. The handle is on the opposite side of the bottle neck or spout and usually does not protrude beyond the normal bottle wall. The handle is thus formed by the elimination of material within the general outline of the bottle and is not arranged on the bottle from the outside. The handle need not have a regular cross-section or an internal passage, although an essentially regular or uniform passage is preferred. The handle should have at least an inner cross section in the range of 1 to 10 cm2, preferably 2 to 5 cm2. The handle is usually so long that it can be easily gripped. A length between 8 and 12 cm was generally determined as such a length. 9 to 11 cm are preferred. The cavity of such a hollow handle can usually be easily filled with the dust-free particles of the free-flowing detergent with a high bulk density; the detergent will easily flow out of the handle cavity when pouring. In this context, a free height above the upper handle passage between the desired filling level of the detergent and the uppermost part of the handle passage is of minimum

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at least 1 cm, preferably at least 5 cm, and for larger containers a height of 10 or 15 cm is advisable. The angle of inclination of the wall 16 is preferably greater than or approximately equal to the angle that the detergent surface has at rest after being deposited during the filling process or after pouring. Accordingly, filling the handle passage and emptying is usually facilitated.

The detergent inside the bottle has, for example, an improved fluidity, an increased bulk density and such a particle size distribution that flow and degassing are favored. The tendency for bridging in the container or in narrowed sections thereof is usually reduced to a minimum. The detergent composition of the particles contains a surfactant and a builder for such a detergent and can contain conventional additives.

Anionic, nonionic, cationic, ampholytic or amphoteric surfactants can be used as the surfactant. Of these, however, the anionic and nonionic surfactants are by far preferred, with nonionic ones being the most suitable for the present composition. Cationic surfactants are usually not used for the present products, especially not when anionic substances are present. Although nonionic surfactants are preferred, mixtures of nonionic and anionic surfactants are sometimes preferred.

The nonionic surfactants can be liquid or semi-solid at room temperature and are usually liquid or sticky at temperatures below 40 ° C. Preferred nonionic surfactants are ethoxylated aliphatic alcohols with a straight or branched chain (preferred are straight chains) with 8 to 22 carbon atoms and 5 to about 30 ethylene oxide units per molecule. Particularly suitable nonionic surfactants of such a type are manufactured by the Shell Chemical Company and put on the market under the trademark Neodol. Of the numerous types of neodol commercially available, Neodol 25-7 (a higher alcohol with 12 to 15 carbon atoms, condensed with an average of 7 ethylene oxide units) and Neodol 45-11 (a higher alcohol with 14 to 15) Carbon atoms, condensed with an average of 11 ethylene oxide units) are particularly preferred. Another suitable class of ethoxylated aliphatic alcohol surfactants is manufactured by the Continental Oil Company under the Alfonic trademark. Here, the preferred type is Al-fonic 1618-65, which is a mixture of primary alcohols with 16 to 18 carbon atoms, which are ethoxylated and have a proportion of 65 mol% of ethylene oxide units.

Additional examples of nonionic surfactants are those marketed by BASF Wyandotte under the Pluronic trademark. Such substances are expediently produced by condensation of ethylene oxide with a hydrophobic base, represented by condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule usually has a molecular weight of about 1500 to 1800, the addition of polyoxyethylene (or ethylene oxide) to such a hydrophobic portion improves the water solubility of the molecule as a whole, with the detergent remaining liquid at room temperature, to a level of about 50% polyoxyethylene. Nonionic surfactants which can also be used are, for example, condensation products of polyethylene oxide with alkylphenols, such as condensation products in which the alkyl group contains 6 to 12 carbon atoms, which can have a straight-chain or branched configuration, and 5 to 25 moles

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Contain ethylene oxide per mole of alkylphenol. The alkyl substituents can be, for example, polymerized propylene, diisobutylene, octene or nonene.

Suitable anionic surfactants include Higher fatty acid soaps, such as natural or synthetic higher fatty acids with 8 to 20 carbon atoms or triglycerides, for example coconut oil, tallow, hydrogenated coconut oil, hydrogenated tallow or mixtures thereof; linear alkylbenzenesulfonates having an alkyl group of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms, for example linear sodium tridecylbenzenesulfonate, paraffin sulfonates, olefin sulfonates and other organic sulfonates and sulfates which have a lipophilic group, usually with a chain of 10 to 18 carbon atoms. The nonionic substances described can be converted into anionic substances by introducing sulfate or sulfonate groups. Usually this happens beforehand at the terminal hydroxyl groups. In such cases, the proportion of ethylene oxide for the preparation of the primary nonionic condensation product usually decreases, so that from 3 to 12 moles preferably 5 to 10 moles of ethylene oxide are present per mole of anionic surfactant.

The anionic detergents are preferably in the form of sodium salts, although potassium salts and occasionally small amounts of ammonium or triethanolamine salts are also used.

Typical cationic surfactants usually have fabric softening and antibacterial properties. This applies in particular to quaternary substances. Examples of such substances are distearyldimethylammonium chloride and 2-heptadecyl-1-methyl-1 - [(2-stearoylamido) -ethyl] -imide-azolinium-methyl sulfate. Numerous amphoteric surfactants are also available, for example. These are generally higher carboxylates, phosphates, sulfates or sulfonates which have a cationic substituent, such as an amino group which is quaternized, for example with a low-chain alkyl group or with a condensation product thereof on the amino group by condensation with a low-chain alkylene oxide, for example ethylene oxide. Typical commercial water-soluble amphoteric surfactants are Deriphat 151; these are sodium N-coco-β-aminopropionate (manufactured by General Mills, Inc.) and Miranol C2M (anhydrous acid, manufactured by Miranol Chemical Company, Inc.).

Other suitable surfactants are described in McCutcheon's "Detergents and Emulsifiers", 1973 Annual and in "Surface Active Agents", Volume II, by Schwartz, Perry and Berch (Interscience Publishers, 1958).

The builder preferably consists of inorganic substances, in particular water-soluble salts, in particular phosphates. However, there are also organic builders such as sodium citrate, sodium gluconate, trisodium nitrilotriacetate and other organic substances which have builder activity and can be processed into a free-flowing detergent. They are often used in mixtures with inorganic substances. The organic substances are usually in the form of the sodium or other alkali metal salts, but sometimes the free acids are also used. Phosphates are particularly preferred for the production of excellently free-flowing particulate materials with a high bulk density, which have a large proportion of surfactants, which are preferably subsequently added to the phosphate base beads; however, other inorganic substances can also be used as builders or in combination with them, such as silicates, borates, carbonates and bicarbonates. Clays with an ion exchange effect, which are used as builders in detergent

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Compositions work by removing ions from the water that cause water hardness, such as Type A (preferably 4A) molecular sieves and other suitable molecular sieves, can also be used as builders, preferably in combination with a suitable phosphate. In the case of detergents which do not contain phosphates, however, they can also be used in combination with nonphosphate builder salts or together with other ion-exchanging zeolites.

In the case of phosphates and other inorganic water-soluble builder salts, the sodium salts are normally used; but potassium salts can also be used. Specific examples of phosphate builder salts are pentasodium tripolyphosphate, other sodium tripolyphosphates such as trisodium tripolyphosphate, trisodium phosphate, disodium phosphate, monosodium phosphate, tetra-sodium pyrophosphate and disodium pyrophosphate. The corresponding potassium salts can also be used, but preferably in mixtures with the sodium salts.

Preferred framework supplements, which are also distinguished by anti-corrosion properties in the detergent described and which aid in the formation of desired beads in the preparation of builders which are subsequently subjected to spraying or spraying on of surfactants, are alkali metal silicates, which are usually in aqueous solutions of approximately 40 up to 60% by weight, usually about 50% by weight, of silicate. Such silicates are preferably sodium silicates with a NazO: SiO 2 ratio between 1: 1.6 and approximately 1: 3.4, preferably from 1: 2 to 1: 3, and in particular from 1: 2.35 or 1: 2.4 .

In the detergent composition, in addition to the surfactants and the structural salt components, numerous additives are present, which are preferably incorporated from a common Crutcher mixture by spray drying together with the particles into the structure of the same or, if they are sensitive to heat, by subsequent addition. Such additives generally include conventional functional and beauty agents such as bleaches, e.g. Sodium perborate, coloring substances, e.g. pigments, colorants and optical brighteners, perfumes, foam stabilizers, e.g. Alkanolamides such as lauric myristine diethanolamide, enzymes e.g. Proteases, amylases, skin-protecting and conditioning substances, for example water-soluble proteins of low molecular weight, which are obtained by hydrolysis of protein-rich materials such as animal hair, glue, gelatin, collagen, foam destroyers, e.g. Silicones, fabric softening agents, e.g. ethoxylated lanolins, bactericides, for example hexa-chlorophene, and buffer substances, for example alkali metal acetate and bisulfates, and substances which improve the flow behavior, for example alumina. In addition, fillers, such as sodium sulfate, mostly anhydrous, and sodium chloride can be present.

The detergent particles normally contain 50 to 98% builders and the rest surfactants. The presence of other substances including water is usually neglected. When other substances are included, the product normally contains 30 to 80% builders, 2 to 35% or 40% surfactants, 0 to 20% additives, excluding fillers, 0 to 50% fillers and 3 to 15% moisture. The detergent according to the invention can be produced in any manner, including spray drying all the necessary heat-stable substances. However, in order to ensure the best fluidity, the lowest dust content, the highest bulk density and a minimum of undesirable chemical reactions and decomposition of constituents, preference is given to the production of a base bead which essentially consists only of the builders and preferably water, with the Surfactant is added afterwards. Such surfactants are liquid non-ionic or mixtures of anionic and non-ionic surfactants, although anionic surfactants can preferably be spray-dried temporarily with the builder. Usually, the base beads in the manufacture of the particles according to the preferred methods consist of approximately 60 to 98% of framework substances and have a porous outer surface and framework-like inner structures. They usually consist of about 2 to 40% surfactants such as those that are liquid or sticky at temperatures below 40 ° C; these are installed inside the beads so that the outer surface of the beads is essentially free of surfactants; the beads are therefore free-flowing. In the preferred embodiments of the invention, the detergent consists of 70 to 95% base beads and 5 to 30% surfactants. The base beads usually consist of approximately 45 to 85% phosphate skeleton salts, approximately 5 to 15% alkali metal silicates and approximately 5 to 15% water. In the particularly preferred embodiments of the invention, the surfactants are nonionic polyethoxylated surfactants, such as those obtained from aliphatic alcohols, which contain 8 to 22 carbon atoms in the chain and are condensed with approximately 5 to 30 moles of ethylene oxide per mole. The phosphates are preferably a mixture of hydrated and anhydrous salts, with a weight ratio of hydrated phosphates, usually pentasodium tripolyphosphate hexahydrate, to anhydrous phosphates, usually pentasodium tripolyphosphate, anhydrous, from about 0.3 to about 0.7, preferably 0. 4 to 0.6. Regardless of the method of manufacture of the detergent, it has been found that for the production of the filled product of the invention it is important that the detergent product has a particle size such that at least 90% of it passes through an 8 mesh sieve and that it passes through a 200 mesh Sieve is retained (US standard sieve). The particles must have a bulk density of at least 0.5 g / cm3 and a fluidity of at least 70% of that of clean dry sand. At least 90% of the detergent should preferably pass through a 20 mesh sieve and be retained by a 200 mesh sieve. It is particularly preferred that over 95% are in the range from 40 to 200 mesh, with less than 0.5% passing through a 200 mesh sieve. A bulk density in the range from 0.55 to 0.8 g / cm 3 is preferred. In terms of fluidity, a value of at least 75% of the fluidity of dry, pure sand is preferred, which can reach up to 100%.

The particles are usually dust-free, so that even after shaking in a transparent container, the space above the product is clear after a short period of time, such as 1 or 2 seconds after shaking has ended, and parts of the product are not adhered to the inner walls of the container. In part, the desired properties of non-dusting are due to the level of nonionic surfactants, which are usually present in sufficient amounts to bind the dust and prevent it from being generated by movement of the particles. The proportion of nonionic surfactants can be 12 to 40% of the product, sometimes 20 or 25 to 40% of the end product. This portion is normally sorbed in the interior of the detergent particles described without making the surfaces sticky or causing the particles to flow poorly. Are typical for particularly preferred nonionic detergents

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the condensation products of an aliphatic alcohol with 10 to 18 carbon atoms in the chain, with 6 to 14 moles of ethylene oxide per mole of the product. Particularly when the detergent contains 20 to 40%, the proportion of detergent particles that passes through 200 or 325 mesh screens is often zero.

Of course, the presence of better absorbable detergents in the particulate product and the associated high bulk density generally lead to lower product consumption per wash cycle. This makes it easier to carry out packaging in bottles, for example, and makes it easier to pour out small amounts of detergent and to measure it in the cap.

In cases where there is only a small amount of dust, the inside of the bottle can be lined with a thin layer of silicone and / or the quaternary ammonium salts mentioned in order to smooth the inside of the bottle and to promote the diffusion of any electrostatic charge in the bottle and thereby counteract adhesion of fine particles to the inside of the bottle. Usually the amount of such substances used is sufficient to produce a thin layer on the inside surface of the bottle, often only 1 to 10 molecules thick.

The bottle cap can be of any suitable nature and can be made of any suitable material. However, screw caps are preferred due to their immediate availability and their suitability for easy closing and measuring. However, complete closure is not usually required because the sealed product is a particulate solid rather than a liquid. It is therefore also possible to use other types of sealing caps which do not have the sealing capabilities of normal screw caps. For example, caps can be used that are press-fitted, such as those that have a slide valve to create a pouring spout. In such or other cases, the bottle neck area can be made flatter than in the case of screw caps and possibly reduced to an opening in the bottle wall. The construction material of the sealing caps can be made of any suitable material, including polymeric plastics, rubber, particularly hard types of rubber, metals and metal alloys; as polymers e.g. Melamine formaldehyde, phenol formaldehyde, polyamides, polystyrenes (compressed or made of foam balls), glass fiber reinforced polyester, polypropylene and polyethylene can be used.

The preferred, internally threaded caps ensure a firm closure of the bottle neck after rotation into the appropriate position. They prevent, for example, a loss of content, an increase in moisture content and other contaminants from the outside, as well as the removal of moisture from the bottle. Because of the nature of the screw cap and the insulating properties of the bottle, an effective and cheap cap is usually obtained.

Special insulating inserts or linings, such as are normally used for packaging detergent powders in the case of permeable containers, are therefore not necessary. In addition, although the cap is relatively small, it can be used to measure the desired amount of detergent particles. In practice, for example, screw caps have been found to be of useful size for closing and opening bottles of a customary size, e.g. B. with a content of 11

to 41, as not large enough to hold the amount of conventional detergent for one wash in an automatic washing machine in one or even four fillings. In the case of a conventionally spray-dried washing powder with a bulk density of approximately 0.3 g / cm 3, onto which a small amount of nonionic surfactants was subsequently sprayed, approximately 90 g or 300 cm 3 of the detergent particles would generally be required for a washing machine drum with a capacity of 64.61 will. The normal bottle cap usually only has a volume of 5 to 15 cm3. Therefore, even with a volume of 15 cm3, in the case of a normal powdery, low-density detergent, one would normally have to measure a volume which would correspond to 20 cap volumes. This would not be acceptable to the consumer, nor would there be any advantage in favor of such a method over the use of a normal measuring cup. According to the invention, however, packaging with only a slightly enlarged closure can be used and allows such a measurement to be carried out. With a larger amount of a surfactant, such as a liquid nonionic surfactant, which can be inserted into the present beads, there is the possibility of reducing the amount of detergent consumption to half per wash. With balls of greater bulk density, for example 0.6, the required volume can be further halved. With a slight enlargement of the closure cap, for example to 20 cm3 instead of 15 cm3, by measuring the closure cap four times, a sufficient amount of detergent powder can be provided for a normal washing cycle in a machine, which is filled from above. For machines that are filled from the side and for which only about half the amount of detergent is conventionally required, a double measurement with the cap is usually sufficient. If the bulk density of the product, its surfactant content and the size of the cap are changed further, an amount of detergent per wash can be used corresponding to the volume of one cap or the volume of three caps. The present invention is therefore a convenient means of measuring a quantity of detergent in a bottle cap of said filled particulate detergent which corresponds to the desired quantity of detergent for a normal washing cycle.

Methods for the production of free flowing particulate laundry detergents with high bulk density and the desired particle sizes are known and can be used in accordance with the invention. Controlled spray drying, spray cooling, agglomeration, solidification and abrasion of crystalline materials etc. are already known and are generally suitable. Nonionic surfactants can be incorporated into the base particles or produced in one with the particles, as long as it is ensured that the particles are of sufficient round or rounded nature for the purpose of free movement and that any liquid or sticky surfactant substances are in the gap system of the particle interior and not on it the surface of the same; normally less than 20%, preferably less than 10%, will be localized on the surface. After the detergent particles have been produced, they are preferably bottled using the method shown in FIG. 8. However, other more complicated and less satisfactory filling techniques can also be used. After the bottle is closed, the shelf life of the product is almost unlimited, and in the

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in most cases there are no undesirable changes for at least 3 years.

The product according to the invention generally has many advantages, many of which have already been mentioned. A comparatively cheap and easily obtainable container with a built-in handle can be provided with conventional closure means, which leads to the product's excellent storage properties. The particles are usually attractively rounded and have a uniform shape and flow behavior like a liquid. For example, they are of sufficient weight to be able to be measured with a comparatively small cap, and they have a multiple washing power with a reasonable bottle size; 11 detergents is sufficient for about 10 to 20, normally about 12, wash cycles, while conventional liquid detergent is only sufficient for 8 wash cycles per 11 detergents. It should also be added that the cap can be graded for finer measurements. The product is easy to manufacture and allows for the convenient incorporation of normally heat unstable components. The stability is also preferably increased with regard to the shelf life. This is usually due to the fact that there is no liquid phase. This allows certain more effective ingredients to be used for the composition, which are normally less stable.

The following examples illustrate but do not limit the invention. Unless otherwise noted, all parts are by weight and all temperatures are given in ~ C.

example 1

An aqueous slurry was prepared consisting of 14.5 parts of pentasodium tripolyphosphate powder (anhydrous), 15.2 parts of a 50% aqueous solution of sodium silicate (Na20: SiO2 = 1: 2.4) and 21 parts of demineralized water. The slurry was brought to a temperature of about 60 ° C and mixed well in a crutcher to obtain the hexahydrate salt of the pentasodium tripolyphosphate. The preliminary crutcher mixture thus prepared was heated to 88 ° C and kept at a temperature of 88 to 93 ° C to prevent hydration of the anhydrous sodium tripolyphosphate powder, which was then added. The complete crutcher mixture was then prepared at a temperature in the 88 to 93 CC range mentioned by adding 28.3 parts of pentasodium tripolyphosphate in powder form (anhydrous) and 21 parts of demineralized water. The resulting mixture contained approximately 45 to 50 weight percent solids. This is due to the hydration of small amounts of anhydrous tripolyphosphate and loss of moisture.

The mixture was pumped into a spray drying tower, which worked according to the countercurrent principle and has a height of 2.8 m. The mixture was sprayed into the dry air at a distribution temperature of 82 ° C at a pressure of about 54 kp / cm 2 (absolute) through a Whirljet 15-1 spray nozzle, which had an initial temperature of about 315 ° C when entering the spray tower.

The spray-dried base beads produced have an internal structure and surface properties like the beads shown in FIGS. 6 and 7, which are rounded, solid particles, with an irregular shape with a sponge-like outer surface and framework-like internal structures. In contrast to this, conventionally spray-dried detergent pellets are characterized by an essentially gapless outer surface and a hollow core.

The spray-dried base beads consist of

77% sodium tripolyphosphate, 13% sodium silicate and 10% moisture. The bulk density is 0.55 g / cm3, the fluidity is 86% of the fluidity of dry sand; the product shows no stickiness. A sieve analysis shows the following: 1% on No. 20 US sieve standard; 19% through No. 20, to No. 40; 50% through No. 40, to No. 60; 20% through No. 60, to No. 80; 6% through No. 80, to No. 100; 3% through No. 100, to No. 200; and 1% through No. 200.

The base beads were placed in a rotary drum mixer operating in batches and subsequently sprayed with Neodol 25-7 and a smaller proportion of coloring substances, perfume and brighteners at a temperature of 49 ° C., so that an end product was obtained which was composed of 78% of the base beads, 19 , 7% Neodol 25-7 and 2.3% minor components. In other experiments, the liquids (Neodol 25-7 and minor constituents or aqueous solutions or dispersions thereof) were applied in the form of drops or a liquid mist to the circulated base beads in Patterson-Kelley double-bowl and Zig-Zag mixers.

The resulting products have a bulk density of 0.68 g / cm3 and a fluidity of 79% and show no stickiness. The analysis shows: 1% on No. 20 US sieve standard, 20% on No. 40; 52% on No. 60; 20% on No. 80; 5% on No. 100; 2% on No. 200; and 0% through No. 200.

The final product obtained after only 10 minutes of mixing was filled into bottles of the type shown in FIGS. 1 to 4 at room temperature in the manner shown in FIG. 8.

The bottles were clear polyvinyl chloride bottles with a volume of approximately two liters. The product was filled by gravity without incident, with the average filling time per bottle being approximately 5 seconds or less and the hollow handle also being filled. There were no problems with this. After filling, the bottles were closed mechanically; the manufactured products were packed in boxes and shipped for storage. Based on previous experience with the storage of coarse detergents and tests, the shelf life of the products can be viewed as a period of over three years.

To produce a concentration of 0.075% in a washing tub of 64.4 liters, 75 cm3 of the detergent are sufficient, that with a cap of approximately 5 cm in diameter and 4 cm in height or in two measuring steps with a cap of 4 cm in diameter and 3 cm in height can be measured. The first-mentioned cap size is used for the bottle explained and is described here.

In a washing machine to be filled from above with a drum capacity of 64.4 liters, a good washing result is achieved with normal laundry of around 4 kg. Similarly, in a washing machine that is filled from the front, half the amount of detergent will result in an effective cleaning of the laundry. When used, the product flows freely out of the bottle and out of the hollow handle, is not easily spilled as in the case of liquids and does not leave any undesirable gel or adhesive-like coatings on the bottle cap or the thread.

The product produced is attractive and is suitable for identifying some or all of the particles, for example by spraying some of the particles with paint.

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Instead of producing the detergent particles according to the method described above, products with the same bulk density, particle size and fluidity, which are also not sticky, can be produced by spray cooling, agglomeration and abrasion techniques, as are known in the production of solid detergents; This results in usable packaged detergents which have the desired washing properties mentioned. However, products made using the method described in this example are considered superior to other detergents made using other such techniques. They are more attractive, flow more freely and have a higher bulk density than products with a similar composition.

Example 2

A product was produced analogously to Example 1 using essentially the same method. This was based on a Crutcher premix consisting of 25 parts of hot water (60 ° C.), 3.5 parts of sodium silicate, solid, and 13 parts of pentasodium tripolyphosphate powder (anhydrous); the slurry was mixed well in a double-walled kettle with steam jacket in order to achieve a hydration of the phosphate to the hexahydrate, then the mixture was heated to 93 ° C. with steam; after this temperature had been reached, 13 parts of anhydrous tripolyphosphate, 25 parts of water, 13 further parts of anhydrous tripolyphosphate and 7.5 parts of anhydrous sodium carbonate were added. During mixing, the temperature must not drop below 82 ° C to prevent hydration of the subsequently added anhydrous tripolyphosphate. The mixture was sprayed under a pressure of 57 kp / cm 2 (absolute) into a spray tower which had a dry air inlet temperature of 343 ° C and an outlet temperature of approximately 113 ° C. The framework particles produced have a particle size distribution such that 90% by weight pass through a No. 20 sieve (US standard sieve) and 90% by weight are retained on a No. 200 sieve. 78 parts of the spray-dried beads were then sprayed according to the method described in Example 1 with 19.5 parts of Neodol 25-7 and 2.5 parts of the smaller amounts of additives (optical brighteners and perfume), while the particles were sprayed at about 5 minutes Residence time were circulated in an inclined, inclined cylindrical circulating device. The product removed had a bulk density of approximately 0.75 g / cm 3, a flow rate of 75% and a moisture content of approximately 5%. It was filled into the described bottles analogously to Example 1 and, as described, examined for its usability as a heavy-duty detergent. It turned out to be very satisfactory and had the desired properties of the product according to Example 1.

631482

Example 3

Analogous to Examples 1 and 2, base beads were prepared from 13 parts of sodium tripolyphosphate hexahydrate, 26 parts of sodium tripolyphosphate, anhydrous, 47 parts of demineralized water, 7.5 parts of organic builder “M” (Monsanto Chemical Company) and 6.5 parts of sodium silicate, solid ( Na20: Si02 = 1: 2.4). 85 parts of the resulting builder beads were sprayed with 12 parts of Neodol 45-11 and 3 parts of the smaller amounts of additives (fluorescent brighteners and perfume). The detergent corresponded to that of Examples 1 and 2 and was a free-flowing, dust-free, attractive detergent with a high bulk density and good washing activity.

Example 4

The procedure was analogous to Example 1, but using Alfonic 1618-65 as the nonionic surfactant, in order to obtain a detergent granulate which has a nonionic surfactant content of 30%, the proportions of the other constituents being reduced accordingly. The product obtained is an excellent detergent and the correspondingly packaged particulate detergent has excellent stability and performance properties.

Example 5

The experiments according to Examples 1 to 4 were repeated with different bottles and detergents. The proportions of the components were varied by + 10%, ± 20% and ± 30% while maintaining the proportions and ratios required according to the invention; Filling into different bottles with caps of different materials and properties was also carried out within the given limits. Products of this type are easy to produce, flow freely, have a high bulk density, and allow simple dimensions with the aid of the closure caps; the detergents obtained are attractive and useful. Detergents and similar products made by other manufacturing techniques than those described and which have the same particle properties are similarly satisfactory.

The invention is a new commercial detergent, namely a particulate coarse detergent, which, for example, avoids the disadvantages that occur with liquid detergents; for the first time, a commercially acceptable use of a particulate heavy duty detergent in a manner similar to that of a liquid heavy duty detergent is possible, but without the disadvantages of such liquid detergents. The bottles are appropriately waterproof, which favors durability. They are preferably attractive, relatively small, resealable, easy to use and yet enable the use of powdered detergents, whereas in the past these bottles were reserved for liquid detergents with the corresponding disadvantages.

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4 sheets of drawings

Claims (14)

631 482 PATENT CLAIMS 1. A particulate detergent packaged in a bottle, characterized in that the bottle has a neck with an outlet opening for dispensing the detergent from the bottle and in the bottle a pourable, free-flowing particulate detergent mixture is provided through the outlet opening, the particles of which are an organic surfactant and one Contain builders for this surfactant and have a particle size such that at least 90% by weight of the particles pass through an 8 mesh US standard sieve and are retained by a 200 mesh US standard sieve, the particles having a bulk density of at least 0.5 g / cm3 and have a fluidity that is at least 70% of the fluidity of pure dry sand. 2. Packaged detergent according to claim 1, characterized in that the bottle neck is in the upper region of the bottle and the outlet opening has a cross section that is less than 40% of the average cross section of the bottle body and that the ten-side are anionic or nonionic surfactants , while the builders contain inorganic builders and the detergent particles have a particle size such that at least 90% by weight of the detergent mixture passes through a 20 mesh screen and is retained by a 200 mesh screen. 3. Packaged detergent according to claims 1 and 2, characterized in that the bottle consists of a plastic or glass and the cross-sectional area in the outlet opening is 2 to 40 cm2 and that the detergent mixture contains phosphates and silicates as builders. 4. Packaged detergent according to claims 1 to 3, characterized in that the bottle has a hollow handle made in one piece therewith, the interior of which is connected to the interior of the bottle, and that the cross-sectional area of the hollow handle is 1 to 10 cm2. 5. Packaged detergent according to claims 1 to 4, characterized in that the bottle has a substantially oval cross-section and the outlet opening or neck has a circular cross-section and is on the horizontal main axis of the oval and closer to one end of this axis. 6. Packaged detergent according to claims 1 to 5, characterized in that the bottle neck opening is covered with a removable sealing cap and that the bottle neck opening is arranged near one end of the horizontal main axis, while the handle is provided at the other end of this axis. 7. Packaged detergent according to claims 1 to 6, characterized in that the bottle neck has an external thread and the closure has an internal thread and is designed in terms of its size as a measuring cup, the> / 2 or 1/3 or 1/4 of the for washing Wash the amount required in a washing machine. 8. Packaged detergent according to claims 1 to 7, characterized in that the bottle consists of transparent material and the detergent mixture is dust-free, so that after dispensing a detergent portion, the bottle and the space above the fill level of the detergent in the bottle is transparent. 9. Packaged detergent according to claims 1 to 8, characterized in that the detergent mixture 60 to 98 wt .-% beads of the detergent builder with a porous outer surface and an inner structure and 2 to 40 wt .-% of a liquid or sticky at below 40 ° C. Contains surfactants, which is deposited in the interior of the beads, so that the outer surfaces of the beads are essentially free of detergents. 10. Packed detergent according to claim 9, characterized in that the detergent contains 70 to 95 wt .-% builders and 5 to 30 wt .-% surfactant and that the builders 45 to 85 wt .-% of a phosphate salt, 5 to 15 wt .-% of an alkali metal silicate and 5 to 15 wt .-% water and that the surfactant is a nonionic, polyethoxylated surfactant. 11. Packaged detergent according to claim 10, characterized in that the phosphate salt as a builder is a sodium tripolyphosphate, that the alkali metal silicate is sodium silicate and that the nonionic surfactant is an ethoxylated aliphatic alcohol with a carbon chain of 8 to 22 carbon atoms and 5 to 30 ethylene oxide units per molecule and that the phosphate salt is present as a mixture of hydrated and anhydrous salt in a weight ratio of 0.3 to 0.7. 12. Packaged detergent according to claim 11, characterized in that the bottle consists of polyvinyl chloride and the detergent mixture has a particle size such that 95% by weight of the particles through a sieve in a range from 40 to 200 meshes and less than 0.5 % By weight pass through a 200 mesh screen and the bulk density of the detergent particles is in a range from 0.55 to 0.8 g / cm 3 and that the fluidity is at least 75% of that of pure dry sand. 13. Packaged detergent according to claim 12, characterized in that the cross section of the bottle neck is in a range of 3 to 20 cm2 and that of the handle in a range of 2 to 5 cm2 and that the sodium silicate present in the detergent is one Na20: Si02 weight ratio in the range of 1: 2 to 1: 3 and has no proportions that pass through a 200 mesh screen, and that the nonionic surfactant is a condensation product of an aliphatic alcohol with 10 to 18 carbon atoms and 6 to 14 moles of ethylene oxide . 14. The method for producing the packaged detergent according to claim 1 by filling the particulate detergent into a bottle with a hollow handle, which is connected to the main space of the bottle, while filling the hollow handle, characterized in that one bottle with an elongated horizontal cross-section and a relatively long and a relatively short horizontal major and minor axes, the long axis forming a vertical plane and the short axis forming a vertical plane intersecting it, and a pouring neck in the upper region of the bottle near one end the long horizontal axis of the upper portion and a hollow handle integrally formed with the bottle at the other end of the vertical plane formed by the longitudinal axis, the hollow interior of the handle being in communication with the main volume of the bottle, holding it in a vertical position and the particulate detergent l through the neck of the bottle into the main interior of the bottle to fill the main volume of the bottle and the handle, and that the filling of the handle is accomplished by pouring the particulate detergent down into the handle when the detergent level rises above this handle without tipping the bottle or feeding the particulate detergent directly into the handle, the passage in the bottle neck has a cross-sectional area of 3 to 20 cm2, which is less than 40% of the average total cross-section of the bottle, and the hollow handle has a part with an inner cross-sectional area in Be2 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 3rd 631 482 rich of 2 to 5 cm 2, and that the particulate detergent has a particle size such that at least 90% by weight of it passes through a 20 mesh screen and is retained by a 200 mesh screen, the particles having a bulk density of at least 0.5 g / cm3 and have a fluidity of at least 70% of that of pure dry sand.