Non aqueous liquid detergent product consisting of two separate base compositions

Description

[0001] The present invention relates to heavy duty and light duty liquid detergents.

[0002] Liquid detergents have been gaining an ever increasing importance as they are more convenient to use than powder detergents. They are divided in two main groups, namely water based liquid detergents and non-aqueous liquid detergents, whose base is formed by an organic liquid medium.

[0003] Most aqueous liquid detergents consists of solutions or microsuspensions of anionic, cationic and non-ionic surfactants, enzymes, perfumes, stabilizers and various adjuvants.

[0004] They have a limited washing action, as they contain limited amounts of substances (so called "builders") apt to sequester the alkaline-earth metal ions, which cause the hardness of the washing waters, as well as the ions of the heavy metals.

[0005] Furthermore, they do not contain stain removing agents of the peroxide type (hydrogen peroxide, inorganic peroxides such as sodium perborate, organic peroxides, organic peracids etc.), as not only such oxidizing agents are not stable in aqueous suspension or solution, but they also interfere with the added enzymes, disactivating them.

[0006] Said aqueous based detergents for machine and hand washing are, therefore mainly founded on the surface-active action and on the stain removing action on stains of proteic type, whereas they do not act on oxidable stains, which constitute the main portion of the soils which are most frequently found.

[0007] The oxidizing action is only possible with non-aqueous detergents, consisting of an organic liquid medium based on polar solvents and surfactants containing in suspension an oxidizing agent of the organic or inorganic peroxide type, in conditions and in presence of other co-formulating agents such that interaction and therefore the decomposition of the oxidizing agent be impossible.

[0008] The DE-C 1 279 878 (Unilever) relates to a non-aqueous based liquid detergent, comprising a mixture of non-ionic and anionic surfactants, ethyl alcohol, builders such as sodium tripolyphosphate, suspending agents such as calcined silica or calcined aluminum oxide, optical brighteners and sodium perborate.

[0009] US-A 3 850 831 (Hellsten et al.) refers to essentially anhydrous liquid detergent compositions, consisting of ionic, anionic and polyhydric solvents, stain removing agents of the persait type, builders such as sodium tripolyphosphate and chelating agents such as polyamino-carboxylic acids.

[0010] US-A 4 316 812 (Hancock et al.) refers to the use of non-ionic surfactants with no solvent (pour point about 1 COC), mixed with builders such as sodium tripolyphosphate, stain removing agents such as sodium percarbonate and perborate as well as with an alkalizing agent such as metasilicate and other typical detergent components, such as CMC (carboxymethyiceiiuiose), sodium borate, carbonate and bicarbonate, kaolin, bentonites etc. to obtain an essentially water free fine grain paste detergent.

[0011] EP-B 0 028 849 (Unilever) refers to a non-aqueous based liquid detergent containing a maleic anhydride copolymer with ethylene or, methylvinyl ether, an essentially polyhydric solvent acting as a suspending agent together with non-ionic surfactants, as well as solid agents such as alkalizing agents, builders, oxidizing agents, bleach activators, enzymes and softeners.

[0012] EP-B 0 120 659 (imperial Chemical Industries) relates to essentially anhydrous liquid detergent compositions, consisting essentially of a non-ionic surfactant, polar solvents with viscosity lowering functions and dispersing agents, builders, alkalizers, persalts, optical brighteners, carboxymethylcellulose, enzymes, such compositions being substantially anhydrous.

[0013] DE-A 3 511 516 (Colgate-Palmolive) refers to a substantially anhydrous laundry detergent, comprising non-ionic surfactants, acid surfactants, sodium tripolyphosphate, sodium perborate, TAED and a copolymer such as SOKALAN CP5(^R).

[0014] DE-A 3 511 515 (Colgate Palmolive) refers to a substantially anhydrous laundry detergent, comprising non-ionic surfactants, acid surfactants, sodium tripolyphosphate, sodium phosphonate, sodium perborate, SOKALAN CP5(^R)-copolymer, sodium carbonate, TAED, optical brightener and protease.

[0015] The above mentioned DE-C 1 279 878, US-A 3 850 831 and US-A 4 316 812 all refer to non-aqueous liquid detergent compositions, having a stain removing action based on non-activated persalts. Said compositions have a limited action on oxidizable stains at low temperatures due to the absence of bleach activators. Furthermore, they have a limited stain removal properties on proteic stains, due to the absence of enzymes, particularly of the proteolytic type. Said absence of enzymes is due to the difficulty in introducing enzymes into this type of compositions, as they would be rapidly disactivated by the action of the oxidizing agent, enhanced by the traces of humidity inevitably to be found in the raw materials during the preparation and the packaging, and anyway easily picked up during the use with the consumer.

[0016] EP-B 0 028 849, EP-B 0 120 659, DE-A 3 511 515 and DE-A 3 511 516 are based on the combined use of oxidizing agents, bleach activators and enzymes to achieve the desired detergency effect.

[0017] It is however known that bleach activator and persalt, if simultaneously present in solvents and polar surfactants based formulations, give rise to early reactions, with formation of peracid and water and possibly developing oxygen. Said reaction is assisted both by the partial solubility of the two components, but mainly by the presence of traces of water.

[0018] It is also well known that the simultaneous presence of enzymes in a system containing oxidizing agents in non-protected form causes the enzyme rapid disactivation.

[0019] Consequently, the detergent compositions described in EP-B 0 028 849, EP-B 0 120 659, DE-A 3 511 515 and DE-A 3 511 516 do not provide a satisfactory solution to the problem of formulation of a complete liquid detergent.

[0020] GB-A 2 000 177 concerns a powder detergent composition made of two parts, separately packaged in a two-compartments non-woven sachet, one part containing acidic components rapidly soluble at cold temperature, the other one surfactants and coated alkali metal carbonates which dissolve only at temperatures higher than 40_°C.

[0021] EP-A 158 508 claims a special bleaching system consisting of a combination of a bleach and a bleach activator (chlorides/bromides mixtures), packaged separately, in a two-compartments multiple container, for controlled dosing off the activator such as to get a controlled, adjustable activation of the bleach at the time of laundering.

[0022] it is therefore the object of the present invention to provide a non-aqueous liquid detergent, able to remove oxidable stains as well as proteic stains and free from the disadvantages of the known detergents of this kind.

[0023] According to a characteristic of the present invention, said object is achieved by providing the said detergent in form of two physically separated base compositions, one containing the oxidizing bleaching agent and the other the bleach activator and the enzyme, in combination with surfactants, builders, optical brighteners, anti-redeposition agents, alkalizing substances, dyes, perfumes, stabilizing agents etc., all said components being dissolved and/or dispersed and/or emulsified in a suitable non-aqueous liquid vehicle, as outlined in claim 1.

[0024] Said liquid vehicle preferably is formed by mixtures of liquid non-ionic surfactants and solvents of the polar type, the latter having the function of lowering the viscosity and the freezing point as well as that of enhancing the dispersibility in water during washing.

[0025] Surfactants of the anionic or cationic type can be also included, if a textiles softening effect is desired.

[0026] The builder may be an anhydrous salt of the kind of the polyphosphates, NTA (nitrilo-triacetic acid), sodium citrate, zeolites, bentonites, montmorillonites, and so on.

[0027] The oxidizing bleaching agents may be chosen chosen among the inorganic persalts, of the kind of the monohydrate sodium perborate, tetrahydrate sodium perborate, sodium percarbonate, sodium, potassium and ammonium persulphate, sodium and potassium monopersulphate, perphosphate and organic per- compounds such as percarbamide, peracids and peroxides and so on.

[0028] The bleach activator, can consist of TAED (tetra-acetyl-ethylene diamine), PAG (penta-acetyl glucose), ESA (sorbitol hexa-acetate), TAGU (tetra-acetyl glycol urile), NAOFS (octyl phenol sulfonate sodium salt) and other known bleach activators.

[0029] The enzymes are mainly of the proteolytic type, also in combination with lipase, amylase and cellulase.

[0030] The optical brighteners employed may be of the diamino stilbene, distyryl-diphenyl and pyrazole type, and anyway of the type normally used in detergents.

[0031] The preferred anti-redeposition substances are of the cellulose derivative type, such as carboxymethyl cellulose and etherified non-ionic celluloses. Furthermore, acrylic acid homopolymers and acrylic acid copolymers with maleic anhydride and the maleic anhydride polar copolymers with methyl-vinyl ether, methyl propenyl ether and so on, are also employed.

[0032] Persalt stabilizing agents may be of type of the phosphonate and amino polycarboxylic complexants, such as EDTA (ethylene diamino tetraacetic acid), DTPA (diethylene triamino pentaacetic acid) etc.

[0033] The enzymes used in the present invention, protease, lipase, amylase, cellulase, can be introduced in the detergent in solid form, as slurry, or in the form of solution, in the organic liquor.

[0034] With respect to the presence of water and other agents having a destabilizing action on the enzymes, stabilizers, such as calcium and magnesium organic and inorganic salts, polar solvents such as ethyl alcohol and polyglycols, boron organic and inorganic compounds such as boric acid and borates, nitrogen compounds such as EDTA, NTA (nitrilo triacetic acid), glycine, monoethanolamine, diethanolamine, triethanolamine, acetamide or glutamic acid can be suitably added.

[0035] According to a preferred form to introduce the enzyme in the detergent composition, the proteolytic enzyme is introduced in form of a slurry in non-ionic surfactant or polar solvent, in fine particles, in post-admixture, to the residual composition, after milling, to avoid undesired degradation. The simultaneous presence of oxidizing agents such as inorganic persalts and organic peracids or peroxides can give rise to interaction between activator and enzyme respectively, with a rapid decay of these compounds.

[0036] Also the simultaneous presence of persalt and bleach activators, in non-protected form, give rise to exothermic decomposition reaction.

[0037] The two base compositions can be prepared according to any suitable procedure.

[0038] The dosing of the liquid detergent in the washing machine may be effected by using the dosing cup provided in the machine or directly into the washing machine.

[0039] The composition of liquids and solids of the two separate base compositions shall be such as to provide similar final density, viscosity and pour point, so as to ensure the same physical stability at low temperatures and constant supply ratio.

[0040] The various solid components of the detergent can be partly soluble or insoluble in the liquid system. In order to ensure a perfect physical stability in time, the undissolved solids must have a very fine grain size, lower than 10 wm.

[0041] Each base composition consists of liquid components, e.g. solvents and non-ionic surfactants, solid components which can be dissolved in the system and suspended solid components, and, if present emulsified liquid components.

[0042] The ratio between solids and liquids ranges between 1:3 and 9:1, preferably between 1:1.5 and 3:1.

[0043] The liquid vehicle is composed preferably of non-ionic surfactants and polar solvents. The ratio between solvents and surfactants ranges between 1:9 and 3:1.

[0044] C₁ to C₄ lower alcohols, ethylene, propylene glycols, oligomers and copolymers thereof, even partly esterified with Ct-C₄ alcohol, glycerine and aprotic polar solvents such as dimethyl sulphoxide are particularly suitable solvents.

[0045] The most suitable non-ionic surfactants are the primary and secondary, natural or synthetic alcohol derivatives, with a number of carbon atoms ranging between Cs and C₂₂, and preferably between C₈ and C₁₈, condensed with ethylene oxide, having 3 to 25 monomer units and preferably 5 to 15, or condensed with propylene oxide, with a monomer unit content between 2 and 10, and preferably between 3 and 6, or condensed together with oxyethylene and oxypropylene units. Non ionic surfactants of the mentioned type can contain the final hydroxyl esterified with C₁-C₃ organic acids.

[0046] Other non-ionic surfactants suitable for the formulation of the liquid detergents according to invention are those derived from condensation of alkyl phenols with alkylene oxides and where the type and content of monomer units is similar to those of the alcohol-based non-ionic ones mentioned above.

[0047] The physical and chemical stability of the two base compositions shall be suitably ensured by a limited presence of water.

[0048] Therefore, as regards the base composition in which, inter alia, the oxidizing bleaching agents of the composition are contained, the free water content must be lower than 2% and preferably be lower than 1%; as regards the base composition containing enzymes and bleach activators, the free water content must be lower than 5%, preferably lower than 3%.

[0049] For the preparation of the two base compositions of the detergent, the liquid and solid components containing crystallization water need to be dehydrated, in order to fulfill the above mentioned conditions.

[0050] The two base compositions forming the detergent are in form of suspensions of solids in liquids, having a viscosity ranging between 100 and 2000 mPa.s, and preferably between 500 and 1000 mPa.s; in order to fulfill this requirement and in order to obtain the same viscosity foor the two base compositions, to ensure a uniform delivery, the solid particles must be adequately fine, i.e. their particle size must be lower than 10 µm.

[0051] This result is obtained by milling the suspension in a suitable machine, such as a ball or microsphere mill, with a duration and a number of stages apt to ensure that the desired result is achieved.

[0052] A modification of the above procedure can consist in the previous milling in solid phase of the single solid components, to be then added to the liquid, so as to obtain a fine suspension (grain size lower than 10 wm) stable to decantation.

[0053] The physical stability, that is to say, non-decantation of the suspensions corresponding to the two detergent base compositions, must be ensured for periods of time between production and consumption, that is to say, at least for a period of time ranging between 6 and 12 months.

[0054] It is therefore useful to add suspending agents, such a calcined silica, calcined alumina, hydrosoluble polymers such as polyvinyl pyrrolidone, to the suspension, before or after milling. The added amounts range between 0.1 and 2.0%, and preferably between 0.3 and 1.0%.

[0055] Calcined silica is silicium dioxide obtained through pyrohydrolisis of chlorosilanes and it is marketed as a low density powder unsoluble in water, with very small particles and surface area comprised between 50 and 400 m²/g. Commercially available types of silica are the HDK(^R) by Walker and AEROSIL(^R) by Degussa.

[0056] Polyvinyl pyrrolidone is used in the 30,000 molecular weight range.

[0057] The invention will be further described by the following examples, given only by way of illustration and not of limitation of same. In the examples, the base containing the oxidizing agents will be referred to as "Base (A)", and that containing enzymes and the bleach activators will be referred to as "Base (B)".

EXAMPLE 1

[0058] Base A and base B are separately prepared as described below, by mixing in a mixer provided with a stirrer the liquid and solid components.

[0059] In order to obtain sufficient physical stability, the solid components of the two bases are subsequently milled in a microsphere mill, until a 6.6 µm average value of the solid particles is obtained.

[0060] The composition of the two bases is the following, in % by weight:

[0061] The two bases have the following chemical-physical characteristics:

EXAMPLE 2

[0062] Following the same operation procedures as in Example 1, the base A and base B are prepared, with the following compositions:

[0063] The two bases in Example 2 have the following chemical-physical characteristics:

EXAMPLE 3

[0064] After milling, two parts of base A and base B of Example 1 are thoroughly mixed, in a 1:1 ratio, to obtain a compounded liquid detergent having the following composition:

Compounded liquid detergent as per Example 1

[0065] 

EXAMPLE 4

[0066] After milling, two parts of base A and base B preparations as per Example 2, have been thoroughly mixed in a 1:1 ratio, to obtain a liquid detergent, having the following composition, in weight %

[0067] 

EXAMPLE 4

[0068] After milling, two parts of base A and base B preparations as per Example 2, have been thoroughly mixed in a 1:1 ratio, to obtain a liquid detergent, having the following composition, in weight %

EXAMPLE 5

[0069] Formulations A and B as per Examples 1 and 2 and the new formulations deriving from their mixture as per Examples 3 and 4, were tested in time and at different temperatures, as regards sodium perborate, bleach activator and proteolytic enzyme stability. The products were kept in sealed glass containers. The test results are shown in the following Tables I and II

[0070] It should be noted that, on opening the containers where formulations as per Examples 3 and 4 were stored to carry out the analyses, an inner pressure caused by gas formation due to a remarkable decomposition of the oxidizing agent was observed.

EXAMPLE 6

[0071] With the liquid detergents as per Examples 1, 2, 3 and 4, stored for 2 months at 23_°C, washing tests were carried out in a washing machine. Meanwhile, a washing test using a commercial water-based detergent containing enzymes was carried out under the same operating conditions. The results of the washing tests are shown in the following table:

[0072] Detergents A + B as per Examples 1 and 2 where dosed by mixing equal weight of the two bases just before testing.

Claims

1. A liquid, non-aqueous detergent product, characterized in that it consists of two, separate, liquid base compositions to be mixed at the moment of use of immediately before, each base composition consisting of a non-aqueous liquid vehicle containing in solution and/or dispersion and/or emulsion the other solid and liquid components of the detergent composition, wherein the first base composition (A) contains the oxidizing bleaching agents and the second base composition (B) contains enzymes and bleach activators, both base compositions containing also a number of further components, selected among builders, anionic and/or cationic surfactants, stabilizers, anti-redeposition agents, pigments, dyes, optical brighteners, perfumes, anti-foam agents; and further having:

a - A liquid to solid components ratio ranging, for both base compositions, from 1:3 to 9:1, preferably from 1:1.5 to 3:1;

b - A free water content lower than 2%, preferably lower than 1%, for base composition (A) and lower than 5%, preferably lower than 3% for base composition (B);

c - A viscosity in the range 100-2000 mPa-s, preferably 500-1000 mPa-s, for both base compositions;

d - A particle size of the suspended solid components smaller than 10 Ilm.

2. A non aqueous liquid detergent product according to claim 1, characterized in that said non-aqueous liquid vehicle consists of one or more non-ionic surfactants and one or more polar solvents.

3. A non aqueous liquid detergent product according to claim 1, wherein said oxidizing bleaching agents are contained in said base composition (A) in amounts ranging between 2 and 35% and preferably between 10 and 25%.

4. A non aqueous liquid detergent product according to claim 1, wherein the bleach activators are contained in said base composition (B) in amounts ranging between 1 and 15% and preferably between 5 and 10%.

5. A non aqueous liquid detergent product according to claim 1, wherein the enzymes contained in the base composition (B) are of the proteolytic and/or amylolitic and/or lipolytic and/or cellulase type, said enzymes being contained in said base composition (B) in amounts ranging between 0.2 and 5%, and preferably between 0.5 and 2%.

6. A non aqueous liquid detergent product according to claim 2, wherein the polar solvents to surfactants ratio in said liquid vehicle ranges between 0.5:9 and 3:1, and preferably between 1:9 and 1:1.

7. A non aqueous liquid detergent product according to any one of the preceding claims, wherein said builders are contained in said two base compositions (A, B) in amounts ranging between 5 and 50%, and preferably between 10 and 30%.

8. A non aqueous liquid detergent product according to any one of the preceding claims, wherein said optical brighteners are contained in said two base compositions (A, B) in amounts ranging between 0.01 and 0.5% and preferably between 0.05 and 0.2%.

9. A non aqueous liquid detergent product according to any one of the preceding claims, wherein said base composition (A) contains a persalt stabilizer, of the amino polycarboxylic acid and/or alkali phosphonate type.

10. A non aqueous liquid detergent product according to any one of the preceding claims, wherein said two base compositions (A, B) furthermore contain stabilizers of the calcined silica, calcined alumina or suspending polymer type.

11. A non aqueous liquid detergent product according to claim 2, wherein the liquid vehicle of the solution and/or dispersion and/or suspension of the components of the said two base compositions (A, B) comprises a non-ionic surfactant, formed by a primary or secondary alcohol, condensed with alkylene oxides.

12. A non aqueous liquid detergent product according to claim 2, wherein the liquid vehicle of the solution and/or dispersion and/or suspension of the components of the said two detergent bases (A, B) comprises a non-ionic surfactant, formed by alkylphenol condensed with alkylene oxides.

13. A non aqueous liquid detergent product according to claim 2, wherein the solvent of the liquid vehicle of the solution and/or dispersion and/or suspension of the components of the said two detergent bases (A, B) is propylene glycol, ethylene glycol or oligomers with 3 to 100 monomeric units, and preferably 5 to 20.

14. A non aqueous liquid detergent product according to claim 2, wherein said solvent is ethanol.

15. A non aqueous liquid detergent product according to claim 2, wherein said solvent is dimethyl sulphoxide.

16. A non aqueous liquid detergent product according to claim 11, wherein the non-ionic surfactant is formed by a Ce-C₂₂, preferably Ce-Ge, primary or secondary alcohol.

17. A non-aqueous liquid detergent product according to claims 11 and 12, wherein the primary and/or secondary alcohol and the alkyl phenols are condensed with 2-25 ethylene oxide units, and preferably 5 to 15 units.

18. A non aqueous liquid detergent product according to claims 11 and 12, wherein the primary and/or secondary alcohol and the alkyl phenols are condensed with 1-10 propylene oxide units, and preferably 3-6 units.

19. A non aqueous liquid detergent product according to claims 11 and 12, wherein the primary and/or secondary alcohol and the alkyl phenols are condensed with 3-25 units of ethylene oxide and propylene oxide simultaneously present, and preferably 5-15 units.

20. A non-aqueous liquid detergent product according to claims 11 and 12, wherein the primary and/or secondary alcohol and alkyl phenols condensed with ethylene oxide and/or propylene oxide are esterified on ther terminal hydroxyl with organic acids containing 1 to 3 carbon atoms.

21. A non aqueous liquid detergent product according to claim 3, wherein the oxidizing bleaching agent employed is monohydrate sodium perborate.

22. A non-aqueous liquid detergent product according to claim 4, wherein the bleach activator employed in said base composition (B) is tetra-acetyl ethylene diamine.

23. A non-aqueous liquid detergent product according to claim 4, wherein the bleach activator employed in said base composition (B) is penta-acetyl glucose.

24. A non-aqueous liquid detergent product according to claim 7, wherein the builder employed is Zeolite A.

25. A non-aqueous liquid detergent product according to claim 7, wherein the builder employed is a potassium or sodium polyphosphate or pyrophosphate.

26. A non-aqueous liquid detergent product according to claim 25, wherein said polyphosphate is sodium or potassium tripolyphosphate.

27. A non-aqueous liquid detergent product according to claim 7, wherein the builder employed is nitrilo-triacetic acid, sodium salt.

28. A non-aqueous liquid detergent product according to claim 7, wherein the builder employed is sodium citrate.

29. A non-aqueous liquid detergent product according to any one of the preceding claims, wherein the anti-redeposition agent is sodium prolyacrylate.

30. A non-aqueous liquid detergent product according to any one of the preceding claims, wherein the anti-redeposition agent is a maleic anhydride copolymer with methyl-vinyl ether.

31. A non-aqueous liquid detergent product according to any one of the preceding claims, wherein the anti-redeposition agent is a maleic anhydride copolymer with acrylic acid.

32. A non-aqueous liquid detergent product according to claim 5, wherein the enzymes contained in said base composition (B) are post-admixed in the composition after milling, in form of solution or of fine particle slurry in non-ionic surfactant or in non-reactive polar solvent.

33. A non-aqueous liquid detergent product according to claim 32, wherein said enzymes are proteolytic enzymes of the type of the maxatase(R), mexacal(^R), savinase(R), espernase(R), alkalase(R), cellulase SP 227(R), thermamyl L(R) type A.

34. A non-aqueous liquid detergent product according to any one of the preceding claims, wherein said two base compositions (A, B) contain anionic and/or cationic surfactants.

35. Use of a non-aqueous liquid detergent product according to claims 1 to 34 above, wherein the two base compositions (A, B) forming the detergent are mixed together in a-fixed ratio, ranging between 1:4 and 4:1, and preferably 1:1.5 and 1.5:1.

36. Use of a non-aqueous liquid detergent product according to claims 1 to 34 above, wherein the mixture of the two base compositions (A, B) takes place when the detergent is introduced in the washing machine or immediately before.

Ansprüche

1. Flüssiges, nicht wässriges Detergensprodukt, dadurch gekennzeichnet, daß es aus zwei getrennten flüssigen Grundzusammensetzungen besteht, die im Augenblick des Gebrauches oder unmittelbar zuvor zu mischen sind, wobei jede Grundzusammensetzung aus einem nicht wässrigen flüssigen Verdünnungsmittel besteht, das in Lösung und/oder Dispersion und/oder Emulsion die anderen festen und flüssigen Bestandteile der Detergentienzusammensetzung enthält, wobei die erste Grundzusammensetzung (A) die oxidierenden Bleichmittel und die zweite Grundzusammensetzung (B) Enzyme und Bleichaktivatoren enthält und beide Grundzusammensetzungen auch eine Anzahl weiterer Komponenten enthalten, die aus Aufbaustoffen, anionenaktiven und/oder kationaktiven Netzmitteln, Stabilisatoren, der Wiederanlagerung entgegenwirkenden Mitteln, Pigmenten, Farbstoffen, optischen Aufhellem, Parfums und der Schaumbildung entgegenwirkenden Mitteln ausgewählt sind und ferner aufweisen:

a - ein Verhältnis der flüssigen zu den festen Bestandteilen, das für beide Grundzusammensetzungen im Bereich von 1:3 bis 9:1, vorzugsweise von 1:1,5 bis 3:1 liegt;

b - einen Gehalt an freiem Wasser unter 2%, vorzugsweise unter 1 % für die Grundzusammensetzung (A) und unter 5%, vorzugsweise unter 3% für die Grundzusammensetzung (B);

c - eine Viskosität im Bereich von 100-2000 mPa-s, vorzugsweise 500-1000 mPa-s für beide Grundzusammensetzungen;

d - eine Teilchengröße der suspendierten festen Bestandteile kleiner als 10 11m.

2. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 1, dadurch gekennzeichnet, daß das nicht wässrige flüssige Verdünnungsmittel aus einem oder mehreren nichtionogenen oberflächenaktiven Mitteln und einem oder mehreren polaren Lösungsmitteln besteht.

3. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 1, dadurch gekennzeichnet, daß die oxidierenden Bleichmittel in der Grundzusammensetzung (A) in Anteilen zwischen 2 und 35% und vorzugsweise zwischen 10 und 25% enthalten sind.

4. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 1, bei dem die Bleichaktivatoren in der Grundzusammensetzung (B) in Anteilen zwischen 1 und 15% und vorzugsweise zwischen 5 und 10% enthalten sind.

5. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 1, bei dem die in der Grundzusammensetzung (B) enthaltenen Enzyme vom proteolytischen und/oder amylolytischen und/oder lipolytischen und/oder Zellulasetyp sind, welche Enzyme in der Grundzusammensetzung (B) in Anteilen zwischen 0,2 und 5% und vorzugsweise zwischen 0,2 und 2% enthalten sind.

6. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 2, bei dem das Verhältnis der polaren Lösungsmittel zu den oberflächenaktiven Mitteln im flüssigen Verdünnungsmittel im Bereich zwischen 0,5:9 und 3:1 und vorzugsweise zwischen 1:9 und 1:1 liegt.

7. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem die Aufbaustoffe in den beiden Grundzusammensetzungen (A, B) in Anteilen zwischen 5 und 50% und vorzugsweise zwischen 10 und 30% enthalten sind.

8. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem die optischen Aufheller in den beiden Grundzusammensetzungen (A, B) in Anteilen zwischen 0,01 und 0,5% und vorzugsweise zwischen 0,05 und 2% enthalten sind.

9. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem die Grundzusammensetzung (A) einen Persalz-Stabilisator vom Typ der Aminopolycarboxyl-Säure und/oder des Alkaliphosphont enthält.

10. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem die beiden Grundzusammensetzungen (A, B) überdies Stabilisatoren vom Typ des kalzinierten Silikas, kalzinierten Aluminiums oder suspendierter Polymere enthalten.

11. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 2, bei dem das flüssige Verdünnungsmittel der Lösung und/oder Dispersion und/oder Suspension der Komponenten der beiden Grundzusammensetzungen (A, B) ein nichtionogenes oberflächenaktives Mittel enthält, das von einem primären oder sekundären Alkohol gebildet ist, der mit Alkylenoxiden kondensiert ist.

12. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 2, bei dem das flüssige Verdünnungsmittel der Lösung und/oder Dispersion und/oder Suspersion der Komponenten der beiden Detergentienzusammensetzungen (A, B) ein nichtionogenes oberflächenaktives Mittel enthält das von Alkylphenol gebildet wird, das mit Alkylenoxiden kondensiert ist.

13. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 2, bei dem das Lösungsmittel des flüssigen Verdünnungsmittels der Lösung und/oder Dispersion und/oder Suspension der Komponenten der beiden Detergentiengrundzusammensetzungen (A, B) Propylenglykol, Äthylenglykol oder Oligomere mit 3 bis 100 monomerischen Einheiten und vorzugsweise 5 bis 20 solcher Einheiten ist.

14. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 2, bei dem das Lösungsmittel Äthanol ist.

15. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 2, bei dem das Llösungsmittel Dimethylsulfoxid ist.

16. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 11, bei dem das nichtionogene oberflächenaktive Mittel von einem Cs-C₂₂, vorzugsweise Ca-C₁₈, primären oder sekundären Alkohol gebildet wird.

17. Nicht wässriges flüssiges Detergensprodukt nach den Ansprüchen 11 und 12, bei dem der primäre und/oder sekundäre Alkohol und Alkylphenole mit 3 bis 25 Äthylenoxideinheiten und vorzugsweise 5 bis 15 Einheiten kondensiert sind.

18. Nicht wässriges flüssiges Detergensprodukt nach den Ansprüchen 11 und 12, bei dem der primäre und/oder sekundäre Alkohol und die Alkylphenole mit 2 bis 10, vorzugsweise 3 bis 6 Propylenoxideinheiten kondensiert sind.

19. Nicht wässriges flüssiges Detergensprodukt nach den Ansprüchen 11 und 12, bei dem der primäre und/oder sekundäre Alkohol und die Alkylphenole mit 3 bis 25 Einheiten, vorzugsweise 5 bis 15 Einheiten Äthylenoxid und gleichzeitig gegenwärtigem Propylenoxid kondensiert werden.

20. Nicht wässriges flüssiges Detergensprodukt nach den Ansprüchen 11 und 12, bei dem der primäre und/oder sekundäre Alkohol und die Alkylphenole die mit Äthylenoxid und/oder Propylenoxid kondensiert wurden in der Endhydroxylgruppe mit organischen Säuren verestert werden, die 1 bis 3 Kohlenstoffatome enthalten.

21. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 3, bei dem das eingesetzte oxidierende Bleichmittel Monohydrat-Natriumperborat ist.

22. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 4, bei der in der Grundzusammensetzung (B) eingesetzte Bleichaktivator Tetra-Acetyl-Äthylen-Diamin ist.

23. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 4, bei dem der in der Grundzusammensetzung (B) eingesetzte Bleichaktivator Penta-Acetylglukose ist.

24. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 7, bei dem der eingesetzte Aufbaustoff Zeolithe A ist.

25. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 7, bei dem der eingesetzte Aufbaustoff ein Kalium- oder Natrium-Polyphosphat oder Pyrophosphat ist.

26. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 25, bei dem das Polyphosphat ein Natrium- oder Kalium-Tripolyphosphat ist.

27. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 7, bei dem der eingesetzte Aufbaustoff ein Natriumsalz der Nitrilo-Triessigsäure ist.

28. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 7, bei dem der eingesetzte Aufbaustoff ein Natriumzitrat ist.

29. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem das der Wiederanlagerung entgegenwirkende Mittel Natrium-Polyacrylat ist.

30. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem das der Wiederanlagerung entgegenwirkende Mittel ein Maleinsäureanhydrid Copolymer mit Methyl-Vinyl-Äther ist.

31. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem das der Wiederanlagerung entgegenwirkende Mittel ein Maleinsäureanhydrid Copolymer mit Acrylsäure ist.

32. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 5, bei dem die in der Grundzusammensetzung (B) enthaltenen Enzyme in die Zusammensetzung nach dem Mahlen nachträglich in Form einer Lösung oder einer feinen Teilchenaufschlämmung in nichtionogenen oberflächenaktiven Mitteln oder in nichtreaktiven polaren Lösungsmitteln eingemischt werden.

33. Nicht wässriges flüssiges Detergensprodukt nach Anspruch 32, bei dem die Enzyme proteolytische Enzyme vom Typ der Maxatase (R), Mexacal (R), Savinase (R), Espemase (R), Alkalase (R), Zellulase SP 227 (R), Thermamyl L (R) Type A sind.

34. Nicht wässriges flüssiges Detergensprodukt nach einem der vorhergehenden Ansprüche, bei dem die beiden Grundzusammensetzungen (A, B) anionische und/oder kationische oberflächenaktive Mittel enthalten.

35. Verwendung eines nicht wässrigen flüssigen Detergensproduktes nach den obigen Ansprüchen 1 bis 34, wobei die beiden den Detergens bildenden Grundzusammensetzungen (A, B) in einem festen Verhältnis zwischen 1:4 und 4:1 und vorzugsweise 1:1,5 und 1,5:1 zusammengemischt werden.

36. Verwendung eines nicht wässrigen flüssigen Detergensproduktes nach den obigen Ansprüchen 1 bis 34, bei dem die Mischung der beiden Grundzusammensetzungen (A, B) stattfindet, wenn das Detergens in die Waschmaschine eingebracht wird oder unmittelbar vorher.

Revendications

1. Produit détergent liquide non aqueux, caractérisé en ce qu'il consiste en deux compositions liquides de base distinctes, à mélanger au moment l'utilisation ou immédiatement avant, chaque composition de base consistant en un véhicule non aqueux liquide contenant en solution et/ou en dispersion et/ou en émulsion les autres constituants solides et liquides de la composition détergente, la première composition de base (A) contenant les agents oxydants de blanchiment et la seconde composition de base (B) contenant des enzymes et des activateurs de blanchiment, les deux compositions de base contenant également un certain nombre d'autres constituants choisis parmi les adjuvants, les agents tensio-actifs anioniques et/ou cationiques, les stabilisants, les agents d'anti-redéposition, les pigments, les colorants, les brillanteurs optiques, les parfums, les agents antimousse; avec en outre:

a. un rapport des constituants liquides aux constituants solides compris, pour les deux compositions de base, entre 1:3 et 9:1 et, de préférence entre 1:1,5 et 3:1;

b. une teneur en eau non combinée, inférieure à 2%, et de préférence, inférieure à 1% pour la composition de base (A) et inférieure à 5% et, de préférence, inférieure à 3% pour la composition de base (B);

c. une viscosité comprise entre 100 et 2000 mPa-s et, de préférence, entre 500 et 1000 mPa-s pour les

deux compositions de base;

d. une granulométrie des constituants solides en suspension inférieure à 10 um.

2. Produit détergent liquide non aqueux suivant la revendication 1, caractérisé en ce que le véhicule non aqueux liquide consiste en un ou en plusieurs agents tensio-actifs non ioniques et en un ou en plusieurs solvants polaires.

3. Produit détergent liquide non aqueux suivant la revendication 1, dans lequel les agents de blanchiment oxydants sont contenus dans la première composition de base, en des quantités comprises entre 2 et 35% et, de préférence, entre 10 et 25%.

4. Produit détergent liquide non aqueux suivant la revendication 1, dans lequel les activateurs de blanchiment sont contenus dans la composition de base (B) en des quantités comprises entre 1 et 15% et, de préférence, entre 5 et 10%.

5. Produit détergent liquide non aqueux suivant la revendication 1, dans lequel les enzymes contenues dans la composition de base (B) sont du type protéolytique et/ou amylolytique et/ou lipolytique et/ou cellulase, ces enzymes étant contenues dans la composition de base (B) en des quantités comprises entre 0,2 et 5%, de préférence entre 0,5 et 2%.

6. Produit détergent liquide non aqueux suivant la revendication 2, dans lequel le rapport des solvants polaires aux agents tensio-actifs du véhicule liquide est compris entre 0,5:9 et 3:1 et, de préférence, entre 1:9 et 1:1.

7. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel les adjuvants sont contenus dans les deux compositions de base (A, B) en des quantités comprises entre 5 et 50% et, de préférence, entre 10 et 30%.

8. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel les brillanteurs optiques sont contenus dans les deux compositions de base (A, B) en des quantités comprises entre 0,01 et 0,5% et, de préférence, entre 0,05 et 0,2%.

9. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel la composition de base (A) contient un stabilisant à base de persel du type acide aminopoly- carboxylique et/ou phosphonate de métal alcalin.

10. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel les deux compositions de base (A, B) contiennent en outre des stabilisants du type silice calcinée, alumine calcinée ou polymère en suspension.

11. Produit détergent liquide non aqueux suivant la revendication 2, dans lequel le véhicule liquide de la solution et/ou de la dispersion et/ou de la suspension des constituants des deux compositions de base (A, B) comprend un agent tensio-actif non ionique formé d'un alcool primaire ou secondaire condensé avec des oxydes d'alcoylène.

12. Produit détergent liquide non aqueux suivant la revendication 2, dans lequel le véhicule liquide de la solution et/ou de la dispersion et/ou de la suspension des constituants des deux bases détergentes (A, B) comprend un agent tensio-actif non ionique formé d'un alcoylphénol condensé avec des oxydes d'alcoylène.

13. Produit détergent liquide non aqueux suivant la revendication 2, dans lequel le solvant du véhicule liquide de la solution et/ou de la dispersion et/ou de la suspension des constituants des deux bases détergentes (A, B) est du propylèneglycol, de l'éthylèneglycol ou des oligomères ayant de 3 à 100 motifs monomères et, de préférence, de 5 à 20 motifs monomères.

14. Produit détergent liquide non aqueux suivant la revendication 2, dans lequel le solvant est l'étha- nol.

15. Produit détergent liquide non aqueux suivant la revendication 2, dans lequel le solvant est le dimé- thylsulfoxyde.

16. Produit détergent liquide non aqueux suivant la revendication 11, dans lequel l'agent tensio-actif non ionique est formé d'un alcool primaire ou secondaire en Ce à C₂₂ et, de préférence, en Ce à C₁₈.

17. Produit détergent liquide non aqueux suivant les revendications 11 et 12, dans lequel l'alcool primaire et/ou l'alcool secondaire et les alcoylphénois sont condensés avec de 3 à 25 motifs d'oxyde d'éthylène et, de préférence, avec de 5 à 15 motifs d'oxyde d'éthylène.

18. Produit détergent liquide non aqueux suivant les revendications 11 et 12, dans lequel l'alcool primaire et/ou l'alcool secondaire et les alcoylphénols sont condensés avec de 2 à 10 et, de préférence, de 3 à 6 motifs d'oxyde de propylène.

19. Produit détergent liquide non aqueux suivant les revendications 11 et 12, dans lequel l'alcool primaire et/ou secondaire et les alcoylphénols sont condensés avec de 3 à 25 motifs et, de préférence, de 5 à 15 motifs d'oxyde d'éthylène et d'oxyde de propylène présents simultanément.

20. Produit détergent liquide non aqueux suivant les revendications 11 et 12, dans lequel l'alcool primaire et/ou secondaire et les alcoylphénols condensés avec de l'oxyde d'éthylène et/ou de l'oxyde de propylène sont estérifiés sur l'hydroxyle d'extrémité par des acides organiques ayant de 1 à 3 atomes de carbone.

21. Produit détergent liquide non aqueux suivant la revendication 3, dans lequel l'agent de blanchiment oxydant utilisé est du perborate de sodium monohydraté.

22. Produit détergent liquide non aqueux suivant la revendication 4, dans lequel l'activateur de blanchiment utilisé dans la composition de base (B) est la tétraacétyléthylènediamine.

23. Produit détergent liquide non aqueux suivant la revendication 4, dans lequel l'activateur de blanchiment utilisé dans la composition de base (B) est le pentaacétylglucose.

24. Produit détergent liquide non aqueux suivant la revendication 7, dans lequel l'adjuvant utilisé est un zéolite A.

25. Produit détergent liquide non aqueux suivant la revendication 7, dans lequel l'adjuvant utilisé est un polyphosphate ou un pyrophosphate de potassium ou de sodium.

26. Produit détergent liquide non aqueux suivant la revendication 25, dans lequel le polyphosphate est le tripolyphosphate de sodium ou de potassium.

27. Produit détergent liquide non aqueux suivant la revendication 7, dans lequel l'adjuvant utilisé est le sel sodique de l'acide nitrilotriacétique.

28. Produit détergent liquide non aqueux suivant la revendication 7, dans lequel l'adjuvant utilisé est le citrate de sodium.

29. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel l'agent d'anti-redéposition est du polyacrylate de sodium.

30. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel l'agent d'anti-redéposition est un copolymère d'anhydride maléique et d'éther méthylvinylique.

31. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel l'agent d'anti-redéposition est un copolymère d'anhydride maléique et d'acide acrylique.

32. Produit détergent liquide non aqueux suivant la revendication 5, dans lequel les enzymes contenues dans la composition de base (B) sont post-mélangées dans la composition, après broyage sous la forme d'une solution ou d'une suspension de fines particules dans un agent tensio-actif non ionique ou dans un solvant polaire non réactif.

33. Produit détergent liquide non aqueux suivant la revendication 32, dans lequel les enzymes sont des enzymes protéolytiques du type de la maxatase (marque de fabrique), mexacal (marque de fabrique), savinase (marque de fabrique), espemase (marque de fabrique), alkalase (marque de fabrique), cellulase SP 227 (marque de fabrique), thermamyl L de type A (marque de fabrique).

34. Produit détergent liquide non aqueux suivant l'une quelconque des revendications précédentes, dans lequel les deux compositions de base (A, B) contiennent des agents tensio-actifs anioniques et/ou cationiques.

35. Utilisation d'un produit détergent liquide non aqueux suivant les revendication 1 à 34 ci-dessus, dans laquelle les deux compositions de base (A, B) formant le détergent sont mélangées ensemble en un rapport fixe compris entre 1:4 et 4:1 et, de préférence, entre 1:1,5 et 1,5:1.

36. Utilisation d'un produit détergent liquide non aqueux suivant les revendications 1 à 34 ci-dessus, dans lequel le mélange des deux compositions de base (A, B) a lieu quand le détergent est introduit dans la machine à laver ou juste avant.