Non-aqueous laundry detergent comprising nonionic surfactant, fabric-treating solid particles, and an organophilic clay as a suspending agent

Patent Board

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The Netherlands © ATerinlaglaidging © 8801547 © NL © Non-aqueous liquid cleaning composition, method of using it and packaging for it.

© Int.CI⁴C11D 17/00, C11D3 / 12.

© Applicant: Colgate-Palmolive Company in New York, New York, Ver. St. v. Am.

Av .: Ir. Th.AHJ Smulders et al. Vereenigde Octrooibureaux Nieuwe Parklaan 107 2587 BP The Hague.

© Application Nr. 8801547.

© Submitted June 17, 1988.

© Priority from 17 June 1987, 21 March 1988.

© Country of priority: Ver. St. v. Am. (US).

© Numbers of the priority requests: 63199, 171341.

© Laid out for January 16, 1989.

The documents attached to this sheet are a print of the originally submitted description with claim (s) and any drawing (s).

VO 0 001 166

Title: Non-aqueous liquid cleaning composition, method of using it and packaging for it.

The invention relates to non-aqueous liquid compositions for the treatment of fabrics. More specifically, the invention relates in one aspect to non-aqueous liquid detergent compositions for laundry that have been made stable against phase separation and gel formation by incorporation of organophilic clay and are easily pourable, and to the use of these compositions for cleaning dirty fabrics. In another aspect, the invention relates to unitary dosing packages for non-aqueous liquid compositions for the treatment of fabrics, in particular little or no phosphate-containing liquid laundry detergent compositions for heavy work.

Liquid non-aqueous laundry detergent compositions for heavy work are well known in the art. Compositions of that type may, for example, contain a liquid nonionic surfactant, in which particles of a builder are dispersed, such as e.g.

described in U.S. Patent Nos. 4,316,812, 3,630,929, 4,264,466, 4,615,820 and 4,661,280.

Liquid detergents are often considered easier to handle than dry powdered or particulate products and are therefore preferred by many consumers. They can have one or more of the following benefits: easily measurable; quickly dissolved in the wash water; easy to apply in concentrated solutions or dispersions to dirty parts of garments to be washed; no dust formation; takes up less storage space; may contain heat sensitive materials. Liquid detergents often also have certain disadvantages,

eg that some such products show separation on storage while others show separation on cooling and are not easily redispersed; the product viscosity can change and either

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become too thick to be poured, or so thin that the product appears watery. On standing, some products become turbid and others gel.

It is known that such suspensions can be stabilized against settling by adding inorganic or organic thickeners or dispersants, such as, for example, very large surface inorganic materials, such as finely divided silica, clay, etc., organic thickeners, such as cellulose ethers, acrylic acrylamide polymers , polyelectrolytes, etc. However, increasing the viscosity of the slurry is limited by the requirement that the liquid slurry must be easily pourable and liquid even at low temperatures. Moreover, such additives do not contribute to the cleaning behavior of the product.

It is known that aqueous swelling colloidal clays, such as bentonite and montmorillonite clay, can be modified by exchanging the metal cation groups with organic groups, thereby changing the hydrophilic clay to organophilic clay. The use of such organophilic clay as gel-forming clay is described in U.S. Pat. No. 2,531,427. Improvements and modifications of organophilic gel-forming clay are e.g. described in U.S. Patents 4,105,578, 4,208,218, 4,287,086, 4,434,075 and 4,434,076. According to said patents, these gel-forming organophilic clays are useful in lubricating greases, oil-based drilling muds, well bore filling fluids, paints, paint-varnish-lacquer removers, adhesives, sealants, inks, polyester gel coatings and the like. However, use as a stabilizer in a non-aqueous liquid detergent composition for washing fabrics is not proposed.

Also disclosed is the use of clay in combination with quaternary ammonium compounds (often referred to as QA compounds) to impart fabric softening properties to detergent compositions, e.g., in British Patent Application GB 2,141,152A.

According to U.S. Pat. No. 4,264,466, the physical stability of a dispersion of particulate materials, such as detergent builders, is improved in a non-aqueous liquid phase by using a clay type with an tactile chain structure, including sepiolite, attapulgite and palygorskite clay, as a primary suspending agent. . The said patent states and it is shown by comparative examples that other clay types, such as montmorillonite clay, eg Bentolite L, hectorite clay (eg Veegum T) and kaolinite clay (eg Hydrite PX), even when used in combination with an auxiliary suspending agent, including cationic surfactant compounds, including QA compounds, are poor suspending agents.

In one aspect of the invention it was found that by adding a small amount of an organophilic modified clay to the non-aqueous liquid suspension an elastic network structure is obtained and an improvement in the cohesion of the suspension is achieved, which together with the natural tendency of the finely divided solid suspended particles to flocculate, is effective in inhibiting settling of the suspended solid particles, e.g. detergent builder material, bleaching agent, antistatic agent, etc.

In this aspect, the invention provides a heavy duty liquid laundry composition composed of a suspension of a detergent builder salt in a liquid nonionic surfactant, which composition contains an amount of organophilic clay to increase the stability of the suspension. In a specific embodiment of this aspect of the invention, a non-aqueous liquid nonionic heavy duty laundry detergent composition is provided, comprising a non-aqueous liquid composed of a non-ionic surfactant, solid particles suspended in the non-aqueous liquid. treatment of tissues, and up to about 1% by weight of an organophilic water-swellable smectite clay, modified with a cationic nitrogen-containing compound, containing at least one long hydrocarbon chain of 8-22 carbon atoms, forming an elastic network or structure throughout the entire slurry to increase the yield stress of the composition and increase its stability, ie to prevent settling of suspended particles, preferably with a reduction or at least without a substantial increase in the plastic viscosity (viscosity under shear conditions) of the composition.

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To a certain extent, instability or viscosity problems, especially if they can be perceived by the consumer, can be solved in whole or in part by including the detergent composition in a unitary package. With unitary packaging is meant a disposable packaging for single use containing a quantity of composition for tissue treatment, suitable for a single full or partial (eg 1/4 or 1/2) load of laundry. For a unitary package, phase separation need not be so significant, since the entire package with contents is put in the washing machine.

There are many proposals for unitary packaging for compositions for the treatment of fabrics. Pre-packaged detergent compositions offer several advantages, such as eliminating the need to measure bulk detergent from a large vessel and dosing in measured amounts, less dusting, less handling of potentially irritating ingredients such as high alkalinity components, bleaching components, etc.

Representative patent literature relating to unique packages for dispersing powdered, liquid or pasty compositions for treating fabrics in aqueous media includes U.S. Pat. Nos. 3,186,869, 3,277,009, 3,322,674,

3,528,925, 3,892,905, 4,115,292, 4,348,293, 4,356,099, 4,416,791

4,608,187, 4,610,799, 4,626,372 and Canadian Patent No. 1,112,534.

U.S. Patent No. 4,348,293 describes a package for a powdered detergent comprising an outer water-insoluble, water-permeable bag and a water-soluble or dispersible inner protective layer. The package may be in the form of a laminate or of separate sheets, properly folded to encapsulate the powdered detergent. The protective inner layer, which is essentially non-porous, prevents dusting of the powdered composition during the filling of the bag and during the use of the package.

For liquid detergent compositions, for example suspensions of detergent build-up particles in liquid non-ionic surfactant, dust formation is not a problem, but the liquid phase of the composition, in particular for liquid mixtures with a relatively low content, can be formed.

- 5 ring viscosities, for example of less than approximately 10,000 centipoise, do leak through the protective inner layer or through possibly not well formed seams or welds. The same applies, although to a lesser extent, to more viscous liquids, pastes, gels and creams.

It has now been found according to another aspect of the invention that a double-walled bag construction can be adapted to any of these pourable low-viscous, highly-viscous, pasty, gel-shaped or cream-shaped non-aqueous liquid detergent compositions by suitable choice of the material of the water-soluble or dispersible inner protective layer, which will prevent leakage of the non-aqueous liquid phase, but will dissolve or disperse in cold, warm or hot wash water within a relatively short time while releasing the contents to the wash water.

In another aspect, therefore, the invention provides a disposable, single-use package for dispensing a non-aqueous build-up liquid laundry detergent composition, which package comprises a multi-component bag containing an outer bag made of water-insoluble, water-permeable non-woven material, and an inner bag made from a film of water-soluble or dispersible, liquid-impermeable material, that heat can be welded at least along the outer edges.

A possible problem with the double-walled bag construction is that when the outer water-insoluble, water-permeable bag is sufficiently porous to allow rapid penetration of the wash water into the interior of the package to dissolve the inner water-soluble bag and to release the detergent composition, when the bag is stored under conditions of high humidity or in case of accidental contact with water, water-soluble bag can be prematurely dissolved or soaked such that leakage of the liquid contents can occur. In a preferred embodiment of this aspect of the invention, therefore, a third, outer removable layer or enclosure of water-insoluble and water-impermeable material is provided to protect the water-soluble inner bag from exposure to or contact with moisture, including atmospheric moisture and / or dirt or other potentially contaminating material.

88? ⁽* ·; 7

As already mentioned, the provision of the liquid detergent compositions in unitary packages will not detect the problem of phase separation, gel formation and the like by the consumer, so that no particular stabilization systems or other precautions appear to be necessary during the preparation of the composition. Nevertheless, product stability is an important issue for the producer, since in many cases there can be a significant lapse of time between the bulk preparation of the product and its packaging in the unitary packages. The preparation can also take place at one location and the packaging at a second, far-away location. In both cases it is important to keep the product as homogeneous as possible from the moment the composition is prepared until the composition is filled in the individual packages. It is also important that the physical properties of the detergent compositions, such as viscosity, gel formation, agglomeration of suspended solid particles, are not significantly altered over time or have a chance to occur, eg during storage, transport or during filling of the packages. Any such changes in physical properties can cause serious drawbacks to the filling and filling equipment, and can, for example, lead to over or underfouling of the packages, clogging of the filling nozzles or similar problems.

According to a preferred embodiment of the invention that applies to both of the above-described aspects, therefore, the non-aqueous heavy duty laundry detergent composition is prepared with suitable rheology modifiers, including one or more viscosity modifiers, anti-geoformers, and physical stabilizers in addition to the essential liquid detergent component and the suspended solid particles, preferably comprising detergent builder salt and other optional functional or aesthetic laundry detergent additives.

The washing power of synthetic non-ionic surfactant detergents in laundry detergent compositions is increased by the addition of builder salts. Sodium tripolyphosphate is one of the preferred builder salts. However, the use of polyphosphate builder salts in detergents has several disadvantages, such as the tendency of the polyphosphates to hydrolyze to pyro and orthophosphates, which are less valuable builder salts.

In addition, the polyphosphate content of detergents is considered to be a cause of the undesirably high phosphate content of surface water, which may contribute to stronger algae growth with the consequence that the biological balance of the water can be adversely affected.

In another and specific aspect, therefore, the invention provides a detergent product comprising a double-walled bag containing a water-soluble, liquid-impermeable inner layer surrounding a non-aqueous liquid detergent composition, and a water-insoluble, water-permeable bag surrounding the inner layer, which liquid detergent composition comprises a little or no phosphorus-containing non-aqueous liquid laundry detergent composition, containing a non-aqueous liquid composed of non-ionic liquid surfactant material, tissue-treating solid particles suspended in the non-aqueous liquid, and an alkylene glycol monoalkyl ether solvent in an amount effective for reducing viscosity and reducing gel formation temperature of the product, wherein at least 50% by weight of the fabric-treating solid particles consists of a salt of hydroxy polycarboxylic acid as a detergent builder.

In a preferred embodiment of this aspect, the invention provides a detergent product comprising a heavy duty liquid detergent composed of a hydroxypolycarboxylic acid builder salt, stably suspended in a liquid nonionic material, and an alkylene glycol alkyl ether solvent in an amount that makes the suspension pourable even at temperatures as low as 5 ° C or lower, which liquid composition is packed in a bag, comprising a closed water-insoluble, water-permeable outer bag and an inner layer of a water-soluble, liquid-impermeable material, which separates the liquid composition from the outer bag, and preferably around the outer bag a removable sheath of water-insoluble and water-impermeable material to protect the water-soluble inner bag from exposure to or contact with moisture and dirt, before the bag is added to an aqueous washing bath_e 8 8 8 U * 7 added.

The non-aqueous liquid detergent compositions according to the invention contain a non-aqueous liquid phase composed of a liquid non-ionic surfactant as at least the main component and, if desired, but preferably one or more viscosity modifying and gel-inhibiting organic solvents, as well as in suspension liquid-particle-treated or detergent-reinforcing solid particles in the liquid phase.

According to the first aspect of the invention, the stability of the suspended solid particles is increased by incorporating into the composition an effective amount, usually up to about 1% by weight of the composition, of an organophilic clay. The organophilic clay comprises a swelling smectite clay, modified with a nitrogen-containing compound, containing at least one long chain hydrocarbon chain with 8 22 carbon atoms.

According to the second aspect of the invention, the non-aqueous liquid detergent composition with or without the stabilizing organophilic clay is provided in a unitary package formed by a pouch with an outer layer of a water-permeable, water-insoluble plastic film or textile fabric, an inside of the outer layer inner layer formed from a water-soluble polymer film-forming material, wherein the liquid tissue-treating composition is contained within the inner layer in an amount of 50-150 g.

In the third aspect of the invention, a non-aqueous, little or no phosphate-built, liquid composition for treating fabrics is used in the unitary package, as described above for the second aspect of the invention, which composition is at least 20 wt. % liquid non-ionic surfactant and at least 20% by weight of an alkali metal salt of a hydroxy polycarboxylic acid with 4-8 carbon atoms, calculated on the total composition, and a low alkylene glycol alkyl ether solvent in sufficient amount to reduce the viscosity and gel formation temperature of the composition such that the composition remains pourable at temperatures of 5 ° C and below.

According to the second and third aspect of the invention and, if

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also in accordance with the first aspect, a non-aqueous liquid laundry detergent, preferably one that is easily pourable, is prepackaged in metered single-dose dosage forms in disposable packages or pouches.

A multi-component disposable bag is used of the type described in U.S. Patent No. 4,348,293. Certain details concerning the construction, the materials and the manufacture can be found in the said patent. Therefore, only the preferred embodiments and unique aspects of the pouches to be used according to the invention are described here. The package contains an outer bag of water-permeable or porous, water-insoluble film or fabric and an inner bag of a water-soluble or dispersible, liquid-impermeable film. The inner bag is filled with the appropriate dose of the non-aqueous liquid detergent composition and is then closed. The outer bag is closed around the inner bag, which can be freely movable within the outer bag, ie is not adhered to the walls of the outer bag, or may be attached to one or more edges or walls of the outer bag, eg by adhesives, heat seals, staples, sewing, etc. In use in the aqueous wash bath, the water of the bath will penetrate or flow through the outer bag and come into contact with the inner bag, which then dissolves in contact with the water, exposes the detergent composition to the wash water inside the bag and the detergent, building material etc. from the outer bag to the aqueous washad. In this way the composition according to the invention can be introduced into the washing bath gradually during the washing cycle, preferably in the course of one or more minutes, e.g. within 1-5 minutes, such as about 2-3 minutes. Although the water-insoluble outer bag can be made from a perforated water-insoluble material, e.g. resin impregnated paper, paraffin paper, viscose, polyolefin film, polyester film and the like, it is preferable to manufacture the outer bag from non-woven textile from fibers of natural and / or synthetic origin. Non-woven polyester materials with a density of 10 - 40 g / m², preferably from 15-30 g / m² and in particular at 35 without 18-24 g / m² have proved effective in practice.

. &amp; 8 th 1 '«7

Another preferred material for the outer bag is highly porous spun-bonded non-woven polypropylene. The density thereof can be the same as described for the non-woven polyester materials.

Examples of other suitable fiber materials are polyamides, polyacrylics, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, etc., polyvinyl chloride, polyvinylidene chloride, rayon, cellulose and the like.

It has been found suitable for most product compositions to use 50-150 g of the detergent composition, preferably 60-120 g, such as 70, 80, 90, 100 or 110 g per wash, which amount easily fits into a single package with dimensions of eg 7.6 - 10.2 or more centimeters per side, such as 8.9 cm or 9.5 cm or 10.2 cm per side.

Polyvinyl alcohol with a degree of hydrolysis of at least 60%, preferably from 80 - 100%, such as 85 - 98%, eg 88%, is preferably used as the water-soluble film or sheet for forming the water-soluble, liquid-soluble impermeable inner bag of the package. Other water-soluble films or sheets may also be used. For example, mention can be made of polyethylene oxide, methyl cellulose, gelatin, polysaccharides, polyacrylic acid and the like.

In order for the water-soluble film material to be impervious to the non-aqueous liquid phase, it is important that the material be non-porous. Such non-porous films are commercially available. Furthermore, the film material must have a suitable thickness. Depending on the nature of the water-soluble film material, thicknesses of at least 0.1 ram and preferably of at least 0.25 mm are generally chosen. On the other hand, the film should not be so thick that an excessive amount of time is required for dissolution after placing in the wash bath. Therefore, a thickness of up to about 2.5 mm, preferably up to about 1.25 mm, is selected.

Another important factor for the selection of suitable water-soluble film-forming material to obtain the required impermeability for the non-aqueous liquid phase at acceptable dissolution properties is the molecular weight of the film. In the case of polyvinyl alcohol films, it provides a molecular weight of about 40,000

A good dissolution rate, even in cold water, but such films may be partially permeable to the non-aqueous liquid phase. Polyvinyl alcohol films with a molecular weight of about 80,000 are non-permeable to the non-aqueous liquid phase and require more time to dissolve in cold water, but dissolve quickly in warm water (about 30 ° C or higher). To be able to use liquid detergent compositions in an acceptable manner with cold wash water, polyvinyl alcohol films with molecular weights of 45,000 to 75,000 are therefore preferred, although lower or higher molecular weights may also be acceptable.

For use with hot water, higher molecular weights provide

eg from 60,000 - 100,000, an acceptable dissolution rate with good liquid impermeability.

Suitable molecular weight ranges for other water-soluble film-forming materials and for a particular non-aqueous liquid detergent composition can be easily determined by routine testing.

As an alternative to the use of water-soluble films for the inner protective bag layer, it is possible to use perforated films of water-insoluble materials, the perforations of which are filled or blocked with a water-soluble substance, such as the above-mentioned water soluble substances. The perforations can e.g. 20 - 80% of the total surface area of ​​one or both of the main sides of the inner bag and can cover an area of ​​0.80 - 3.20 cm². The perforations can be made in any desired geometric configuration and arrangement, eg circular perforations in a square pattern, star-shaped perforations in a circular pattern, etc.

The use of a double-walled bag in which the outer wall is formed from a closed, water-insoluble, water-permeable material has several advantages. The water-insoluble outer bag can protect the water-soluble inner bag from exposure to moisture during storage, but will allow water-permeable exposure of the water-soluble film and the liquid detergent product to the aqueous wash bath, so that the detergent and the tissue treating components during the wash cycle on the fabrics

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can be dispersed. Furthermore, since the outer bag of the package is closed and also remains closed during washing, rinsing, and centrifuging of the washing machine, any residue of the water-soluble inner bag will be held within the package and not deposited on the fabric to be washed. For example, portions of the partially hydrolyzed polyvinyl acetate may be water-insoluble and may form lumps upon dissolution of the water-soluble portions. These kibble then remain within the water-insoluble outer bag. It may also be advantageous in some cases to render the inner bag partially water-insoluble, for example through a paraffin coating, to increase storage stability. This paraffin coating will also remain within the permeable but insoluble outer bag of the package.

However, it has been found that in practice to protect the water-soluble inner bag and its liquid contents against premature exposure to moisture, either water vapor in moist environments, or accidental contact with water or dirt during storage, transport or during use and handling. by the consumer, the packaging can be provided in a simple and efficient way with a removable protective, water-insoluble and water-impermeable wrap as the outermost layer.

For this purpose, any water-insoluble and water-impermeable (e.g., non-porous) film-forming material can be used. For example, mention may be made of polyolefin films, polyester films, polyvinyl chloride films, polyvinylidene chloride and other polymeric materials, water-resistant paper, paraffin paper, metal foil, eg aluminum foil and the like.

In this context, the water-insoluble and water-impermeable protective outer wrap should be distinguished from the removable water-insoluble protective agent as used in the aforementioned U.S. Patent No. 4,348,293, which protective agent is applied as a coating on the water-insoluble and water-permeable film and can only be removed by dispersion in the wash bath.

The outer wrapper can be formed in any suitable structure

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which allows easy removal by the consumer. For example, baggy-type (eg PVDC) bags can be used, the open end of which is temporarily closed with a cord or by a closing fit or peelable adhesive bond. Heat-sealable plastic materials can also be heat-welded along all open edges (e.g. all four edges, when two separate film sheets are used, or over three edges, when a single film sheet is collapsed) and provided with a breakable score line or at one edge provided with a notch to allow easy tearing open. Biaxially oriented polypropylene film is easily tearable and highly watertight. When metal foil is used as the outer protective wrapper, it can also be closed temporarily in any suitable manner, for example with the aid of adhesive, while the metal foil can also easily be accurately folded together according to known methods.

Thanks to the outer protective waterproof wrap, the detergent product can be stored under high humidity conditions or otherwise exposed to water without causing premature dissolution of the inner water-soluble bag or leakage of the liquid detergent composition.

In addition to the protective function against exposure to moisture, the outer protective wrap also protects the water-permeable outer bag from contact with dirt and dust from the environment, which could adversely affect the permeability of the product.

With an outer bag of non-woven material, dirt or dust particles can become trapped in the fiber material, which would make the article unacceptable to the end user.

Although the outer protective wrap has been described as a separate, independent cover, it is also possible to laminate the outer wrap to the water-insoluble, water-permeable outer bag with peelable adhesive material or by heat welding along one or more edges.

In any case, it is a simple task for the consumer to remove the outer protective wrapper before the detergent product is introduced into the washing machine.

As described in U.S. Pat. No. 4,348,293, it is also possible to affix suitable signs, e.g., printed advertising, images, instructions for use, and the like, to the outer water-tight protective wrap and / or the outer, water-permeable bag.

It is also within the scope of the invention to apply to the fibers of the outer bag a water-insoluble and water-permeable non-woven material a coating of a fabric softening composition, such as a cationic quaternary ammonium salt, possibly with an aqueous insoluble wax, so that the softening agent is not activated (released) before the package together with the washed textile fabrics has been transferred to a tumble dryer. Such fabric softening materials are known per se.

Similarly, the non-woven material can be impregnated with perfume or perfume for transfer to the washed articles.

The detergent products can also be manufactured in interconnected form in one of the described embodiments, for example in a strip with breakable compounds, to facilitate the dosing of different number of bags, such as suitable for different washing conditions and washing loads.

The liquid detergent composition of the detergent product is described in more detail below.

The liquid phase of the non-aqueous liquid detergent composition according to the invention for each of the various aspects consists of liquid non-ionic synthetic organic detergent and optionally, but preferably, alkylene glycol monoalkyl ether as a viscosity regulator and anti-gel-forming agent. However, a portion of the liquid phase may consist of other organic solvents which may enter the composition as solvent carriers or as carriers for one or more of the solid particulate ingredients, such as in enzyme suspensions, perfumes, and the like.

In the practice of the invention, any of a wide variety of non-ionic synthetic organic detergents can be used, which are well known and are described, for example, in Surface Active Agents, Vol. II, Schwartz, Perry and Berch, published in 1958 by_t 8 8 0 1 5 4 7

35

Interscience Publishers, and in McCutcheon's Detergents and Emulsifiers, 1969 Annual. Typically, the nonionic detergents are poly (low) alkoxylated lipophiles, wherein the desired hydrophilic-lipophilic balance has been achieved by attaching a hydrophilic poly (low) alkoxy group to a lipophilic moiety. A preferred class of non-ionic detergents is the poly (low) alkoxylated (high) alkanols, in which the alkanol contains 10-22 carbon atoms and in which the number of moles (low) of alkylene oxide (with 2 or 3 carbon atoms) is 3-20. Of such materials, preferably those are used in which the alkanol is a fatty alcohol with 10 to 11 or 12 to 15 carbon atoms and which contain 5 to 18, preferably 6 to 14, lower alkoxy groups per mole. The lower alkoxy groups are often ethoxy groups, but may in certain cases preferably be mixed with propoxy. Examples of such ethoxylated alcohols are those in which the alkanol contains 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, eg Neodol

25-7 and Neodol 23-6.5, which products by Shell Chemical Company, Inc. are being produced. The former product is a condensation product of a mixture of fatty alcohols with an average of 12-15 carbon atoms with about 7 moles of ethylene oxide, and the latter product is a corresponding mixture in which the carbon atom content of the fatty alcohol is 12-13 and the number of ethylene oxide groups on average about 6, 5. The higher alcohols are primary alkanols. Other examples of such detergents are Tergitol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates produced by

Union Carbide Corp. The former product is a mixed ethoxylation product of one^cij ~^c15 linear secondary alkanol with 7 moles of ethylene oxide, and the latter being a similar product but with 9 moles of ethylene oxide.

Also in the present compositions, as a component of the non-ionic detergent, higher molecular weight non-ionic materials may be used, such as Neodol 45-11, which are similar condensation products of fatty alcohols having 14-15 carbon atoms and about 11 ethylene oxide groups per mole. These products are also produced by Shell Chemical Company.

Shell Chemical Company markets another group of liquid non-ionic materials under the brand name Dobanol, eg Dobanol 91-5, an ethoxylated C_Q-C ,. fatty alcohol with an average of 5 moles of ethylene oxide; and Dobanol 25-7, an ethoxylated one^C.^ 2^_^ 15 fatty alcohol with an average of 7 moles of ethylene oxide; etc.

Other very useful nonionic materials are represented by the commercially well-known class of nonionic compounds, which are the reaction product of a high linear alcohol and a mixture of ethylene and propylene oxides, and which have a mixed chain or blocks of ethylene oxide and propylene oxide containing, ending in a hydroxyl group. Examples are the nonionic materials that are marketed by BASF under the trade name Plurafac, such as one^c^^-c^ 5 fatty alcohol, condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, a C 1-6 fatty alcohol, condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, a fatty alcohol, condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, etc.

In general, the condensation products of fatty alcohol and a mixture of ethylene oxide and propylene oxide are represented by the general formula

RO {CH.O) (CHO) H 3 6 p 2 4 q wherein R is a linear or branched, primary or secondary aliphatic hydrocarbon group, preferably alkyl or alkenyl, particularly preferably alkyl, with 6-20 carbon atoms, preferably 10 - 18 carbon atoms, in particular 12 to 18 carbon atoms, p is a number with a value of 2-8, preferably 3 - 6, and q is a number with a value of 2-12, preferably 4 - 10. These condensation products can be used advantageously when low foaming is desired. Furthermore, these surfactants have the advantage of low gel formation temperatures. Mixtures of two or more of these mixed ethylene oxide-propylene oxide / fatty alcohol condensation products can be used, as well as mixtures of these condensation products with one or more of the alkoxylated non-ionic compounds described above, while mixtures of the ethoxylated nonionic materials can also be used.

In view of the low gel formation temperatures and low pour points 35, another class of non-ionic surfactant deserves

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bonds are preferred, in particular the C 1 -C 4 ^{secun &lt;}^^ai^re fatty alcohols with a relatively narrow range of ethylene oxide levels within the range of 7-9 moles, in particular about 8 moles of ethylene oxide per molecule, and the C 8 -C 10, especially fatty alcohols, ethoxylated with about 6 moles of ethylene oxide.

The compositions according to the invention preferably contain an organic alkylene glycol alkyl ether solvent, which acts as a viscosity regulator and inhibitory agent for the liquid nonionic surfactant, Alkylene glycol alkyl ethers, such as the compounds marketed under the trade names Carbopol and Carbitol, which relatively short hydrocarbon chain lengths (C₂-Cg) ^{and a}low alkylene oxide content (about 2-6 ethylene oxide and / or propylene oxide units per molecule), are particularly suitable viscosity regulators and anti-gel-forming solvents in the compositions of the invention. Suitable glycol ethers can be represented by the general formula

R² i I

RO (CH_CHO) H

2 n 2 wherein R is a C 1 -C 4, preferably C 1 -C 4 alkyl group and R is hydrogen or

1 o represents methyl and n is a number with an average value of 1-6, preferably of 1-4.

The glycol ethers can also be considered as condensation products of C -C_O alcohols with ethylene oxide or propylene oxide in mole ratios of alcohol to alkoxide of 1: 1 to 6: 1.

Specific examples of suitable solvents are ethylene glycol monoethyl ether (C ^ H ^ -O-CH ^ CH ^ OH), diethylene glycol monobutyl ether (C ^ Hg-O- (CH₂CH₂O) ₂H), tetraethylene glycol monoctyl ether (ΟθΗ ^ -Ο (CH₂CH₂O), tripropylene glycol methyl ether (CH 4 -O- (CH₂CH (CH 2) 0), etc. Diethylene glycol monobutyl ether and tripropylene glycol monomethyl ether are preferred, of which tripropylene glycol methyl ether is particularly preferred.

The amount of non-ionic surfactant is generally 20 to 70%, such as 30 to 60%, e.g. 35% or 40% of the weight of the composition. The amount of alkylene glycol is usually up to 20%, preferably up to 15%, e.g. 0.5 - 15%, preferably 5.0 - 12.5%,

f. &lt;5 4 $ i 7 such as 8%, 10% or 12%. The weight ratio of non-ionic surfactant to alkylene glycol ether is between 100: 1 and 1: 1, preferably between 50: 1 and 2: 1, such as 10: 1.8: 1.6: 1,: 1 or 3: 1.

The detergent compositions of the invention may also contain, as an essential component, at least one finely divided fabric treating solid particulate material. This includes detergent builder salts (inorganic or organic), bleaching agents, bleach activators, anti-redeposition agents and dirt suspending agents, enzymes, optical brighteners, pigments, thickeners and the like, and generally mixtures of two or more different classes of suspended solid particles will be present to be. Particularly preferred fabric-treating particles are the water-soluble and / or water-dispersible detergent builder salts of hydroxy polycarboxylic acid with 4-8 carbon atoms. These builder salts may contain 2 or 3 carboxyl groups and 1 to 4 hydroxyl groups per molecule. They preferably contain 4-6 carbon atoms including the carboxyl carbon atoms, per molecule. Examples of suitable acids are malic acid, HC 4, CC 2 CH (OH) CO 2 H; tartaric acid, HC ^ CCH (OH) CH (OH) CC ^ H? citric acid, HO 2 CCH 2 C (OH) (CO 2 H) C 4 C X 4 H; isocitric acid, HO 2 CCH 2 CH (CX-H) CH (OH) CC&gt; 2-tricarballylic acid (1,2-dihydroxy-1,2,3-propylenetricarboxylic acid), HO₂CCH₂C (ÖH) (ΟΟ₂Η) ΟΗ (ΟΗ) ΟΟ₂Η? trihydroxyglutaric acid, HO₂CCH (OH) CH (OH) CH (OH) CO₂H; mucic acid, HO₂CCH (OH) CH (OH) CH (OH) CH (OH) CO₂H. Citric acid and tartaric acid are preferred.

As the cation of the salts of these acids, the alkali metals such as sodium and potassium are preferred, in particular sodium. Furthermore, the salts may be in the form of the mono, di or tri salt, such as monosodium, disodium or trisodium citrate, preferably the latter. However, when the monosodium or disodium citrate is used, it is preferable to add an additional alkaline builder salt, such as sodium silicate, e.g. disodium silicate, to bring the pH to about the same level as that obtained when the trisodium citrate is used. Similarly, when using monosodium tartrate, additional alkaline compounds can be added to increase the pH level to the desired alkaline range. Furthermore, the salts can be used in their anhydrous or hydrated form, e.g., sodium citrate dihydrate.

The alkali metal mono- or polyhydroxy-di- or tricarboxylic acid salts have the advantage of a high calcium and magnesium binding capacity, which enables them to inhibit the formation of insoluble calcium and magnesium salts; the builder salts to be used according to the invention are in particular superior anti-crust agents.

In order to function effectively as anti-crusting agents, the hydroxypolycarboxylic acid builder salts are present in the composition in amounts of at least 10% by weight, preferably at least 20% by weight and up to about 60% by weight, preferably up to about 50% by weight, e.g. in amounts of 15 or 20% by weight to 50-66% by weight, particularly preferably in amounts of 25-45% by weight, calculated on the total composition.

They preferably constitute at least 50% by weight, in particular at least 75% by weight, of the total amount of suspended solid particles present in the composition.

In addition to or instead of the hydroxy polycarboxylic acid salts, other inorganic and / or organic builder salts, preferably not of the polyphosphate type, may also be included in the composition. Examples of suitable builder salts are described in said U.S. Patent Nos. 4,316,812, 4,264,466, 3,630,929, 4,661,280 and many others. Examples of water-soluble inorganic alkaline builder salts that can be used are alkali metal carbonates, borates, bicarbonates and silicates (ammonium or substituted ammonium salts can also be used). Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate, and potassium bicarbonate.

Although it is preferred that the detergent composition be free of phosphate or polyphosphate builder salts, in some cases small amounts of the conventional polyphosphate builder salts may be added where local legislation permits. Specific examples of such builder salts are sodium or potassium tripolyphosphate, sodium potassium pyrophosphate, sodium hexametaphosphate, sodium mono- and diorthophosphate. Sodium tripolyphosphate (TPP), usually in amounts of up to about 30% to 40%, preferably up to about 20%, such as 5-15%, 6801547 is particularly preferred when phosphate-containing components are not prohibited. Nevertheless, the amount of phosphate or polyphosphate builder salt is not greater than 10%, e.g. 0-6%, preferably 0-3%. Phosphate-free compositions are particularly preferred.

Another class of inorganic builder salts that can be used are the water-insoluble aluminosilicates, both of the crystalline and the amorphous type, e.g. crystalline zeolites.

Examples of organic alkaline sequestrating builder salts that can be used alone with the detergent or mixed with other organic and inorganic builder salts are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, eg sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA ) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable.

Suitable additional builder salts of the organic type are carboxymethyl succinates, tartronates and glycolates and the polyacetal carboxylates.

The total amount of suspended detergent builder salt, including the preferred hydroxy polycarboxylic acid salt or one of the other inorganic and / or organic builder salts, calculated on the total composition, is usually 10-55% by weight, such as 20-50% by weight, e.g. 40-40% by weight. %. Above about 55%, it becomes extremely difficult to form fluid and pourable compositions easily, even at high solvent levels.

It is often desirable to supplement the builder salt with an auxiliary builder material, such as a polymeric carboxylic acid with a high calcium / magnesium binding capacity to further inhibit crust formation, which could otherwise be caused by formation of insoluble calcium or magnesium salts. Such auxiliary builder materials are common known and include e.g. polyacrylic building materials, such as Sokolan CP5, a copolymer of approximately equal molar amounts of methacrylic acid and maleic anhydride, completely neutralized to form its sodium salt. The amount of auxiliary building salt is generally not greater than 6% by weight, preferably 1/4 - 4%, such as 1%, 2% or 3%, calculated on the total weight of the composition.

<img file="NL8801547A_D0008.tif" />

V

Other tissue-treating solid particulate additives or auxiliaries, which may be present in the detergent product, usually in minor amounts, to impart further desirable properties of a functional or aesthetic nature are dirt suspending or anti-redeposition agents, e.g., polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, etc., usually in amounts up to 10% by weight, e.g. 0.1 - 10%, preferably 1 - 5%; optical brighteners, eg cotton, polyamide and polyester brighteners such as stilbene, triazole and benzidine sulfone compositions, preferably stilbene brightener in amounts of up to 2% by weight, preferably up to 1% by weight, such as 0.1-0.8% by weight.

Bluing agents such as ultramarine blue; enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypain and pepsin, as well as amylase-type enzymes, lipase-type enzymes, and particularly preferably mixtures of two or three different classes thereof; bactericides, e.g. tetrachlorosalicylic anilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives; ultraviolet absorbers; anti-yellowing agents such as sodium carboxymethyl cellulose; pH modifiers and pH buffers; color-safe bleaching agents; perfumes; antifoaming agents or suds suppressors, e.g., silicone compounds, may also be used.

The bleaching agents are conveniently classified as chlorine bleaching agents and oxygen bleaching agents. Oxygen bleaching agents are preferred and are represented by per compounds which release hydrogen peroxide in solution. Preferred examples are sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, in particular sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator therefor. Suitable activators that can lower the effective operating temperature of the peroxide bleach are described, for example, in U.S. Pat. No. 4,264,466 or in Column 1 of U.S. Pat. No. 4,430,244. Polyacylated compounds are preferred activators; Among these compounds, tetra-

<img file="NL8801547A_D0009.tif" />

Acetylethylenediamine (TAED) and pentaacetyl glucose are particularly preferred.

Other suitable activators are, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and salts thereof, ethylidene carboxylate acetate and salts thereof, alkyl and alkenylsuccinic anhydride, tetraacetylglycouril (TAGU) and derivatives thereof.

Preferably, a sequestering agent with high complexing capacity is included to inhibit undesired reactions between peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred sequestering agents are capable of forming a complex with Cu (II) ions such that the stability constant (pK) of the complex formation is equal to or greater than 6 at 25 ° C in water of an ionic strength of 0.1 mol / liters. Examples of suitable sequestering agents other than those mentioned are compounds such as diethylenetriamine pentaacetic acid, diethylenetriamine pentamethylene phosphoric acid and ethylenediaminetetramethylene phosphoric acid.

According to the first aspect of the invention, the physical stability of the suspension of the detergent builder compound or compounds or any other suspended additive, such as bleaching agent and the like, in the liquid carrier is drastically improved by the presence of a stabilizing agent, which according to the invention consists of a elastic network forming organophilic modified clay.

The organophilic modified clay can be based on any swelling clay, modified to display high gel-forming efficiency in the organic liquid carrier. As examples of such swelling clay materials that can be used (after suitable modification, as described below), there may be mentioned the smectite clays, in particular bentonite, e.g. sodium and lithium bentonites; montmorillonites, e.g. sodium and calcium montmorillonites; saponites, eg sodium saponites; and hectorites, e.g. sodium hectorites. Other representative clays are beidellite and stevensite.

Said smectite-type clays are three-layer clay materials, characterized by the ability of the layered structure to increase its volume several times by swelling or expanding in the presence of water to form a thixotropic gelatine.

<img file="NL8801547A_D0010.tif" />

nasal dust. There are two main classes of clay materials of the smectite type: in the first class, aluminum oxide is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. Atomic substitution by iron, magnesium, sodium, potassium, calcium and the like can occur within the crystal lattice of the smectite clay materials. It is common to distinguish between clay materials based on their predominant cation. For example, a sodium clay a clay in which the cation is predominantly sodium. Aluminum silicates, in which sodium is the predominant cation, are preferred, eg bentonite clay. Among the bentonite clay materials, those from Wyoming (commonly referred to as Western or Wyoming bentonite) are particularly preferred.

Preferred swelling bentonite is commercially available as industrial bentonite under the Mineral Colloid brand from Benton Clay Company, affiliated with Georgia Kaolin Co. These materials, which were the same as those previously sold under the brand name THIXO-JEL, are selectively extracted and treated bentonite and the most useful are available as Mineral Colloid Nos. 01, etc., corresponding to THIXOJEL 1, 2, 3 and 4. These materials have a pH (6% concentration in water) of 8 - 9.4, maximum free moisture content of about 8% and specific weights of about 2.6, and for the powdered quality at least about 85% ( and preferably 100%) passed through a screen with a mesh size of 0.074 mm. The swelling capacity of the bentonite in water is usually 2-15 ml / g and its viscosity at a 6% concentration in water is usually 8-30 centipoise.

Instead of THIXO-JEL or Mineral Colloid bentonite, one can use products such as the American Colloid Company, Industrial Division, marketed as General Purpose Bentonite Powder,

325 mesh, of which at least 95% has a diameter of less than 44 micrometres (moist) and at least 96% has a diameter of less than 74 micrometres (dry). Such water-containing aluminum silicate consists mainly of montmorillonite (90% minimum) with small amounts of feldspar, biotite and selenite. A typical anhydrous analysis is 63.0% silica, 21.5% alumina, 3.3% iron (III) (as Fe 2 O 4), 0.4% iron (II) (as Fe 2), 2, 7% magnesium (as Mg), 2.6% sodium and potassium

<img file="NL8801547A_D0011.tif" />

(as Na 2 O), 0.7% calcium (as CaO), 5.6% crystal water (as H 2 O) and 0.7% trace elements.

Although western bentonite is preferred, other bentonite can also be used, such as obtained by treating Italian or analogous bentonite, which has relatively low monovalent metals (sodium and potassium), with alkaline materials, such as sodium carbonate, to increase the cation exchange capacity of such products. The Na 2 O content of the bentonite is at least about 0.5%, preferably at least 1% and in particular at least 2%, so that the clay exhibits a satisfactory swelling. Preferred swelling bentonite of the types described above is available under the brand names Laviosa and Winkelmann, eg Laviosa AGB and Winkelmann G-13. Other examples are Veegum F and Laponite SP, both sodium hectorites, Gelwhite L, a calcium montmorilionite, Gelwhite GP, a sodium montmorillonite, Barasym LIH 200, a lithium hectorite.

The smectite clay materials described above are hydrophilic, ie they exhibit swelling properties in aqueous media. Conversely, they are organophobic and do not show swelling in non-aqueous or predominantly non-aqueous systems.

According to the invention, the organophobic nature of the smectite clay materials is converted to an organophilic nature, e.g. by exchange of the metal cation, e.g. Na, K, Li, Ca, etc. of the clay against an organic cation, at least on the surface of the clay particles. This is possible be accomplished by mixing the clay, organic cation and water together, preferably at a temperature between 20 and 100 ° C, for sufficient time for interaction of the organic cation and the clay particles, at least on the surface thereof, followed by filtration, washing, drying and grinding. For further details reference is made to U.S. Pat. Nos. 2,531,427, 2,966,506, 4,105,578, 4,208,218, 4,287,086, 4,424,075 and 4,434,076.

The organic cationic material is preferably a quaternary ammonium compound, particularly one with capillary-active properties, indicating at least one long-chain hydrocarbon group (e.g., 8-22 carbon atoms), although capillary-active properties or other beneficial properties for tissue are not required, while nor is it essential whether the non-ionic modification agent is itself suitable as a suspending agent. Nevertheless, the cationic surfactants, referred to as U.S. Pat. No. 4,264,466 in columns 23-29, can be used to modify the smectite clay material to make it organophilic. The organic cationic nitrogen compounds described in U.S. Pat. No. 2,531,427 or mentioned in U.S. Pat. Nos. 2,966,506, 4,105,578, etc., can also be used advantageously.

The preferred modifiers are the quaternary ammonium compounds of formula ƒr₁r₂r₃r₄n J⁺ X wherein R, R₂, R ^ and R ^ each independently represent hydrogen or a hydrophobic organic alkyl, aryl, aralkyl, alkaryl or alkenyl group of 1-30 carbon atoms, preferably of 1-22 carbon atoms, with at least two R groups preferably Contain 1-6 carbon atoms and contain at least one group R, preferably at most two groups R 8 - 22 carbon atoms, and X represents an anion which may be inorganic, such as halide, e.g. chloride or bromide, sulfate, phosphate, hydroxide or nitrate, or organic, such as methyl sulfate, ethyl sulfate, or fatty acid, e.g., acetate, propionate, laureate, myristate, palmitate, oleate, or stearate.

Examples of preferred organophilic modifiers are the mono- and dialkyl quaternary compounds, wherein the alkyl group has a long chain (e.g. Οθ - in particular Representative examples of the monoalkyl with long chain quaternary ammonium capillary -active compounds are stearyl trimethyl ammonium chloride, tallow trimethylammonium chloride, benzyl stearyldimethylammonium chloride, benzyl hydrogenated tallow dimethylammonium chloride, benzyl cetyldimethylammonium chloride, and the corresponding sulphates, sulphates, sulphates, acetates, sulphides, acetates, sulphides, sulphates mentioned before. Typical representative examples of the di-alkyl with long chain quaternary ammonium compounds are dimethyldistearylammonium chloride, dimethyldicetylammonium chloride, dimethylstearylcetylammonium chloride, dimethylditallow ammonium chloride, dimethyl myristyl cetylammonium chloride, and the corresponding bromides, iodides, sulfates, methosulfates, acetates and other anions previously mentioned. Other representative compounds are octadecyl ammonium chloride, hexadecyl ammonium acetate, etc.

In addition to the quaternary ammonium (QA) compounds, other quaternable nitrogen-containing organic cations can also be used to form organophilic clay particles. For example, mention can be made of imidazolinium compounds, such as e.g. 1- (2-hydroxyethyl) -2-dodecyl-1-benzyl-2-imidazolinium chloride, and compounds containing a heterocyclic nitrogen ring, such as long-chain hydrocarbon substituted pyrrolidones, pyridenes, morpholines, and the like, such as N, N-octadecylmorpholinium chloride.

The amount of organic cation substitution need only be that amount sufficient to impart the required organophilic property to the clay to provide the desired greater stabilizing property. This amount may, depending on the nature of the organic substituent, be 10 - 100%, preferably 100%, such as 30%, 40%, 50% or 60% of the available base exchange capacity of the clay material. Usually and preferably at least sufficient of the organic compound is used to cover or coat the surface of the clay particles.

Suitable organophilic clay materials which can be used according to the invention are commercially available, for example, products marketed under the Bentone brand of NL Industries, New York, such as Bentone 27, a hectorite clay (magnesium montmorillonite), modified with benzyldimethyl hydrogenated tallow ammonium chloride; and Bentone 38, a hectorite clay, modified with dimethyldioctadecylammonium chloride. Other sources of organophilic clay materials are eg Sud-Chemie, Munich, West Germany; Laviosa, Livorno, Italy; Laporte, France; and Perchem, United Kingdom.

The organophilic clay materials are used only in minor amounts, generally less than 1.0% by weight, preferably less than 0.7% by weight, based on the total composition. Normally, amounts of at least about 0.1% by weight, preferably 0.2% by weight, such as 0.25%, 0.3%, 0.35% or 0.4%, are sufficient for the preparation

<img file="NL8801547A_D0012.tif" />

of stable thixotropic non-aqueous liquid suspensions of finely divided detergent builder or other water-soluble or dispersible tissue treating agent.

The organophilic modified clay can be incorporated directly as a powder in the non-aqueous liquid dispersion of the suspended particulate ingredients or after first being dispersed in a portion of the liquid carrier of the suspension, eg the liquid nonionic surfactant, which latter method is preferred. Furthermore, the organophilic clay, either directly added to the suspension as a powder or pre-gelated in a portion of the liquid carrier, can be added to the suspension before or after the suspension is ground to the required average particle size of no more than 15 micrometers. , preferably no more than 10 microns, in particular from 1-10 microns and most preferably from 4 to 8 microns.

In a preferred embodiment, the organophilic clay is first pre-dispersed, either in a portion of the liquid nonionic surfactant, which forms the main liquid carrier, or in another nonionic surfactant or in a solvent or diluent, as previously described, or in a suitable mixture of one or more surfactants and / or one or more solvents and / or one or more diluents. The pre-dispersed clay suspension can be ground if necessary in a high shear milling device to form an organophilic clay pre-gel. Separately, the remaining solid particulate material is suspended in the liquid nonionic surfactant and, if desired, diluent / solvent and then ground. The clay pre-gel and the suspension of particulate material can be ground to the final desired average particle size before being mixed together, while the pre-gel and the suspension can also be mixed and then further ground. In the latter case, the suspended particulate material may further contribute to the friction of the organophilic clay particles.

Other suspension stabilizing agents, rheological additives and anti-gelling agents can also be added within the scope of the invention.

Other suspension stabilizers can also be used. For example, the aluminum salts of higher fatty acids, in particular aluminum stearate, as described in U.S. Patent No. 4,661,280, can be added to the composition, e.g. in an amount of 0-3% by weight, preferably 0-1% by weight. , such as 0.05 - 0.8% by weight.

Another potentially useful stabilizer is an acidic organic phosphorus compound with an acid -POH group. The acidic organic phosphorus compound may, for example, be a partial ester of phosphoric acid and an alcohol, such as an alkanol with a lipophilic character, containing, for example, more than 5 carbon atoms, e.g. 8-20 carbon atoms. A specific example is a partial ester of phosphoric acid and a C 1 -C 4 alkanol. Marchip Empiphos 5632 consists of approximately 35% monoester and 65% diester. If used, amounts of the phosphoric acid compound up to about 3%, preferably up to 1%, are sufficient.

A nonionic surfactant that has been modified by converting a free hydroxyl group into a molecular moiety with a free carboxyl group, such as a partial ester of a nonionic surfactant and a polycarboxylic acid, may be included in the composition to further improve the theological properties . For example, amounts of the non-ionic surfactant with terminal acid group up to one part per part of the non-ionic surfactant are sufficient.

Preferred detergent compositions according to the invention are composed of the ingredients listed below in the preferred (broad), more preferred (in-between) and most preferred (narrow) amounts:

wt. % wide between tightly non-ionic surfactant alkali metal hydroxypolycarboxylic acid builder salt 1)

20-50

20-42 anti-crusting agent, eg copolymer of methacrylic acid and maleic anhydride, alkali metal salt

0-5

28-50

22-40

1-3

30-46

25-37

1.5-2.5

<td></td><td>other building salt (s) 2) alkylene glycol alkyl ether, viscosity reducing solvent / anti-gel form</td><td>0-30</td><td>0-20</td><td>0-10</td>

<td></td><td>agent</td><td>0-20</td><td>6-15</td><td>8-12.5</td>

<td>5</td><td>alkanol phosphoric acid ester nonionic surfactant</td><td>0-1</td><td>0-0.5</td><td>0-0.2</td>

<td></td><td>with terminal acid group</td><td>0-10</td><td>0-8</td><td>0-4</td>

<td></td><td>bleach</td><td>0-20</td><td>8-15</td><td>9-13.5</td>

<td></td><td>bleach activator</td><td>0-8</td><td>3-6</td><td>3.5-5.5</td>

<td>10</td><td>alkali metal silicate corrosion inhibitors</td><td>0-20</td><td>0-15</td><td>0-10</td>

<td></td><td>sequestering agent</td><td>0-4</td><td>0.2-1.0</td><td>0.4-0.6</td>

<td></td><td>anti-remover agent</td><td>0-5</td><td>0.6-1.5</td><td>0.8-1.25</td>

<td></td><td>optical clearer</td><td>0-0.8</td><td>0.2-0.6</td><td>0.25-0.4</td>

<td></td><td>enzymes</td><td>0-2</td><td>0.1-1.3</td><td>0.4-0.7</td>

<td>15</td><td>perfume</td><td>0-1</td><td>0.2-1.0</td><td>0.4-0.6</td>

<td></td><td>colorant and / or pigment</td><td>0-1</td><td>0.2-0.6</td><td>0.3-0.5</td>

<td></td><td>anti-foaming agents and suds suppressors</td><td>0-15</td><td>0-5</td><td>0-3</td>

<td></td><td>organophilic clay 3)</td><td>0.05-1.0</td><td>0.1-0.7</td><td>0.2-0.5</td>

1) Trajectories are specified for the third aspect; for the other aspec20 an optional ingredient.

2) Trajectories specified for the third aspect; for other routes, the wide route, the intermediate route and the narrow route are subject to quantities of resp. 10 - 50% by weight, 20 - 45% by weight and 22 - 40% by weight.

3) Trajectories are specified for the first aspect; an optional ingredient for other aspects.

In a preferred embodiment of the invention, which is applicable to all aspects of the invention, the mixture of liquid non-ionic surfactant and solid ingredients is milled, e.g. in a sand mill or ball mill. Particularly suitable are friction type mills, e.g. as marketed by Wiener in Amsterdam or Netzsch in Germany, in which the particle size of the solid ingredients is reduced to less than about 15 microns, e.g. up to an average particle size of 2-10 microm35 ter or even smaller (eg 1 micron). Preferably has less than

10%, in particular less than about 5% of all suspended particles, a particle size of more than 15 micrometres, preferably 10 micrometres. Since the hygroscopicity of the ground particles, especially when present, generally increases as the particle size decreases, it is also preferable that the average particle size is at least 3 micrometers, in particular about 4 micrometers. Compositions whose dispersed particles have such a small size have improved stability against separation or settling on storage. Other types of mills can also be used, such as a tooth mill, cone mill and the like.

When grinding, it is preferable that the amount of solid ingredients is large enough (e.g., at least about 40%, such as about 50%) for the solid particles to come into contact with each other and not be shielded from each other by the non-ionic surfactant liquid. Mills in which grinding balls (ball mills) or similar mobile grinding elements are used have produced very good results. A laboratory-operated working mill with 8 mm steatite balls can be used. For work on a larger scale, a continuously operating mill can be used in which grinding balls with a diameter of 1 mm or 1.5 mm operate in a very small gap between a stator and a rotor rotating at a relatively high speed (e.g. a CoBall mill)? when using such a mill, it is desirable to first pass the mixture of non-ionic surfactant and solid through a mill in which no fine grinding is achieved (e.g. a colloid mill) while reducing the particle size to less than 100 micrometers (e.g. to about 40 microns), before the material is milled in the continuous ball mill to an average particle diameter of less than 15 microns.

The powdered solid material can also be ground to the desired size, e.g. in a jet mill, before being mixed with the liquid matrix.

The compositions according to the invention are, according to the first aspect of the invention, ie with the organophilic clay, gel-like liquid suspensions, which generally exhibit non-Newtonian flow properties, in particular thixotropy, i.e., reduced viscous. 8 8 0 1 5 4 7 sity under applied stress or shear, and behave rheologically almost according to the Casson equation. The compositions are characterized by a yield stress between 2.5 and 45 pascal, usually between 10 and 55 pascal, such as 15, 20 or 25 pascal. If the product is shaken or exposed to tension, eg if it is pressed through a narrow opening in a squeeze bottle, the product will flow smoothly.

The compositions according to the invention can, in particular in the embodiments of the second and third aspect, and are preferably formulated as easily pourable liquid suspensions with viscosities of 50 - 8000 mPa.sec (50 - 8000 centipoise), usually 80 - 6000 mPa.sec, such as 160, 200 or 240 mPa.sec on the low side or 2000, 2500, 3000, 4000 or 5000 mPa.sec on the high side, such that the product flows smoothly, even at temperatures of 5 ° C or less. In order to achieve the preferred viscosity range and easy castability, the solids content of the slurry, including build-up material, bleaching agent and the like, is generally maintained depending on factors such as particle size, ingredients of the liquid phase, types of the suspended particles and the like. at a total amount of less than about 55%, in particular less than

50%, calculated on the weight of the composition. In that case, thickeners and stabilizers, such as the organophilic clay material used in the embodiments of the first aspect, aluminum stearate and the like should be avoided or used at very low levels, e.g. 0.01 - 0.2% of the organophilic clay and 0.01 - 0.1% aluminum stearate or other mono- or polyvalent metal salt of one^C.^ 2^-C22 ^alove^at:i-^sch fatty acid.

The non-aqueous liquid detergent compositions according to the invention can be packaged in ordinary containers, such as glass or plastic, rigid or flexible bottles, bowls or other containers, in addition to the unitary packages described above. Since the compositions generally flow at temperatures of 5 ° C or less, they are easily pourable and can be dosed directly from the vessel into the aqueous washing bath, such as in an automatic washing machine, in the usual amounts, such as 60 - 350 ml , eg 120 ml, per laundry load (of, for example, about 1.5-7 kg) for each laundry load, usually in

- 70 liters of water. The preferred compositions will also remain stable (no more than 1 or 2 mm liquid phase separation) if left alone for periods of 3 months or longer.

It is also possible, in particular when thickeners have been added to the composition, to adjust the thickened (e.g. transfer thixotropic or gel-like composition (some shaking or shear may be necessary or conducive) into a perforated dosing device (referred to as doserette) such as a plastic (water-insoluble) ball with an inner volume, which is preferably just enough to hold 350 ml or another amount recommended with the maximum recommended particles for a large laundry load. For this purpose the ball is provided with a closable, large filling opening, through which the composition can be cast and which can then be closed, for example a screw cap, friction cap or the like. The perforations are sufficiently small in diameter, eg 0.4 - 3 mm, preferably 0.4 - 1.6 mm, to prevent the thickened composition from flowing freely out of the perforations of the doserette. On the other hand, the perforations are large enough to allow the water from the aqueous wash bath to flow freely into the doserette and there to dilute the thickened suspension sufficiently to allow the composition to over the first few minutes of the wash cycle, e.g. 1-3 minutes from the doserette in the aqueous wash bath is rinsed. In this way, the consumer can fill the doserette to the appropriate level for the quantity and type of laundry to be washed and place the filled doserette (after closing the filling opening) directly in the washing machine with the laundry load. The doserette is preferably made from sufficiently strong plastic, such as polystyrene, polyethylene, polypropylene, polyvinyl chloride, etc., to withstand repeated use.

In the preferred embodiment of the invention, wherein the non-aqueous liquid detergent composition is provided in the form of a unitary package, as described above, it is of less critical importance to assemble the composition with ingredients that inhibit phase separation where there are fewer problems using the correct amount of ingredients, where the entire package is normally added to the washing bath. Similarly when used

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for single-use packaging, the castability itself is not an essential criterion and the compositions may be more viscous, e.g. up to about 50,000 centipoise or more, or gel-like or thixotropic.

Here, too, easily castable compositions are preferred, in particular with viscosities of 1000 to 8000 centipoise, preferably 2000 to 6000 centipoise. Filling the packages is often facilitated within the preferred viscosity range. Furthermore, with these still fluid and pourable compositions, the dissolution rate of the composition in the wash bath is often greater than with a similar but more viscous or thickened product, which may have a greater tendency to settle on the bottom of the wash bath or as a coherent continue to exist. This means that the less viscous, pourable compositions, which dissolve faster in the wash bath, can begin to perform their cleaning action more quickly throughout the wash bath without unnecessary and often undesirable high local concentrations of detergent or other functionally active ingredients arise. In this respect, the detergent products according to the invention are considered advantageous in comparison with previously proposed unitary packages filled with highly viscous, gel-shaped or pasty products.

Where in this description and in the claims there is non-aqueous, this means the absence of water, provided that small amounts of water, e.g. up to about 5%, preferably up to about 2%, may be present in the compositions so that non-aqueous compositions may contain such small amounts of water that may be added directly or as a carrier or solvent for any of the other ingredients in the composition may have ended up or is crystal water (eg sodium citrate dihydrate).

The invention is further illustrated by the following examples in which all amounts and percentages are by weight unless otherwise stated, and in which atmospheric pressure is applied unless otherwise indicated.

EXAMPLE 1

A non-aqueous liquid detergent composition according to the invention is prepared by mixing and grinding to a particle size of about 4 microns of the following ingredients in the FF II. 4 7 the components B:

% by weight (calculated on A + B) of following quantities (ground base A), followed by addition to the resulting dispersion with stirring of Ground base A nonionic surfactant i) 32 diethylene glycol monobutyl ether 10.5 sodium tripolyphosphate (hydrate) 30

Sokolan HC 9786 2) 2 carboxymethyl cellulose 1 sodium perborate monohydrate 11 tetraacetylethylenediamine 4.5

DEQUEST 2066 3)

Tinopal ATS-X (optical brightener) 0.3

TiO 2 (rutile) 0.4

Bentone 27 4) 0.45

Post-addition B enzyme suspensions 5) 0.55 non-ionic surfactant 1) 3

1) Involved from BASF, a mixed propylene oxide (4 mol) - ethylene oxide (7 mol) condensate of a fatty alcohol with 13 - 15 carbon atoms

2) Copolymer of methacrylic acid and maleic anhydride

3) Diethylenetriamine pentamethylene phosphoric acid.

4) Hectorite clay, modified with dimethylbenzyl hydrogenated tallow ammonium chloride, 35% cation-exchanged, purchased from NL Industries

5) Mixture of Alcalase 2.5 L (0.25%), Savinase 8SL (0.2%), Termamyl 300 SL (0.1%) enzyme suspensions (in non-ionic surfactant) (NOVO products).

After 1 day the composition had a yield stress of 20 Pa and a plastic viscosity of 150 mPa.sec. This composition and a comparison composition without the organophilic clay stabilizer are each filled in three 1 liter glass vessels and left at 4 ° C, room temperature (about 22 ° C) and 35 ° C for 3 months, after which the amount of free liquid at the top of each sample. is being measured. The results are given in the table below.

_t H 5 4 7

22 ° C 35 ° C (1) 1 (1) (5) 18 (8) the results stated.

PHYSICAL STABILITY AFTER 3 MONTHS

Liquid separation (mm) temperature ° C example (with Bentone) 1 (1) comparison (without Bentone)) (3)

In the table above there are brackets obtained when the test is repeated, but the bottles are vigorously shaken by hand once every 2 weeks for 15 seconds.

The results show that the addition of small amounts of organophilic clay significantly improves the physical stability of the non-aqueous suspensions. Although it is not intended to bind the invention to any theory, the organophilic clay appears to give sufficient body to the composition, thereby obtaining a structure analogous to an elastic network of particles that supports the physical stability and configuration of the maintain product, even when the product is subjected to sufficient shaking or shear to cause breakage of the flocculated network of the suspended building materials and / or other tissue treating particles.

Repeating the example, but with Bentone 38 (hectorite clay, modified with dimethyldioctadecylammonium chloride) instead of Bentone 27, analogous results are obtained. Similar results are obtained when replacing the nonionic surfactant with other mixed ethylene oxide / propylene oxide alcohol condensates, such as C₃C fatty alcohol, condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, or C 3-10 fatty alcohol, condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, or Dobanol 2.5-7 or Neodol 23-6.5.

EXAMPLE II

A non-aqueous liquid detergent composition of the invention is prepared by mixing and grinding to about 4 microns of the following ingredients in the following amounts:

10 wt. % non-ionic surfactant 1) 13.5 non-ionic surfactant 2) 10.0 non-ionic surfactant 3) 10.0 non-ionic surfactant with terminal acid group 4) 5.0 trisodium citrate 29.6 copolymer of methacrylic acid and maleic anhydride, sodium salt 4.0 diethylene glycol monobutyl ether 10.0 alkanol phosphoric acid ester 0.3 sodium perborate monohydrate 9.0 tetraacetylethylenediamine 4.5 diethylenetriamine pentamethylene phosphoric acid sodium salt 1.0 carboxymethylcellulose, Na salt / methyl cellulose (1: 2 mixture) 1.0 optical clearer 0.5

Esperase SL8 (protease enzyme) 1.0 perfume 0.5925 dye 0.0075

100,000

1) Mixture of equal parts of a condensation product of C-fatty alcohol with 7 moles of propylene oxide and 4 moles of ethylene oxide, and a condensation product of C-C fatty alcohol with 5 moles of propylene oxide and 10 moles of ethylene oxide.

2) Secondary C 1-4 fatty alcohol, ethoxylated with 7 moles of ethylene oxide (narrow distribution).

3) Secondary C 1-4 fatty alcohol, ethoxylated with 9 moles of ethylene oxide (narrow distribution).

4) Half ester of C 8 -C 18 fatty alcohol, ethoxylated with 5 moles of ethylene oxide, and succinic anhydride.

EXAMPLE III

The following non-aqueous liquid laundry detergent composition is prepared:

wt% fatty alcohol condensed with 7 moles of ethylene oxide and 4 moles of propylene oxide 37.9 tripropylene glycol methyl ether 10.3 sodium citrate dihydrate 30.5 sodium perborate monohydrate 11.3 tetraacetylethylenediamine 4.6 sodium carboxymethylcellulose 1.0 ethylenediaminetetraacetic acid, sodium salt 0.51 enzymes

Alcalase 2.5 SL 0.26

Savinase 8.0 SL 0.20

Termamyl 300 SL 0.10

TiC&gt; 2 (rutile) 0.41 optical brightener (Tinopal ATS-X) 0.31 copolymer of methacrylic acid and maleic anhydride, sodium salt 2.1 perfume 0.51

100.00

The composition had a viscosity at 25 ° C of about 5000 cps. EXAMPLE IV

This example relates to a unitary package according to the invention. Two polyvinyl alcohol films with a width of approximately 8.5 cm and a length of 9.5 cm are heat-welded together along both longitudinal edges and along a line at a distance of approximately 0.5 cm from the bottom edge. The polyvinyl alcohol films used were of the NEDOL 210EF brand (about 85% hydrolyzed polyvinyl alcohol) from Nedi Co., France. The PVA bag is then filled through the opening in the upper part with about 100 g of the composition described in Example III. Thereafter, the upper part is also heat-sealed along a line at a distance of about 0.5 cm from the top edge. The welding is carried out under a welding pressure of approximately 2.0 kg / cm² for about 1 second with welding rods, heated to a temperature of 35 - 70 ° C, depending on the relative humidity. For example, at a relative humidity of 40%, a welding temperature of about 55 - 60 ° C is satisfactory, while at 70% the relative humidity is a temperature of 43 - 49 ° C; at a relative humidity of 80%, a temperature of 38 - 43 ° C is recommended.

The outer bag is formed from a non-woven polyester, which contains approximately 40% binder fibers, has a density of 24 g / m² and is available from Kendall Co., Boston, Massachusetts. Two sheets of the non-woven material, each having a width of about 9.5 cm and a length of about 10.2 cm, are placed on both sides of the inner bag of polyvinyl alcohol such that the side edges of the polyester material are positioned on are equal distances from the side edges of the inner pocket, while the top and bottom edges of the inner and outer pockets correspond to each other. The polyester sheets are then heat-sealed along its four outer edges to form the outer bag. In addition, the outer bag is heat-sealed to the inner bag along lines at distances of about 0.25 cm from the top and bottom edges of the bag.

When the package is placed in a conventional automatic washing machine, all liquid detergent will be dosed into the wash water during the first few minutes of the wash cycle. Lumps of unresolved polyvinyl alcohol remaining from the inner bag remain substantially within the package at the end of the wash cycle - including the rinse and spin cycles.

Example V

Example IV is repeated, but the composition of example I or example II is filled in the PVA bag. Analogue results are obtained.

Example VI

Example IV is repeated, but the outer bag is not formed from non-woven polyester material, but from spun-bonded polypropylene with a density of approximately 20 g / m². The results are analogous to those of Example IV.

V

EXAMPLE VII

To demonstrate the effect on crust of replacing sodium tripolyphosphate with an equivalent amount of trisodium citrate detergent builder salt, the detergent composition of Example II with 29.6 wt% trisodium citrate for a single wash cycle in a washing machine was compared to the same composition in which the trisodium citrate was replaced by 29.6% by weight of sodium tripolyphosphate. Separate wash cycles were performed with the trisodium citrate and detergent compositions containing sodium tripolyphosphate at wash water concentrations of each of the detergent compositions of 1, 2, 3.5, 5, 7 and 9 g / liter.

After each detergent composition was used in a washing machine, the resulting amount of crust formation, ie, the percentage of ash deposited, was measured. The percentage of ash deposited is measured by calcining washed textile samples.

The observed results are shown in the graph of Figure 1 and show that at detergent composition concentrations of 1 - 5 g / l wash water, the trisodium citrate is considerably better than sodium tripolyphosphate for preventing crusting or ash deposition. At detergent composition concentrations of 5-9 g / l wash water, the behaviors of trisodium citrate and sodium tripolyphosphate detergent builder salts are approximately the same with regard to their anti-crust properties. EXAMPLE VIII

The effect of cumulative scaling in repeated washing cycles in a washing machine was tested with the same compositions as used in Example VII.

The repeated wash cycles were performed at concentrations of 5 g / l wash water from each of the detergent compositions for 12 wash cycles. The cumulative crust formation, ie cumulative percentage of ash deposit was measured in each washing machine after 3, 6, 9 and 12 washes.

The results of cumulative crusting are shown in the graph of Figure 2. Regarding cumulative crusting, no cumulation was observed with the sodium tripolyphosphate detergent builder salt.