LIQUID WASHING COMPOSITION WITH SEPARATE COMPONENTS FOR WASHING CLOTHES AND ITS EQUIPMENT, AND WASHING METHOD FOR AUTOMATIC WASHING MACHINES.

Abstract

A fluid washing composition with four separate components and a corresponding laundry kit are described. The four components are housed in separate tanks of a washing machine equipped with a program for separate selection, dosing, and delivery of detergent. The separate components have the following formulations: Component 1 - a detergent formulation with a pH ranging from 4.0 to 12.0, providing high detergent effectiveness in washing programs at temperatures between 40° and 60°C, with specific action on cotton fibers and, in particular, white garments; Component 2 - a detergent formulation with a pH between 8.0 and 12.0, with high detergent effect in washing programs at temperatures within the range of 15°-40°C, with specific action on synthetic, colored and animal-derived fibers; Component 3 - enzyme-based stain-removing formulation based on at least protease and lipase and possibly amylase with a pH between 5.0 and 6.0 and preferably between 5.0 and 5.5, stabilized with sorbitol and calcium chloride; Component 4: conditioning formulation for after washing, with a pH ranging from 2.0 to 4.0.

Description

LIQUID WASHING COMPOSITION WITH SEPARATE COMPONENTS FOR WASHING CLOTHES AND ITS EQUIPMENT, AND WASHING METHOD FOR AUTOMATIC WASHING MACHINES FIELD OF INVENTION

[0001] The present invention relates to a liquid washing composition comprising a plurality of separate concentrated components. The composition is intended for washing clothes in automatic washing machines, equipped with separate reservoirs for each of said separate washing composition components, as well as with a program for selecting and measuring the various separate washing composition components, according to the varying characteristics of the individual laundry required by the user.

[0002] The washing composition is arranged so that the different separate components can be introduced into the washing chamber of the washing machine, at pre-established times of the washing cycle, by means of suitable selection, measuring and supply devices with which the washing machine is equipped.

[0003] Herein and in what follows, the term separate component liquid washing composition means a composition consisting of at least two liquid phase components that are used, simultaneously and / or sequentially, to carry out a complete laundry cycle in a washing machine, to achieve the washing and subsequent conditioning of the fibers of the washed garments. PRIOR ART STATE AND UNSOLVED PROBLEMS THEREIN

[0004] Domestic laundry, in developed markets, is now carried out almost exclusively with the support of a washing machine.

[0005] For this type of machine, suitable detergent products have long been available on the market, which have a complex universal formula, fluid or powder, so that they can be introduced into the washing chamber of the machine manually or by means of delivery devices with automatic programming.

[0006] However, the consumer is often forced to wash items made of special materials, for which multipurpose detergents are ineffective and / or harmful to the fibers.

[0007] Therefore, in the market for household laundry detergents, a number of product types with optimized performance for specific groups of fabrics and / or colors of items have expanded.

[0008] Most consumers, in order to meet all their requirements, are forced to buy and use various products: for example, for white items, colored items, wool items, synthetic items, or sporting goods. RFzonn / zznz / E / YiAi

[0009] On the other hand, the use of a single product could represent, on the one hand, a possible risk of damaging items made of more delicate fibers, which in fact deteriorate noticeably due to products with a greater detergent and bleaching effect or, on the contrary, reduced effectiveness for less delicate garments with persistent dirt stains.

[0010] This first group of detergent products is further expanded with other types of products that are used to carry out specific functions during washing, such as stain removers for the removal of the most resistant stains or organic stains, fabric softeners, fragrances or specific additives for the conditioning of natural fibers.

[0011] While this multiplicity of washing products, on the one hand, allows for effective washing of different types of fabric and soiling, it naturally implies, on the other hand, some drawbacks, such as: greater complexity of supply for the consumer, a larger volume in the domestic rooms where washing takes place, a certain skill in the modes of use, prolonged non-optimal storage, with the consequent loss of washing effectiveness, especially of the enzymatic components of the detergents, and finally, the risk of using incorrect products when the available stocks are not complete and yet there is an urgency to carry out a laundry.

[0012] Another drawback of this conventional method of using laundry products stems from the fact that laundry is done much more frequently today than in the past: instances requiring high washing power are therefore less frequent. Consequently, some detergent ingredients on the market are overdosed relative to the requirements of typical laundry, thus needlessly increasing the environmental impact of these products.

[0013] Furthermore, it should be noted that the greatest degreasing effectiveness of each of the surfactants that make up the detergent occurs in a well-defined range of different temperatures: therefore, the compositions of multi-purpose detergents available on the market, which must be able to carry out washing activity across the entire range of possible temperatures for the different items to be washed, must necessarily comprise several surfactants; therefore, however, some of those surfactants may be deficient or nonexistent, depending on the temperature of the washing program chosen by the consumer, and thus represent a useless waste.

[0014] In order to address these different problems, washing machines equipped with several separate tanks, containing simpler, individual concentrated components, each with a different function, have recently begun to expand in the market. This separation allows for a high number of wash cycles, in which the dosing of the different components is carried out automatically, also at different points in the cycle. RFzonn / zznz / E / YiAi washing (a well-known and widespread example is that of Miele's TwinDos® washing machines), calibrating it based on the type of wash being carried out and the type of garments being washed. The individual components can thus be used in the correct quantity, without requiring any random user intervention, obtaining optimized efficiency for the individual wash cycle.

[0015] Documents CN-108951007, DE-102016106777, WO-2015 / 143820, EP-2566943, EP-2524079, EP-2196574, EP-1995368, US-7784310, EP-474848 disclose washing machine solutions or methods of using washing machines, providing a plurality of separate washing component tanks, which are automatically dosed during successive washing cycles.

[0016] As regards the particular type of washing composition with separate components used in such multi-tank washing machines, the current state of the art is represented, by way of example, by the documents briefly discussed below.

[0017] WO 2017 / 211697 discloses a washing composition provided in a combination of tanks to address enzyme compatibility issues; the composition is divided into a first tank with a component containing an enzyme protease base, a second tank with a component containing an enzyme lipase and / or a cellulase base, and a third tank containing a detergent. Alternatively, the detergent can be added to either the first or second tank.

[0018] EP 2521811 and the corresponding US2013036772A1, according to which the pre-characterizing portion of claim 1 is a draft, describes a washing machine comprising an external multi-tank connected to the internal drum of the washing machine. The multi-tank comprises a first tank containing at least one enzyme, an enzyme stabilizer, and a surfactant, which is a typical formulation of a conventional detergent; a second tank containing at least one bleach and a complexing agent, which is a known stain remover and sanitizer formulation; and a third tank containing at least one fragrance and / or an optical brightener and / or a fabric softener. The specific compositions disclosed herein do not have an innovative formulation and simply represent an example of different complex washing agents, delivered according to requirements.The complex contents of each tank are delivered under certain conditions, but this does not allow for the effective construction of a formulation that optimizes the quantities of the ingredients. Furthermore, it should be noted that one of the components contains enzymes and surfactants, which are therefore delivered together in the wash cycle. This is no different from the state of the art of a common detergent, where the two ingredients are defined a priori and the modulation, the determination of which is not possible in use, exceeds the limit of waste of (costly) enzymes in many cases where they are not needed and renders such a component useless in the presence of animal protein-based materials (such as wool and silk) that deteriorate due to enzymes. Finally, the division of the separate components into three compartments, with the components in a 1:4:1 ratio (where... RFzonn / zznz / E / YiAi (the largest quantity is for the alkaline bleaching agent), is inconsistent with washing requirements (for which a larger quantity of surfactants and solvents is usually necessary) and therefore results in inefficient use of available volumes, making it unsuitable for application in any washing machine supply system. In particular, a solution like the one illustrated in EP3623524, where the components must be integrated into tanks housed in a circular section of a washing machine door, is not optimally divided into three components for space utilization, given the average type of garments to be washed. Furthermore, it should be noted that the washing machine door transfers some of the washing heat to the washing formulation tanks, which are therefore no longer in a neutral environment (as might occur if the tanks were located above the washing machine).EP 2521810 describes a washing machine comprising an external multi-tank connected to the inner drum of the washing machine. The multi-tank comprises a first tank containing at least one enzyme selected from the amylase, mannanase, cellulase, lipase, and / or pectate lyase group and at least one surfactant and / or complexing agent; a second tank containing at least one protease and one surfactant and / or complexing agent; and a third tank containing at least one fragrance and / or optical brightener and / or fabric softener.

[0019] WO 2009 / 95003 describes a washing machine comprising a multi-tank system in which each individual type of washing component is housed in a respective tank. This completely avoids harmful interactions between different types of enzymes and allows for precise dosing of each individual component; however, there is a significant drawback to having to manage a large number of different tanks, both in terms of volume and the frequency and method of refilling.

[0020] Based on the framework of the prior art reported above, it seems evident that inefficiencies remain in compositions with separate components of the prior art. In particular, splitting the components is effective only when a large number of separate tanks can be used, while splitting involves compromises that render washing ineffective and inflexible when only three separate tanks are chosen.

[0021] In particular, solutions that suggest assigning each enzyme family to a respective tank, as proposed in WO 2009 / 9503, suffer from the drawback already described above of too large a number of tanks for good system efficiency and for rapid acceptance of the same by consumers, who in fact would not see in them a sufficient advantage over the current situation of using a plurality of washing compositions suitable for each specific washing situation.In contrast, in solutions where it is suggested to associate each enzyme family with other components of the washing composition with which no harmful interaction effects occur, for example, surfactants, bleaching agents or softening agents - as proposed for example in document EP 2521811 - it is indeed possible to keep the number of different tanks reasonably low, but the disadvantage is that the enzymes and their associated components cannot be dosed independently, thus determining an inevitable waste of the over-dosed component.

[0022] These problems are further accentuated in cases where individual tanks have dimensional limitations because they must be housed in compartments of a pre-established geometry, as proposed in EP3623524.

[0023] The objectives of the present invention are therefore to provide a washing composition with separate components that allows for independent dosing of the main components of the composition under a wide range of different possible washing conditions, while generally maintaining a reasonably low number of separate components and relative quantities among the various components that are suitable for having independent reservoirs that optimize the available space in a circular sector of a washing machine door. The invention also aims to minimize the total volume of ingredients, to increase the washing machine's independence to up to 75 washing cycles (with an average load of 4.5 kg) without the need to refill the components, to reduce the use of plastic materials for packaging the washing unit, and the resulting environmental impact.

[0024] Finally, another objective is to propose a group of components that is particularly suitable for maintaining good efficiency over time even under critical temperature conditions, such as those that may be encountered in contact with a washing machine door during exposure to several hot wash cycles. BRIEF DESCRIPTION OF THE INVENTION

[0025] These objects are achieved by means of a washing composition with several separate components having the characteristics defined in appended claim 1. Other preferred characteristics of said washing composition are defined in the dependent claims.

[0026] In particular, the present invention consists of the formulation of a washing composition to treat all possible garments and other textile articles for family use, made of any type of natural or synthetic fabric and in any state of dirt or stains.

[0027] According to the present invention, said washing composition consists of four separate liquid-phase components, which are sold to the consumer in respective containers and which, when used in a washing machine in combination with each other according to predefined quantities, which vary according to the type of fabric, the degree of soiling or the presence of stains, allow for the optimal washing and treatment of any type of fiber and garment, without the need for the addition or alternative use of any other component. RFzonn / zznz / E / YiAi of some other washing product, stain remover or fabric softener, thus guaranteeing the universality of the proposed solution to solve the problem of effective domestic laundry.

[0028] Integrating the washing composition with separate components of the present invention into a washing machine equipped with an automatic dosing system is therefore able to allow a drastic reduction not only in the number of products that need to be used for washing clothes, but also in the internal areas intended to preserve stocks of such products. BRIEF DESCRIPTION OF THE DRAWING

[0029] Other features and advantages of the invention will in any case be more evident from the following detailed description of a preferred embodiment thereof, provided merely as a non-limiting example and also illustrated in the accompanying drawing which represents a schematic view thereof of a washing machine door with four reservoirs for components according to the invention. DETAILED DESCRIPTION OF PREFERRED MODALITIES

[0030] To solve the problem noted above, the Applicant has carried out extensive studies on the stability of the enzymes during preservation and on the opportunity to optimize the division and quantities of the different washing components, in view of the need to treat different materials without residues and to occupy a limited space in a circular sector compartment.

[0031] At the end of this experimentation, it was found that a division into four different components allowed for the optimal occupation of a compartment of circular section (figure 1) with differentiated volumes of components 1, 2, 3, 4 shown in figure 1 in the proportions of 5:4:1:2 to 4:3:1:3, respectively, preferably in the proportion 4.2:3.3:1:2.5.

[0032] It has also been noted that under particular pH conditions it was possible to maintain enzymes from different families, and in particular protease and lipase, in a stable mixture without significant losses of activity.

[0033] The results of these studies have made it possible to surpass the previously described prior art by devising a liquid washing composition in which all the necessary enzymes are combined into a single component. This has allowed for the innovative use of the remaining components, separating the surfactants into two components based on their optimal activity range temperatures and their compatibility with the fibers, and adding a fourth component for the final conditioning of the fibers, thus devising the liquid washing composition with separate components of the present invention.

[0034] In fact, this method allows the two protease and lipase-based enzymes, along with any other enzymes that may be necessary to optimize stain removal, to be contained in a single, small-volume container (the volume of component 3 in Figure 1). This occupies the entire available volume of the container, while the surfactant component is transferred to separate, larger, independent containers. This allows for better distribution (compared to the known technique) of the various components into four different, independent volumes, appropriately separating the components (typically enzymes and surfactants) that should be used under different washing conditions.

[0035] The four separate components that constitute the liquid washing composition of the present invention therefore have the following general formulations: • Component 1 - washing formulation with a pH between 4.0 and 12.0, which has a specific action on cotton garments and in particular white garments; • Component 2 - washing formulation with a pH between 8.0 and 12.0, with specific action on synthetic, colored and animal-derived fibers; • Component 3: enzyme-based stain remover formulation with a pH ranging from 4.0 to 6.0; • Component 4 - formulation for conditioning fibers at the end of the washing operation, with a pH between 1.0 and 4.0.

[0036] The components that occupy the respective volumes designated 1, 2, 3 and 4 in Figure 1.

[0037] As outlined in Figure 1, the components are contained in cartridges in concentrated form and in sufficient quantity to carry out a number of washes between 50 and 100, taking into account the average frequency of use of the same, with an effectiveness higher than the average of conventional liquid washing products present on the market.

[0038] The four cartridges 1-4 of the washing composition of the invention are installed in a special washing machine, equipped with a receiving seat with separate extraction units for the four cartridges (as described in EP3623524). The machine is further equipped with an automatic and independent extraction and dosing system for the four components, with a software program that defines the respective dosage of the individual components, according to the user's selections regarding the type of soiling and the type of fabric. The lid of the cartridges itself represents the connection to the distribution line provided on board the machine and is equipped with a ventilation system to equalize the internal pressure.

[0039] The invention is based on the experimental observation that it is possible to maintain the stability and relative washing efficiency of lipase enzymes in a mixture with certain types of protease enzymes when these enzymes are incorporated into a formulation having a pH below 6.0 and using a specific solvent mixture. Preferably, the pH of the formulation should be above 4 and even more preferably above 5.

[0040] In particular, due to the possible housing of the ingredient containers in a position potentially exposed to increased temperature during washing cycles, stability over time must be ensured not only at 37°C, a temperature typically identified in the industry as a boundary temperature parameter related to standard storage conditions for a detergent, but even up to approximately 40°C.

[0041] Separating this component, previously identified as a third component, from those containing washing surfactants allows for precise dosing only when needed and compatible with the type of fabric being treated. The enzymes, contained in a single package without other washing components, have a larger volume available, making it possible to administer a higher dosage of this third component per unit of time. This allows for superior stain removal and eliminates the need for a pretreatment or washing additive. Furthermore, it is possible to perform a refreshing wash on garments made of animal-derived materials (wool, silk) using, for example, the second surfactant-based component—without necessarily damaging them with the enzymes, which are only essential in the presence of organic stains.

[0042] The washing formulation of the first component, on the other hand, is characterized by the predominant presence of anionic surfactants, which are highly active on plant-based fibers, explaining its peak effectiveness at medium-high temperatures, for example, 60°C. This formulation can also be enhanced with oxygen-based brighteners to increase effectiveness on oxidizable stains and with optical brighteners to achieve maximum whiteness enhancement.

[0043] The washing formulation of the second component is characterized by the predominant presence of non-ionic surfactants, which explains its maximum effectiveness at temperatures ranging from 15° to 30°C. It can be enhanced with color-stabilizing components and vegetable proteins to generally improve the hydration of animal-based fibers, as well as with odor-eliminating ingredients to allow for optimal washing of synthetic and technical garments.

[0044] The formulations of the individual separate components of the washing composition of the invention will now be illustrated in greater detail. Component 1

[0045] Component 1 is a concentrated detergent base that exhibits its maximum effectiveness at temperatures of 40°C or higher. The detergent surfactant system consists primarily of a mixture of anionic and non-ionic surfactants, with an overall amount ranging from 20% to 50% active agent. The mixture must contain anionic and non-ionic surfactants in active ingredient ratios between 75:25 and 50:50. In the context of this application, reference is made to the amount of active agent because surfactants (or other substances that may be considered) are normally sold transported and diluted in water or other agents, such as alcohols or glycols, which are considered a “non-active” component for detergent purposes.

[0046] To allow maximum effectiveness, with the active ingredient being the same, on cellulose fiber articles and on a wide spectrum of stains, the mixture should preferably consist of a combination of at least four different molecules.

[0047] The preferred types of anionic surfactants belong to the group consisting of alkylbenzene sulfonates, alkyl ether sulfates, and alkyl sulfates.

[0048] The preferred alkylbenzene sulfonates have an alkyl chain ranging from C10 to C15 and are commercially available under the trade names TENSARIL™ (manufactured by KLM Oleo), SOLPHODAC™ (manufactured by SASOL), MARLON™ (manufactured by SA-SOL), and CAFLON™ (manufactured by UNIVAR). Alkylbenzene sulfonates are typically inserted into the formulation in their acidic form and neutralized in situ with strong bases such as sodium hydroxide, monoethanolamine, or triethanolamine. The addition of such bases also serves to adjust the pH of the formulation to the desired value.

[0049] Among alkyl ether sulfates, surfactants with a chain length ranging from C10 to C16 and ethoxylation moles ranging from 1 to 3 are preferred. Examples of usable raw materials are commercially available under the trade names ZETESOL™ (manufactured by Zschimmer & Schwarz), EMPICOL™ (manufactured by INNOSPEC), TENSAGEX™ (manufactured by KLM Oleo).

[0050] The surfactant mixture may also contain an alkyl sulfate with an alkyl chain ranging from C10 to C16 available on the market under the trade names SULFOPON™ (manufactured by BASF), SULFETAL™ (manufactured by Zschimmer & Schwarz), STEPANOL™ (manufactured by STEPAN).

[0051] Among nonionic surfactants, primary and secondary ethoxylated fatty alcohols are preferred, with a degree of ethoxylation greater than or equal to 7 moles and alkyl chains ranging from C10 to C18 commercially available, for example, under the trade names LUTENSOL™ (manufactured by BASF), CAFLON™ (manufactured by UNIVAR) or EMPILAN™ (manufactured by INNOSPEC).

[0052] Other non-ionic surfactants may be selected from the categories of alkyl polyglucosides or alkyl polypentosides.

[0053] Soap may finally be added to the surfactant mixture at an active agent concentration ranging from 1 to 10%. The preferred soaps are obtained from olive oil and coconut oil.

[0054] To the above surfactant mixture, other types of surfactants may be added to stabilize the viscosity or foaming power of the mixture, but such additional surfactants do not have a significant effect on improving the washing performance of cellulosic fibers.

[0055] The mixture must also be supplemented, in a manner compatible with washing formulations according to known technique, with scouring, sequestering, and solvent molecules.

[0056] To improve washing efficiency, polymers with dispersing, residue-removing, and soil-eliminating properties should also be added. These components can be selected from products available on the market under the SOKALAN™ brand (manufactured by BASF), TEXCARE™ (manufactured by CLARIANT), or REPEL-O-TEX™ brand (manufactured by SOLVAY). The percentages of these components in the formulation may vary between 2 and 10%.

[0057] Given that component 1 is primarily intended for use in white cellulose fiber fabrics, the formulation is enriched with an optical brightener, preferably selected from products derived from 4,4'-Distyryl biphenyl (DSBP), such as those marketed under the brand name TINOPAL™ (manufactured by BASF). The concentration of this raw material ranges from 0.05% to 1%.

[0058] The formulation is completed with water and the mixture may contain other functional ingredients such as fragrances, theological modifiers, preservatives and colorants.

[0059] Hydrogen peroxide can also be added to the formulation of component 1 to enhance the brightening action on oxidizable stains and to provide a specific sanitizing effect. Acidic pH adjusters are essential in this case to maintain the pH level between approximately 4 and approximately 12. Component 2

[0060] Component 2 is a concentrated detergent base active at low temperatures, characterized by an extremely gentle action on fibers of animal origin such as wool and silk.

[0061] Like component 1, component 2 is also based on a mixed surfactant system of anionic and nonionic surfactants in a total amount ranging from 30% to 60% active agent. While anionic surfactants do not account for its maximum effectiveness at low temperatures, they are useful for stabilizing the hyperconcentrated formulation. Therefore, the mixture should contain anionic and nonionic surfactants in an active ingredient ratio of between 25:75 and 50:50.

[0062] The anionic surfactants used in component 2 are selected from the same categories already cited for component 1. The applicant has noted, however, that the complete elimination of anionic surfactants from the alkyl sulfate and alkyl ether sulfate categories and their replacement with sulfonated olefins noticeably improves (experimentally verified by a consumer panel) the softness and elasticity of the garments and prevents the wool from becoming hot due to chemical dehydration. For example, usable sulfonated olefins can be selected from the product ranges under the trademarks HOSTAPUR™ (manufactured by CLARI-ANT), WEYLCLEAN (manufactured by WEYLCHEM), or MERSOLAT™ (manufactured by LANXESS).

[0063] The preferred non-ionic surfactants for this component, as for component 1, are primary and secondary ethoxylated fatty alcohols with a degree of ethoxylation greater than or equal to 7 moles and alkyl chains ranging from C10 to C18, commercially available for example under the brand names LUTENSOL™ (manufactured by BASF), CAFLON™ (manufactured by UN1VAR), EMP1LAN™ (manufactured by 1NNOSPEC) and in any case alkyl polyglucosides.

[0064] The applicant has further verified that the preferential use of glucomides, in combination with olefins, helps to maintain the softness of wool fibers.

[0065] Preferably, the formulation also contains disodium capryloyl glutamate, in a concentration of the active ingredient ranging from 1% to 5%, which explains a bacteriostatic function and aids in the elimination of odor derived from sweat and other body fluids.

[0066] Regarding component 1, the mixture of component 2 should preferably be supplemented with chelating and sequestering molecules.

[0067] In order to improve the effectiveness of washing, polymers with dispersant, anti-residue and dirt-removing functions should preferably be introduced, selectable from the same range of commercial products indicated for component 1; the concentrations of use are also comparable and range between 2 and 10%.

[0068] Component 2 is preferentially indicated for the washing treatment of colored articles and is therefore further integrated with additives that have an anti-color transfer function. Suitable solutions may be selected from polyvinylpyrrolidone derivatives, cationic aliphatic polyamine derivatives, for example, those commercially available under the trademarks SOKALAN™ (manufactured by BASF), TEXCARE™ (manufactured by CLARIANT), REILLINE™ (manufactured by VERTELLUS).

[0069] The formulation is completed with water and other functional ingredients such as solvents, fragrances, rheology modifiers, preservatives, colorants and pH adjusters may be contained in the mixture. Component 3

[0070] This component, as previously indicated, contains substantially an enzyme load. The enzyme base of the load contains a mixture of enzymes that are essential to ensure the stain-removing power (particularly on stains of organic origin) of the washing composition of the invention. The mixture normally contains at least one protease, one amylase, and one lipase. In addition, the base may preferably contain one cellulase and / or one mannanase.

[0071] The mixture must be stable at temperatures up to 40°C, therefore above 37°C, the temperature at which enzyme manufacturers test enzyme stability. This is because placing the containers near the hatch can expose the mixture, in the case of high-temperature washes, to an increase in the internal temperature of the liquid, accelerating enzyme breakdown.

[0072] Among proteases, the use of subtilisin is especially recommended in this application; Only some types, particularly those provided by manufacturers in a previously unstabilized form, allow for maximum long-term stability of component 3. In fact, if the raw material already contains stabilizing active ingredients, it is not possible to achieve an overall balance of mutual stability between all the necessary enzymes, which negatively affects the effectiveness of the washing process.

[0073] In particular, an experimental accelerated stability result has been defined as optimal, which allows, after conditioning at 40°C for 12 weeks, a loss of effectiveness of less than 20%.

[0074] Experimental research leading to the present invention has shown that the stable coexistence of these enzymes in the same formulation, particularly between protease and lipase, is optimal when the pH is maintained between 4 and 6 or even better between 5 and 6.

[0075] For optimal stabilization, it has been found that careful selection of available subtilisin enzymes is necessary. This selection is based on the enzyme co-formulants introduced into the commercial raw material by the manufacturer, the specific stain-removing efficacy, and the degrading power imparted to the lipase. In fact, without a suitable enzyme mixture, compatibility issues arise at these pH levels, leading to instability over time and a loss of efficacy.

[0076] Empirical wash trials at time zero and accelerated aging periods at Tests at 40°C for up to 12 weeks, with specific monitoring of blood, grass, cocoa, olive oil, and tallow stains, have shown that maximum stability and effectiveness are obtained by mixing preferably with commercially available subtilisin-type enzymes under the trade names Preferenz™ P100 (available from DU PONT) or LAVERGY™ PRO 104 L (available from BASF), since enzymes, even the newest on the market and those with the best performance in conventional detergent applications, have proven to deteriorate much faster. RFzonn / zznz / E / YiAi

[0077] The protease in the formulation may contain up to 3% active enzyme protein (AEP), preferably up to 2% AEP.

[0078] In addition to the protease, the formulation contains a lipase selected from those commercially available, for example, under the trade names L1PEX™ and LIPEX EVITY™ available from NOVOZYMES and PREFERENZ™ L available from DU PONT. The formulation may contain lipase up to 1% of the total active ingredient (TAI).

[0079] In addition to protease and lipase, the third component formulation may also contain an amylase enzyme selected from those commercially available, for example, under the trade names AMPLYFY PRIME, STAINZYME, TERMAMYL™, and TERMAMYL UL-TRA™ available from NOVOZYMES, and PREFERENZ™ S available from DU PONT. The formulation may contain amylase up to 1% ape, preferably up to 0.5% ape. Furthermore, the system may also contain cellulase and mannanase, both at a concentration of up to 0.5% ape.

[0080] The formulation of the third component is finally stabilized by the addition of polyols, preferably glycerol or even better, sorbitol, and a salt chosen from calcium chloride and sodium formate. The choice of stabilizing system must preclude the use of monopropylene glycol (MPG) in the formulation. MPG added unintentionally to the formulation, but derived from byproducts of commercially available raw materials, must not exceed 10% of the active agent. In fact, MPG concentrations generally above 10% have been found to cause physicochemical instability of the solution, resulting in a cloudy mixture and precipitation of denatured enzymes with a consequent dramatic loss of staining and elimination of efficacy. Component 4

[0081] The fourth component of the washing composition of the invention is a fiber conditioning product designed to increase the softness of natural fiber garments and significantly reduce static cling in synthetic garments. The formulation of this component typically contains at least one cationic surfactant, preferably of the estherquat type. Polypropylene glycol or alcohol may be added to this surfactant. The cationic surfactant may be present in concentrations ranging from 5% to 20% active agent.

[0082] Lactic acid may optionally be added to the formulation at a concentration of up to 2% to adjust the pH and emulsion stability. The addition of lactic acid imparts bacteriostatic properties to the product and eliminates the need for additional preservatives.

[0083] According to the invention, a functionalized inulin polymer is preferably added to component 4 to increase the softness of the articles and eliminate the roughness of the cellulose fibers to a significant degree, thus achieving a result comparable to inulin-free formulations that have a 20% higher concentration of the cationic surfactant. Since an excessively high concentration of cationic surfactant in fabric fibers leads to undesirable side effects such as excessive oiliness and consequent water repellency (particularly problematic in articles intended for water absorption, such as hand towels and bathrobes), the addition of functionalized inulin derivatives offers the opportunity to limit the dosage of the cationic surfactant, resulting in a noticeable improvement in the sensory appearance of the washed and conditioned garments.Inulin is dosed in component 4 in an amount ranging from 0.2% to 2% of the active ingredient and can be chosen from the products available on the market under the brand name QUATIN® (manufactured by ROYAL COSUN).

[0084] It is known that some hydrolyzed or functionalized vegetable proteins derived from wheat and silk, when added in an amount of active raw material ranging from 0.1% to 3%, provide a softening effect on textile fibers, superior to lanolin. The Applicant, however, has demonstrated that the use of vegetable proteins derived from rice, used in the prior art only in the cosmetics sector, in addition to having an effect on the hydration and softness of keratin fibers, also improves (which can be clearly demonstrated by a consumer panel test) the hydration of cellulose fibers and the relaxation of silk and cotton fibers, thus facilitating the ironing of garments. These vegetable proteins derived from rice are dosed in the formulation in an amount of active ingredient ranging from 0.2% to 3%.0% and can be chosen from commercially available products, for example those of the GLUADIN® brand (manufactured by BASF) and ORYSOL™ (manufactured by KELISEMA).

[0085] Treatment with component 4 of garments made from animal fibers, at the end of the washing operation, opposes the dehydration normally caused by the washing process and reduces the aging of the fibers due to wear.

[0086] The formulation of component 4 may also contain secondary active agents such as silicones, enzymes of the cellulase category, and odor-neutralizing active ingredients. Dosage of components 1-4 separated

[0087] The separate components 1-4 described above can be dosed independently during the program; however, for each wash cycle at least one of the detergent-effect components 1 and 2 must always be dosed, with the optional addition of components 3 and 4 according to the criteria indicated below.

[0088] In particular, with reference to a standard load of laundry of about 4.5 kg, the dosed quantities of the separate components of the washing composition of the invention are preferably as follows: κρζοηη / ζζηζ / Ε / γίΛΐ • the total quantity of component 1 and component 2 will be within the range of 10 mi to 40 mi; • the quantity of component 3 must be between 1 and 10 ml; • The quantity of component 4 must be within the range of 5 to 20 ml.

[0089] Components 1, 2 and 3 must be dosed in the main wash step and can be added to the wash liquid simultaneously or in different steps, according to the wash program.

[0090] In addition, components 1 and 2 can also be dosed during a pre-wash step. Finally, component 4 will be dosed in the final rinse.

[0091] The composition of the components according to a preferred embodiment, taking into account the relative dosage requirements that are on average detected in the use of washing machines, requires a total volume of less than 4 liters, preferably 3.25 liters with volumes thus distributed:

[0092] Component 1: 1250 ml

[0093] Component 2: 1000 mi

[0094] Component 3: 300 mi

[0095] Component 4: 700 mi

[0096] Such a choice of volumes allows for an optimal distribution of the containers in the housing provided in the appliance and allows for up to 75 washing cycles to be carried out, avoiding excessively staggered consumption of the components over time with difficulties in replacement for the user. EXAMPLES

[0097] The following describes in detail and schematically some preferred examples of the individual liquid washing components according to the present invention. The complex formulation of the washing composition is then created during the washing machine's operating cycle, through a process stored on board the machine that allows the selection, dosing, and delivery of the four components according to the requirements, in technical forms per se within the scope of a person skilled in the art. COMPONENT 1 EXAMPLE 1: 17% of C10-13-sec-alkylbenzene 4-sulfonic acid 2.5% NaOH 8% lauryl sulfate (MEA Lauryl sulfate) 8% ethoxylated fatty alcohol (C13-C15 alcohol, 7EO) 6% ethoxylated fatty alcohol (isotridecanol 8EO) κρζοηη / ζζηζ / Ε / γίΛΐ 5% Potassium Cocoate 5% BMM 2% MGDA (Trilon M Liquid) 5% EPEI (Sokalan HP20) 2% Fragrance 0.4% Optical Brightener (Tinopal CBS-X) Preservative and Water as needed to 100% pH 9.5-10.5 EXAMPLE 2 20% C10-13-sec-alkylbenzene 4-sulfonic acid 3.9% AMM 5% Sodium Lauryl Ether Sulfate, 3EO 10% Ethoxylated Fatty Alcohol (C13-C15 Alcohol, 7EO) 8% C10-C16 Alkyl Polyglucoside 5% Potassium Cocoate 5% BMM 2% MGDA (Trilon M Liquid) 6% EPEI (Sokalan HP20) 2% Fragrance 0.4% Optical brightener (Tinopal CBS-X) Preservative and water as needed up to 100% pH 8.5-9.5 COMPONENT 2 EXAMPLE 1 10% C10-13-sec-alkylbenzene 4-sulfonic acid 5.05% TEA 6% C14-17-sec-alkyl sulfonic acid, sodium salt 15% ethoxylated fatty alcohol (C13-C15 branched and linear alcohols, 7EO) 10% D-Glucitol, l-deoxy-l-(methylamino)-, N-C8-10 acyl derivatives 5% potassium coconate 5% BMM 0.5% of MGDA (Trilon M liquid) 4% of EPEI (Sokalan HP20). krzon / zzz / E / yLi 2% polyvinylpyrrolidone (Sokalan HP56) 2% fragrance Preservative and water as needed to 100% pH 8.0-9.0 5 EXAMPLE 2 10% C10-13-sec-alkylbenzene 4-sulfonic acid 5.05% TEA 6% C14-17-sec-alkyl sulfonic acid, sodium salt 20% ethoxylated fatty alcohol (C13-C15 alcohol, 7EO) 10 5% D-Glucitol, l-deoxy-l-(methylamino)-, N-C8-10 acyl derivatives 5% disodium capriolyl glutamate 5% potassium coconate 5% BMM 2% MGDA (Trilon M liquid) 15 2% EPEI (Sokalan HP20) 2% Polyvinylpyrrolidone (Sokalan HP56) 2% fragrance Preservative and water as needed to 100% pH 8.0-8.5 20 COMPONENT 3 EXAMPLE 1 3% sodium formate 45% sorbitol 2% protease aep (Lavergy PRO 104L) 25 0.80% lipase aep (Preferenz L100) 0.50% amylase aep (Preferenz SI 10) 0.03% citric acid Water as needed to 100% pH 4.5-5.0 30 EXAMPLE 2 3% calcium chloride 45% sorbitol 2% protease aep (Lavergy PRO 104L) 0.60% aep lipase (Lipexevity 100L). 0.45% amylase aep (Amplify prime 100L) 0.30% aep cellulase (Medley Glow 200 L) 0.15% aep mannanase (Mannaway) 0.03% citric acid Add water as needed up to 100% pH 5.0-5.5 COMPONENT 4 EXAMPLE 1 15% Estherquat (TETRANYL Ll / 90 S) 2% rice protein hydrolysate (ORYSOL) 2% Hydroxypropyltrimonium Inulin (QUATIN 680 TQ-D) 3% silicone emulsion (Ersil 66) 3% fragrance 0.6% lactic acid (2-hydroxypropanoic acid) Add water as needed up to 100% pH 2.0-3.0 EXAMPLE 2 20% Estherquat (TETRANYL Ll / 90 S) 1% rice protein hydrolysate (ORYSOL) 3% hydrolyzed wheat protein (COLTIDE™ HSI) 3% silicone emulsion (Ersil 66) 3% fragrance 0.6% lactic acid (2-hydroxypropanoic acid) Water as needed up to 100% pH 2.0-3.0 κρζοηη / ζζηζ / Ε / γίΛΐ

[0098] The dosages of the components can be determined by the logic unit on board the washing machine in the quantities shown in Table 1 according to the specific requirements of the different washing cycles: Washing temperature Component 1 (ml) Component 2 (ml) Component 3 (ml) Component 4 (ml) White tablecloths 60°C 35 0 7 10 Colored tablecloths 40°C 0 35 5 10 Normally soiled cotton garments 20°C 20 10 Synthetic fabrics 30°C 12 15 0 0 Technical / sports fabrics 30°C 0 15 3 0 Wool 0 18 0 16 RFzonn / zznz / E / YiAi Table 1

[0099] As can be understood from the description provided above, the division into the four components and the specific formulation of each component allows for a very effective washing composition and achieves the objectives set out in the preliminary observations.

[0100] In fact, with a volume sufficient to efficiently fill the circular sector compartment, the appropriate components are provided to automatically achieve the most effective washing formulations for various types of items. The specific composition of the four components allows for optimization of the nature and quantity of the individual formulations, resulting in long-lasting preservation of the active ingredients, reduced waste and environmental pollution during washing cycles, and minimal handling—a compromise that is possible for the user.

[0101] In a suitable form, the washing composition of the invention can be used with any washing machine equipped with four independent tanks suitable to be controlled by a suitable program of selection, dosing and differentiated supply.

[0102] However, it is understood that the invention should not be considered limited to the particular provisions illustrated above, which are only examples of a modality thereof, but that different variants are possible, all of them within the reach of a person skilled in the art, without departing from the scope of protection of the invention, which is defined exclusively by the following claims.

[0103] For example, although reference has always been made to more or less thick liquid components, it is not ruled out that the washing composition may also use, at least in part, completely dehydrated components, for example in powder or small granules (hence still fluid, so that it can be easily transported to the washing chamber of a washing machine).

Claims

CLAIMS 1. A fluid washing composition with four separate components housed in respective independent tanks of a washing machine equipped with a program for the selection, dosage and differentiated delivery of said separate components according to the variable characteristics of the individual laundry batch, characterized in that said separate components have the following formulation: Component 1 - detergent formulation with a pH of between 4.0 and 12.0, with high detergent effect in washing programs at temperatures in the range of 40°-60°C, with specific action on cotton fibers and, in particular, on white garments; Component 2 - detergent formulation with a pH of between 8.0 and 12.0, with high detergent effect in washing programs at temperatures in the range of 15°-40°C, with specific action on synthetic, colored and animal-derived fibers; Component 3 - enzyme-based stain-removing formulation based on at least protease and lipase and possibly amylase with a pH ranging from 5.0 to 6.0 and preferably from 5.0 to 5.5, stabilized with sorbitol and calcium chloride; Component 4: conditioning formulation for after washing, with a pH ranging from 2.0 to 4.

0.

2. The washing composition according to claim 1, characterized in that said component 1 consists of a mixture of anionic and non-ionic surfactants in active ingredient ratios ranging from 75:25 to 50:50, wherein said anionic surfactants are selected from alkylbenzenesulfonates, alkylbenzene ether sulfates and alkyl sulfates, and said non-ionic surfactants are selected from ethoxylated fatty alcohols, alkyl polyglucosides or alkyl polypentosides, both primary and secondary.

3. The washing composition according to claim 2, characterized in that it contains surfactants in an amount in the range of 20% to 50% of active agent, soaps in an amount in the range of 1% to 10% of active agent, various additives with a stabilizing, dispersing, anti-residue and degreasing function, collectively in an amount in the range of 2%-10% of active agent, oxidizing brighteners and optical brighteners in the amount in the range of 0.05% to 1% of active agent and water up to 100%.

4. The washing composition according to any of the preceding claims, characterized in that said component 2 consists of a mixture of anionic and non-ionic surfactants in active agent ratios ranging from 25:75 to 50:50, wherein said anionic surfactants are selected from alkylbenzene sulfonates and sulfonated olefins, RFzonn / zznz / E / YiAi optionally supplemented with glucomides, and said non-ionic surfactants are selected from ethoxylated fatty alcohols, both primary and secondary, having a degree of ethoxylation greater than or equal to 5 moles and alkyl chains between C10 and C18.

5. The washing composition according to claim 4, characterized in that it contains surfactants in an amount ranging from 30% to 60% of the active ingredient, additives with bacteriostatic function and odor elimination aids in an amount ranging from 1% to 5% of the active ingredient, miscellaneous additives with a stabilizing, dispersing, anti-residue and degreasing function, overall in an amount between 2% and 10% of the active ingredient, and water up to 100%.

6. The washing composition according to any of the preceding claims, characterized in that said component 3 consists of a mixture of enzymes comprising at least a protease, a lipase and an amylase and, optionally, a cellulase and / or a mannanase.

7. The washing composition according to claim 6, characterized in that in component 3 the content of said protease is up to 3% of aep, the content of said lipase is up to 1% of aep, the content of said amylase is up to 0.5% of aep and any content of said cellulase and mannanase is up to 0.5% of aep each.

8. The washing composition according to claim 7, characterized in that said protease is a subtilisin.

9. The washing composition according to claim 7, characterized in that component 3 further contains a stabilizing additive consisting of polyols, preferably selected from glycerol and sorbitol.

10. The washing composition according to claim 9, characterized in that the total monopropylene glycol content does not exceed 10% of the active agent.

11. The washing composition according to claim 1, characterized in that said component 4 comprises a cationic surfactant of the esterquat category, possibly with added propylene glycol or alcohol.

12. The washing composition according to claim 11, characterized in that component 4 contains said cationic surfactant in an amount in the range of 5% to 20% active agent, a lactic acid-based bacteriostatic additive in an amount in the range of 2% active agent, an inulin-based softening additive in an amount in the range of 0.2% to 2% active agent, a rice protein-based softening additive in an amount in the range of 0.4% to 3% active agent, and water up to 100%.

13. The washing composition according to any of the preceding claims, characterized in that said components 1 to 4 are arranged in respective tanks with