Automatic dishwashing composition in unit dose form comprising an anti-scaling polymer

ES 2 328 680 T3

DESCRIPTION

Composition for automatic dishwashers in unit dose form comprising an antifouling polymer.

Technical field

The present invention relates to the field of dishwashing. In particular, it relates to dishwashing compositions in unit dose form comprising an antifouling polymer. The compositions and products provide excellent gloss benefits.

Background of the invention

Polyphosphates are desirable components in dishwasher detergent compositions because they are very effective scale inhibitors but present a significant drawback. Polyphosphates over time hydrolyze to orthophosphate. Orthophosphate does not act as a scale inhibitor and will actually scale with calcium (calcium phosphate). A similar problem occurs when the wash solution contains a high level of calcium or the solution is in some other semi-structured way. Scale deposits not only form films and stains on the dishes, cutlery and glassware but also inside the dishwasher, especially on the heating element (hydrolysis is favored at elevated temperatures), thus negatively affecting the efficiency of the cooking process. dishwasher safe.

Carbonates are also common components in dishwashing detergent compositions and can also cause fouling and therefore filming and staining problems on washed items. Traditionally, filming and staining problems have been ameliorated by using salt to soften the water (to reduce the concentration of cations, especially Ca²⁺ and Mg²⁺) and using sequestrant that contains rinse aid, dispersant and surfactant that to some extent help to control the hardness of the ions present in the water and to reduce the surface tension of the dishwashing solution, thus avoiding the formation of liquid droplets. and allowing uniform drying of washed utensils, reducing filming and staining problems.

The use of sulfonated polymers to reduce scale formation in the dishwasher is known in the art. In EP-A-851,022 a polymer comprising an olefinically unsaturated carboxylic acid monomer and at least one monomeric unit selected from copolymerizable sulfonated monomers, copolymerizable non-ionic monomers and mixtures thereof is used in a rinse-inhibiting composition. EP-A-1,111,037 discloses a detergent bar having two separate regions, wherein one of the regions comprises dissolution retarding materials and wherein said region may also comprise an antifouling agent.

WO-A-01/72941 describes a dishwashing composition comprising a builder additive and at least one polymer comprising carboxylate groups and sulfonate groups. US 6,191,088 describes a powder dishwashing composition comprising a polymer containing sulfonic acid groups.

In FR 2 802 548 the use of a dishwasher tablet is described in a process for washing dishes in which no rinse aid or salt is added to the machine and is not part of the tablet. The bar comprises more than 45% by weight of a builder additive and has a defined distinct region A which is at most 30% by weight of the total weight of the bar. The distinct region A further comprises a material that controls the dissolution in water of the region. In addition, region A may also comprise an anti-sealant polymer that is present at a supply level of 1-100 ppm in a 5 liter rinse.

In US 6 172 020 a composition for dishwashing which can be in the form of a tablet is described which generally comprises a hydrated alkali metal phosphate builder salt, an anhydrous alkali metal phosphate builder salt, a carbonate alkali metal, a dialkali metal disilicate, a nonionic surfactant, a polymer containing sulfonic acid groups, a peroxygen bleach, a peroxygen bleach activator, a protease enzyme, an amylase enzyme, a hydrotrope, and a clay.

US 5 958 855 describes a dishwashing composition which may be in the form of a tablet comprising an alkali metal phosphate and alkali carbonate builder salt, a dialkali metal disilicate, a nonionic surfactant, a polymer of Alkali metal metasilicate containing sulfonic acid groups, a chlorine bleaching compound, a hydrotrope, and a clay.

In US 4 776 455 a multi-compartment sachet product is described for supplying treating agent to the washing machine or dishwasher that comprises a first compartment capable of releasing its contents (solid or liquid) within three minutes from the start of the process of washing and a second compartment of water-permeable material provided with a pore-occluding coating and / or in the form of a sachet within another sachet so that the release of its content (powder) is delayed at least five minutes from the restart of the wash cycle.

WO 01/83657 A2 describes a multi-compartment bag made from a water-soluble film having at least two compartments, wherein said multi-compartment bag comprises a composition that

ES 2 328 680 T3 comprises a solid component and a liquid component, wherein; (a) a first compartment comprises a solid component comprising (by weight of the solid component) at least 10% water-insoluble solid material; and (b) a second compartment comprises a liquid component. A second embodiment comprises a multi-compartment bag, wherein; (a) a first compartment comprises a solid component comprising at least 15% by weight of particles containing at least 20% by weight of the surfactant particle; and (b) a second compartment comprises a liquid component.

The following documents are part of the state of the art according to article 54 (3) EPC: WO 01/96514 A1, WO 02/074891 A2 and WO 03/006594 A1.

WO 01/96514 A1 describes a dishwashing composition including (A) an antifouling polymer formed from (i) 50-99% by weight of the polymer of an olefinically unsaturated carboxylic acid monomer, (ii) at 50% of at least one monomeric unit selected from the group consisting of copolymerizable sulfonated monomers, copolymerizable nonionic monomers, and mixtures thereof; (B) 0.1 to 99.9% of a polymer releasing vehicle at the penultimate and final rinse cycles of a dishwasher wash sequence. In addition, a method of cleaning dishes with said composition and the use of said composition to prevent fouling in mechanical dishwashing is provided.

WO 02/074891 A2 describes a water soluble sachet comprising a dishwashing composition wherein the dishwashing composition is a gel comprising an encapsulated bleach. The water soluble sachet further comprises a dishwashing composition having: (a) a polymer having a molecular weight greater than about 2,000 and comprising a positive charge; and (b) a water soluble polymer that reduces phosphate scale, a compound that reduces carbonate scale, or both, wherein the dishwashing composition is a gel. In addition, there is provided a method of reducing scale formation and a package comprising the dishwashing composition and instructions not to use a rinse aid composition or separate salts.

WO 03/006594 A1 describes a liquid aqueous dishwashing product comprising (a) from 20 to 50% by weight of one or more water-soluble builder additives; (b) 0.1 to 70% by weight of copolymers of i) unsaturated carboxylic acids, ii) monomers containing sulfonic acid groups, iii) optionally other ionic or non-ionic monomers; (c) 5 to 30% by weight of nonionic surfactant (s). It also describes the composition packaged in separate parts in water soluble closures.

Traditionally, the dishwasher washing process involves the steps of dosing detergent into the dispenser at the beginning of each wash and filling the reservoirs with salt and rinse aid at the necessary intervals. Some users may find it difficult to perform all of these steps and prefer a simple process that involves the use of a single product that performs all the functions necessary for the dishwasher washing process. Dishwashing detergent unit dosages have been found to be more attractive and suitable for some consumers and furthermore avoid the consumer having to measure the product thereby providing a more accurate dosing and avoiding unprofitable overdosing or underdosing. For this reason, dishwasher detergent products in tablet form have become very popular. Bag-shaped detergent products are also known in the art.

The dishwashing detergent product is usually placed into the dispenser to be released during the main wash cycle of the dishwashing process. However, the dispensers of some dishwashers are not completely watertight, mainly for two reasons: the dispenser has some openings that allow the entry of water or the dispenser is sealed with a rubber band that can deform over time due to the high temperature of the dishwashing process. The entry of water into the dispenser can cause a premature leakage of the dishwashing product which is consequently lost after the pre-rinse. This problem is especially acute in the case of liquid compositions having a low viscosity in which a considerable amount of the product can be lost before the main wash cycle. In the case of solid compositions, water leakage in the dispenser can also be a problem that can cause, for example, caking of the composition or loss of activity of some ingredients such as bleach.

Summary of the invention

The present invention relates to fortified dishwasher compositions in unit dosage form comprising a sulfonated antifouling polymer and a means for supplying the sulfonated polymer to the main wash cycle of a dishwasher. Compositions that contain a builder and provide a certain level of sulfonated antifouling polymer to the main wash solution have been found to be effective in inhibiting calcium phosphate and calcium carbonate scale formation with consequent reduction of the scale. film formation on washed items and gloss enhancement.

Accordingly, according to a first aspect of the invention, a dishwashing composition is provided in unit dose form for delivery to the main wash cycle of a dishwashing machine, wherein the unit dose form provides 10 to 40 g, preferably 12 to 25 g and most preferably 15 to 22 g of the dishwashing detergent composition to the main wash cycle, wherein the composition comprises

ES 2 328 680 T3 carbonate, a phosphate-type or non-phosphate-type builder and 3% to 6% by weight of the composition of a sulfonated antifouling polymer sufficient to provide at least 125 ppm, even more preferably at least 140 ppm, and especially at least 160 ppm, of polymer by weight of the wash solution.

The carbonate source can be selected from carbonate-containing compounds or carbonate-producing compounds under wash conditions. Preferred carbonate sources are alkali metal carbonates, bicarbonates, percarbonates, and mixtures thereof. In preferred embodiments, the compositions and products of the invention comprise 6 to 50%, preferably 10 to 40%, of the carbonate source by weight of the composition.

The alkali silicate is preferably free of metasilicate. Silicates are preferred where the ratio of SiO₂ and alkali metal oxide (M₂O, where M = alkali metal) is typically 1.8 to 3, preferably 2 to 2.4. Compositions for use in the present invention preferably comprise alkali silicate at a level of 2% to 20%, preferably 3 to 10%, by weight of the composition and are free of metasilicate.

Optimal cleaning and filming benefits are obtained when the builder and polymer are in a weight ratio of 5: 1 to 15: 1. The term "builder additive" as used herein includes sequestering builders (eg, phosphates and citrates) and precipitants (eg. carbonates) but excludes materials that act primarily as alkalis such as caustic soda, caustic potash, and alkali silicates, such as sodium metasilicate and amorphous silicates that have a SiO ratio.₂: Na₂Or greater than 1. As described above, the compositions of the invention may, however, comprise alkali metal silicates to provide protection against corrosion of metals and against attack on tableware, including porcelain and glass materials. , and to control pH, although the compositions are preferably free of metasilicates. Metasilicates produce high pH compositions that can be aggressive and cause corrosion and attack on dishes, cutlery and glassware. Preferably, the composition has a pH in the wash solution of 9 to 11, preferably 10 to 10.8.

The cleaning and finishing action achieved with the composition of the invention can be improved by incorporating detergent enzymes, preferably proteases. These provide significant protein soil removal benefits, especially egg and starch soil. Accordingly, the film-forming benefits provided by the sulfonated polymer and the stain-forming benefits provided by the detergent enzymes combine synergistically to provide outstanding gloss benefits. Accordingly, according to another aspect of the invention, there is provided a composition comprising a sulfonated antifouling polymer; a detergent enzyme and a means for supplying, simultaneously or sequentially, the sulfonated polymer and the detergent enzyme to the main wash cycle of a dishwasher. In a preferred embodiment, the enzyme is a proteolytic enzyme. The amiolytic enzyme is also preferred for use in the present invention.

Due to the excellent properties of the polymer, the absolute amount of detergent used in the dishwashing process can be reduced without reducing the cleaning and finishing ability. Accordingly, the invention provides a unit dosage form adapted to provide 10 to 40 g, preferably 12 to 25 g, and especially 15 to 22 g, of the dishwashing detergent composition to the main wash cycle of a dishwasher. . The polymer is present in the dishwashing composition at a level of 3% to 6% by weight of the composition.

A dishwasher operation typically comprises three or more cycles: a prewash cycle, a main wash cycle, and one or more rinse cycles. In Europe the prewash cycle, when used, is typically a cold water cycle lasting 6 or 7 min. In the main wash cycle, the water enters cold and heats up to 55 or 65 ° C, this cycle lasting 20 min. The rinse usually comprises two or more separate cycles after the main wash, where the first is cold and lasts between 2 and 5 min and the second starts with cold water and heats up to 65 ° C or 70 ° C and lasts 20 min. The dishwasher is filled with cold water at the beginning of each cycle and emptied at the end of each cycle through a filter. Most dishwashing detergent ingredients are formulated to perform more efficiently during the main wash cycle due to the temperature and length of this cycle. Detergent for the main wash is placed in the dispenser, which opens automatically at the beginning of the main wash. However, the design of some dispensers includes some holes that allow water to enter, although other dispensers become less watertight due to wear and tear. The fact that the dispensers are not watertight can lead to different problems. Firstly, the detergent may leak out before the main wash cycle, secondly, some of the detergent ingredients may lose activity before being supplied to the wash solution, and thirdly, especially in the case of solid compositions, sticking and caking problems can occur. In view of these problems it is desirable to protect the dishwasher detergent at least until the main wash cycle, as described in detail below.

Unit dose forms suitable for use in the present invention include single and multi-compartment bags, capsules, and ampoules. For use in the present invention, bags, both single compartment and multi compartment, are preferred. For the purposes of achieving a phased or sequential delivery of detergent actives it is preferred that at least two of the compartments of a multi-compartment bag have different disintegration rates or dissolution profiles under the conditions of use. The solubility of the film can be controlled by, for example, pH, temperature, ionic strength, or by any other means.

ES 2 328 680 T3

Suitable for use in the present invention are products in unit dose form that are practically insoluble in cold water and soluble in hot water to protect detergent during the prewash cycle and release it during the main wash cycle. The unit dose form can be designed to be placed in the dispenser of the dishwasher or alternatively it can be designed to be placed outside of the dispenser of the dishwasher, for example in the cutlery basket, in a net or in the door or the door. dishwasher floor. In a preferred embodiment, the protection of the dishwasher detergent is achieved by making one or more compartments of the bag of a film-like material that is practically insoluble in cold water (that is, at a temperature equal to or less than 20 ° C). and soluble in hot water (that is, at a temperature equal to or greater than 30 ° C, preferably greater than 40 ° C). In a preferred embodiment, and from the point of view of the phased or sequential supply of detergent active substances, at least one of the compartments is made of a material that is practically insoluble in cold water at a temperature equal to or less than 20 ° C and soluble in hot water at a temperature equal to or greater than 30 ° C and at least one other compartment is made of a material that is soluble in cold water at a temperature equal to or less than 20 ° C. Alternatively, the entire bag can be made of a material that is practically insoluble in cold water but soluble in hot water.

Preferably the film material has a water solubility, as defined herein below, of less than 50%, more preferably less than 20% and especially less than 5%, under cold water conditions. (20 ° C or lower) when exposed to water for at least 10 minutes, preferably for at least 15 minutes; and a water solubility of at least 50%, more preferably at least 75% and especially at least 95% in hot water conditions (30 ° C or higher, preferably 40 ° C or higher) when exposed to water for 5 minutes and preferably when exposed to water for 3 minutes. As used herein, such film-like materials are practically insoluble in cold water although soluble in hot water. Sometimes this is simply abbreviated as "soluble in hot water." Apart from providing a phased release, this type of material also solves the problem of gelling of the pouch material when handled with wet hands.

Add 50 grams ± 0.1 grams of bag material to a 400 ml beaker weighed previously and then 245 ml ± 1 ml of distilled water. The mixture is kept at the desired temperature using a water bath and vigorous stirring on a magnetic stirrer set at 600 rpm, for the desired time. The mixture is then filtered through a sintered glass filter with pleated qualitative paper with a maximum pore size of 20 μιη. The water is removed from the collected filtrate by any conventional method and the weight of the remaining material (which is the dissolved or dispersed fraction) is determined. The% solubility or dispersibility is then calculated.

Suitable bags for use in the present invention can be in the form of a single compartment bag where the contents of the bag can be in the form of a liquid, gellable liquid, paste, gel, liquid-solid suspension, loose powder, densified powder, powder. compacted (eg, spheres, noodles), pellet, or mixtures thereof. Single compartment bags are very attractive from the point of view of the simplicity of the process.

Alternatively, the bag of the invention can be a multi-compartment bag. These bags are especially useful for dispensing ingredients in different physical forms, to allow for delayed or sequential release effects, and to separate incompatible detergent ingredients during storage or during the dishwasher washing process. Preferred embodiments for use in the present invention are multi-compartment bags having at least two compartments exhibiting different disintegration rates or disintegration profiles. In a preferred embodiment a multi-compartment bag is provided comprising a first compartment comprising a liquid composition and a second compartment comprising a solid composition. Preferably, the liquid-containing compartment is made of a hot water soluble material, as described hereinbefore, and the solid-containing compartment is made of a cold water soluble material, that is, a material that is soluble at a level of at least 50%, preferably at least 75%, more preferably at least 95%, by weight under cold water conditions (20 ° C or lower) when exposed to water for 5 minutes and preferably when exposed to water for 3 minutes. Due to the way European dishwashers work (they are filled with cold water and the cold water is heated by a heater), the compartment made of hot water soluble material takes longer to dissolve than the compartment made of soluble material in cold water. This form of bag allows a delayed release of the liquid composition providing an optimized use of the detergent composition. Preferred for use in the present invention are bags in which the liquid detergent composition and the solid detergent composition are in a weight ratio of 1:30 to 30: 1, preferably 1: 1 to 1:25 and more preferably from 1:15 to 1:20. Liquid compositions comprising detergent enzyme are preferred as this is advantageous from the viewpoint of stability of the enzyme during storage because the enzyme is separated from bleach and highly alkaline materials contained in the solid composition. Furthermore, the compartment containing the liquid (practically insoluble in cold water and soluble in hot water) will take longer to dissolve or disintegrate than the compartment containing the solid (soluble in cold water), minimizing negative interaction in the wash solution between bleach and enzymes and between surfactant and enzymes and providing better protein stain removal and pretreatment benefits in later stages of the dishwashing process.

The interaction of the negatively charged polymer with surfactants, especially with semi-polar or positively charged surfactants, such as for example amine oxides, can lead to the formation of coacervates that reduce the activity and therefore the cleaning and finishing ability. provided by both materials

ES 2 328 680 T3 therefore it is desirable to place the surfactant and the polymer in different compartments. The compartments of bags containing solid compositions, in particular compositions comprising oxygen-releasing bleach, are usually perforated in order to allow any formed oxygen to escape. However, the drilled holes can also allow the escape of perfumes or bad odors. For example, surfactants frequently have an associated unpleasant odor and when such bags are packaged within a secondary package, the unpleasant odor of the surfactant can concentrate in the headspace of the package to escape each time the user opens the package. This problem can be avoided by including the surfactant in the liquid composition, since the compartments containing the liquid must be free of drilled holes. Thus, according to another embodiment, the liquid composition comprises a surfactant. Another advantage of having the surfactant in the liquid phase is that the problems of loading the surfactant onto the solid material are avoided. Another advantage is that the surfactant is released with a certain delay with respect to the solid composition, which allows a better performance of the bleach and the enzymes, which can be adversely affected by the interaction between the surfactant and the surfaces of the crockery, cutlery and glassware.

Preferably the perfume is introduced into the solid composition and the perforation allows a release of the perfume before using the product in the dishwasher.

Due to the antifouling properties provided by the compositions and products of the invention, the use of salt is not necessary and, due to the shine benefits, the use of rinse aid is not necessary either. Accordingly, according to another aspect of the invention there is provided the use of the composition or product for washing dishes, cutlery and glassware / kitchen utensils in a dishwasher in which no rinse aid or salt is used. The composition of the invention not only provides better shine to washed dishes, cutlery and glassware / kitchen utensils but also prevents the deposition of encrustations on the parts of the dishwasher, especially on the heating element that is more prone to the formation of encrustations. due to the fact that high temperatures favor the formation of phosphate and carbonate scale. The problem of scale deposits on the heating element is not only aesthetic but also the fact that the heat transfer coefficient between the heating element and the water is reduced and consequently the efficiency of the heating process is also reduced. heating the water and washing in the dishwasher.

According to another aspect of the invention, there is provided a method of washing dishes, cutlery and glassware / kitchen utensils in a dishwasher which consists of treating the dishes, cutlery and glassware / kitchen utensils with the composition or the product of the invention. In a preferred embodiment, a bag or other unit dose comprising the compositions of the invention is supplied to the main wash cycle through the dispenser of the dishwasher.

Detailed description of the invention

The present invention contemplates dishwashing compositions in unit dose form comprising a sulfonated antifouling polymer for delivery to the main wash cycle. The compositions and products provide shine benefits and avoid the use of salt and rinse aid. The invention also provides methods and uses of such compositions and products.

Sulfonated antifouling polymer

An essential component of the composition of the invention is a sulfonated antifouling polymer. The composition of the invention comprises from 3 to 6%, preferably from 3.5 to 5%, by weight of the polymer composition. The polymer generally comprises 0.1% to 90%, preferably 1% to 30%, by weight of a sulfonic acid-containing monomer. Examples of sulfonate monomers include, but are not limited to, allylhydroxypropanyl sulfonate ethers, allylsulfonic acids, methallylsulfonic acids, styrene sulfonic acids, vinyl toluenesulfonic acids, acrylamido alkanesulfonic acids, allyloxybenzene sulfonic acids, 2-alkylallyloxybenzene sulfonic acids such as 4-alkylallyloxybenzene sulfonic acids. and the alkali or alkaline earth metal or ammonium salts thereof.

Suitable examples of scale inhibitor copolymers include, but are not limited to, tetrapolymers of 4-sulfophenol methallyl ether, sodium methallylsulfonate, acrylic acid, and methyl methacrylate. The monomeric unit, the methallyl sulfophenol ether, has the formula:

CH₂ = C (CH₃) CH₂OC₆H₄SW₃M where M represents hydrogen, alkali metal, alkaline earth metal, or ammonium ions.

Other suitable examples of scale inhibitor copolymers include, but are not limited to, a copolymer of acrylic acid and 4-sulfophenol methallyl ether; a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulfonate; a terpolymer of acrylic acid, 2-acrylamido-2-methylpropane sulfonate and sodium styrene sulfonate; and a polymer of sulfophenyl methallyl ether, sodium methallylsulfonate, acrylic acid, methyl methacrylate, and 2-acrylamido-2-methyl propane sulfonic acid. Preferably, the polymer is the tetrapolymer of 4-sulphenol methacrylate, sodium methallylsulphonate, acrylic acid, and methyl methacrylate. Preferred for Use Here

Invention ES 2 328 680 T3 are copolymers comprising polyacrylic acid, methyl methacrylate, methallyl ether sulphenol and sodium methallyl sulphonate.

Preferred commercial copolymers include: Alcosperse 240, Aquatreat AR 540, and Aquatreat MPS, available from Alco Chemical; Acumer 3100 and Acumer 2000, available from Rohm & Haas; Goodrich K-798, K-775 and K-797, available from BF Goodrich; ACP 1042, available from ISP technologies Inc .; and polyacrylic acid / acrylamide, available from Aldrich. An especially preferred copolymer is Alcosperse 240, available from Alco Chemical.

Hot water soluble bag material

The bag material is such as to allow the supply of the sulfonated polymer to the main wash cycle, for example, a material that is insoluble in water at a temperature of 20 ° C or lower and soluble or dispersible in water at a temperature 30 ° C or higher, as previously described herein. Apart from the thermodynamic solubility characteristics, the dissolution kinetics of the film and its mechanical stability also play a significant role in the present invention. Commercial polyvinyl alcohols (PVAs) obtained by hydrolysis of polyvinyl acetates are preferred for use in the present invention. The solubility of these films can be selectively adjusted by the degree of hydrolysis of the PVA or by using a cross-linking agent. Examples of commercial PVA suitable for use in the present invention are BP26, sold by Aicello, L10 and L15, sold by Aquafilm, VF-M and VM-S, sold by Kuraray, and E-2060, sold by Monosol, but especially Preferred for use in the present invention is BP26, available from Aicello. Film thickness can affect dissolution kinetics, with films having a thickness of between 10 and 100 µm being preferred for use in the present invention.

Other preferred materials for use in the present invention are starch, starch derivatives, cellulose, and cellulose derivatives, more especially methylcellulose, and mixtures thereof. Especially preferred for use in the present invention are polymers comprising hydroxypropylmethylcellulose.

Surfactant

In the compositions and methods of the invention, the detergent surfactant is preferably low foaming on its own or in conjunction with other components (ie suds suppressors). Suitable surfactants in the present invention include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, alkylglyceryl sulfonates, alkylsulfonates and alkenylsulfonates, alkyl ethoxy carboxylates, N-acylsarcosinates, N-acyltaurates, and alkylsuccinates, and sulfosuccinates moiety, and alkylsuccinates, where alkylsuccinates and sulfosuccinates acyl is C₅-C₂or, preferably linear or branched Cio-Cis; cationic surfactants such as chlorine esters (US-4228042, US-4239660 and US-4260529) and mono N-alkyl or alkenyl C surfactants₆ -C₁₆ ammonium, where the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups; Low and high cloud point nonionic surfactants and mixtures thereof, including alkoxylated nonionic surfactants (especially ethoxylates derived from C alcohols₆-C₁₈ primary), ethoxylated-propoxylated alcohols (eg BASF Poly-Tergent® SLF18), epoxy capped poly (oxyalkylated) alcohols (eg BASf Poly-Tergent® SLF18B; see WO-A -94/22800), surfactants of the type terminal poly (oxyalkylated) alcohols protected with ether groups and polymeric polyoxyethylene-polyoxypropylene block compounds such as PLURONIC^®, REVERSED PLURONIC® and TETRONIC® from BASF-Wyandotte Corp., Wyandotte, Michigan; Amphoteric surfactants such as C12-C2 alkyl amine oxides (preferred amine oxides for use in the present invention include lauryl C₁₂ dimethyl amine and C oxide₁₄ and C₁₆ hexadecyl dimethyl amine) and alkyl type amphocarboxylic surfactants such as Miranol ™ C2M and zwitterionic surfactants such as betaines and sultaines and mixtures thereof. Suitable surfactants in the present invention are described, for example, in US-3,929,678, US-4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874. Surfactants are typically present at a level of 0.2% to 30% by weight, more preferably 0.5% to 10% by weight, and most preferably 1% to 5% by weight, of the composition. The surfactants of preferred use in the present invention are low foaming surfactants and include low cloud point nonionic surfactants and mixtures of high foaming surfactants with low cloud point nonionic surfactants which act as suds suppressants therefor.

Builder Additive

Suitable builder additives for use in the detergent and cleaning compositions of the present invention include those builder additives that form water soluble hardness ion complexes (sequestering builder additive) such as citrates and polyphosphates, p. ex. sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed salts of sodium and potassium tripolyphosphate, and those builder additives that form hardness precipitates (precipitating builder additive) such as carbonates, e.g. ex. sodium carbonate. The builder is typically present at a level of 30 to 80%, preferably 40 to 70%, by weight of the composition. It is also preferred that the ratio of the sequestering builder to the precipitating builder is 10: 1 to 1: 1, preferably 8: 1 to 2: 1.

ES 2 328 680 T3

Silicates

Suitable silicates for use in the present invention include partially water-soluble or water-insoluble builder additives such as crystalline layered silicates (EP-A-0164514 and EPA-0293640) and aluminosilicates, including zeolites A, B, P, X, HS and MAP.

Amorphous sodium silicates that have a SiO ratio₂: Na₂Or 1.8 to 3.0, preferably 1.8 to 2.4 and most preferably 2.0, can also be used in the present invention albeit from the point of view of long-term storage stability Compositions containing less than 22%, preferably less than 15%, total silicate (amorphous and crystalline) are highly preferred.

Enzyme

Preferred enzymes for use in the present invention are proteolytic enzymes such as Esperase^®, Alcalase^®, Durazym^® and Savinase^® (from Novo) and Maxatase^®, Maxacal^®, Properase^® and Maxapem^® (from Gist-Brocades). Other suitable enzymes for use in the present invention include bacterial and fungal cellulases such as Carezyme and Celluzyme (ex Novo Nordisk A / S); peroxidases; lipases such as Amano-P (from Amano Pharmaceutical Co.), M1 Lipase® and Lipomax® (from Gist-Brocades) and Lipolase® and Lipolase Ultra® (from Novo); cutinases; α and β amylases such as Purafect Ox Am^® (from Genencor) and Termamyl^®, Ban^®, Fungamyl^®, Duramyl^® and Natalase^® (from Novo); pectinases; and mixtures thereof. The enzymes are preferably added in the present invention as pellets, granules or cogranulates at a level typically in the range of 0.0001% to 2% pure enzyme by weight of the composition.

Bleaching agent

Suitable bleaching agents in the present invention include chlorine bleaches and oxygen-releasing bleaches, especially inorganic perhydrate salts, such as sodium perborate monohydrate and tetrahydrate and optionally coated sodium percarbonate to provide a controlled rate of release (see, for example, sulfate coatings / carbonate in GB-A-1466799), Preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and / or transition metal containing bleach catalysts (especially manganese or cobalt). The perhydrated inorganic salts are typically incorporated at a level in the range of 1% to 40% by weight, preferably 2% to 30% by weight, and more preferably 5% to 25% by weight, of the composition. Sodium percarbonate is preferred for use in the present invention as part of the carbonate source. Preferred peroxyacid bleach precursors for use in the present invention include perbenzoic acid and substituted perbenzoic acid precursors; cationic peroxyacid precursors; peracetic acid precursors, such as TAED, sodium acetoxybenzene sulfonate, and pentaacetylglucose; pernonanoic acid precursors, such as sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386) and benzoxazine peroxyacid precursors (EP-A-0332294 and EP-A-0482807). Bleach precursors are typically incorporated at a level in the range of 0.5% to 25%, preferably 1% to 10%, by weight of the composition although the previously formed organic peroxyacids themselves are typically incorporated into a level in the range of 0.5% to 25% by weight, more preferably 1% to 10% by weight, of the composition. Preferred bleach catalysts for use in the present invention include manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); the bispyridylamine of Co, Cu, Mn and Fe and related complexes (US-A-5114611) and the acetate of pentamine and cobalt (III) and related complexes (US-A-4810410).

Low cloud point nonionic surfactants and suds suppressors

Suds suppressors suitable for use in the present invention include nonionic surfactants that have a low cloud point. The term "cloud point", as used herein, is a well known property of nonionic surfactants whereby the surfactant becomes less soluble as the temperature increases, the temperature at which the "cloud point" is increased. a second phase appears (see Kirk Othmer, pp. 360-362). Herein, a "low cloud point" nonionic surfactant is defined as an ingredient of the nonionic surfactant system having a cloud point of less than 30 ° C, preferably less than 20 ° C, even more preferably less than 10 ° C and most preferably less than 7.5 ° C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Also such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g. Poly-Tergent® SLF18 from BASF) and end-capped polyoxyalkylated alcohols with epoxy groups (e.g., BASF's Poly-Tergent® SLF18B series of nonionic surfactants, as described, for example, in US Pat. .576.281).

ES 2 328 680 T3

Preferred low cloud point surfactants are ether capped polyoxyalkylated suds suppressors having the formula:

<img file="ES2328680T3_D0001.tif" />

where R¹ is a linear alkyl hydrocarbon having an average of 7 to 12 carbon atoms, R² is a linear alkyl hydrocarbon of 1 to 4 carbon atoms or, R³ is a linear alkyl hydrocarbon of 1 to 4 carbon atoms, x is an integer from 1 to 6, y is an integer from 4 to 15, and z is an integer from 4 to 25.

Other low cloud point nonionic surfactants are ether capped polyoxyalkylated surfactants having the formula:

RjOfRn O)_nCH (CH3) OR_m where R_I is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having 7 to 12 carbon atoms; R_II may be the same or different and is independently selected from the group consisting of C alkylene₂ to C₇ branched or linear in any molecule; n is a number from 1 to 30; and R_III is selected from the group consisting of:

(i) a 4- to 8-membered substituted or unsubstituted heterocyclic ring containing 1 to 3 heteroatoms; and (ii) linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms;

(b) provided that when R² is (ii) then or: (A) at least one of R¹ is other than C2 to C3 alkylene or (B) R² has from 6 to 30 carbon atoms and with the proviso that when R² has 8 to 18 carbon atoms, R is other than C1 to C alkyl₅.

Other suitable components in the present invention include organic polymers having detergent dispersant, anti-redeposition, soil release or other properties according to the invention at levels of 0.1% to 30%, preferably 0.5% to 15%. , most preferably 1% to 10%, by weight of the composition. Preferred antiredeposition polymers in the present invention include acrylic acid containing polymers, such as Sokalan PA30, pA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acid copolymers acrylic / maleic acid, such as Sokalan CP5, and acrylic / methacrylic copolymers. Preferred soil release polymers in the present invention include alkyl celluloses and hydroxyalkyl celluloses (US 4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on esters of ethylene glycol terephthalate, propylene glycol and mixtures thereof.

Heavy metal sequestrants and crystal growth inhibitors are suitable for use in the present invention at levels generally 0.005% to 20%, preferably 0.1% to 10%, more preferably 0.25% to 7, 5% and most preferably 0.5% to 5%, by weight of the composition, for example diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene- 1,1-diphosphonate, nitrilotriacetate, ethylenediaminetetracetate, ethylenediamine-N, N'-disuccinate in their salt and free acid forms.

The compositions of the present invention may contain a corrosion inhibitor such as organic silver coating agents at a level of 0.05% to 10%, preferably 0.1% to 5%, by weight of the composition (especially paraffins such as Winog 70 available from Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibiting compounds (for example benzotriazole and benzimadazole - see GB-A-1137741) and Mn (II) compounds, especially Mn (II) salts of organic ligands at a level of 0.005% to 5%, preferably 0.01% to 1%, more preferably 0.02% to 0.4%, by weight of the composition.

Other suitable components in the present invention include colorants, water soluble bismuth compounds such as bismuth acetate and bismuth citrate at a level of 0.01% to 5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach removers at a level of 0.01% to 6%, lime soap dispersants (see WO-A-93/08877), suds suppressants (see WO-93/08876 and EPA-0705324), polymeric dye transfer inhibitors, optical brighteners, perfumes, fillers and clays.

The liquid detergent compositions of the present invention may contain small amounts of low molecular weight primary or secondary alcohols, such as methanol, ethanol, propanol, and isopropanol. Others

ES 2 328 680 T3 Suitable solvent carriers used in small amounts include glycerol, propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol, and mixtures thereof.

Bag

Especially useful unit dose forms for use in the present invention are bags. The bag of the present invention is typically a closed structure preferably comprising two or more compartments and made from the materials described herein. Subject to the limitations of fitment to the dispenser, the bag can be of any shape, configuration and material that is suitable for containing the composition, e.g. eg, by preventing the composition from being released from the bag before the bag comes into contact with water. The exact implementation will depend, for example, on the type and quantity of the composition in the bag, the number of compartments in the bag, its characteristics required to contain, protect and deliver or release the composition and / or components thereof. .

The composition, or components thereof, are contained in the internal volumetric space and are typically separated from the external environment by a barrier of water-soluble material. Typically, different components of the composition contained in different compartments of the bag are separated from each other by a barrier of water-soluble material.

In the case of multi-compartment bags, the compartments can be of different colors, for example, a first compartment can be green or blue and a second compartment can be white or yellow. One compartment of the bag can be opaque or semi-opaque and a second compartment of the bag can be translucent, transparent or semi-transparent. The compartments of the bag can be the same size, have the same internal volume, or they can be different sizes with different internal volumes.

For reasons of deformability and fit of the dispenser under compression forces, bags or compartments of the bag containing a component that is liquid will usually contain an air bubble having a volume of up to 50%, preferably up to 40%, more preferably up to 30%, more preferably up to 20%, more preferably up to 10%, of the volumetric space of said compartment.

The bag is preferably made of a bag material that is soluble or dispersible in water under hot water conditions, and preferably has a water solubility of at least 50%, preferably at least 75% or even at least 95%, measured by the method described hereinabove.

Preferred bag materials are polymeric materials, preferably polymers that are formed into a film or sheet. The bag-shaped material can be obtained, for example, by molding, blow molding, extrusion or blow extrusion of the polymeric material, as is known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for use as bag material are selected from polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid , cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic acid / acrylic acid copolymers, polysaccharides including starch and gelatin, and natural gums such as xanthan gum and carrageenan gum. The most preferred polymers are selected from polyacrylates and copolymers of water soluble acrylate, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, maltodextrin, and more preferably are selected from polymethyl cellulose, maltodextrin, and more preferably selected from poly (vinyl alcohols), poly (vinyl alcohol) copolymers, partially hydrolyzed poly (vinyl acetates) and hydroxypropyl methyl cellulose (HPMC), hydroxybutyl methyl cellulose (HBMC), and mixtures thereof. Preferably, the level of polymer in the bag material, for example a PVA polymer, is at least 60%.

The polymer can have any weight average molecular weight, preferably from 1000 to 1,000,000, more preferably from 10,000 to 300,000, and even more preferably from 20,000 to 150,000.

Polymer blends can also be used for the bag material. This can be beneficial in controlling the mechanical and / or dissolution properties of the compartments or the bag, depending on the application of the same and the needs required. Suitable mixtures include, for example, mixtures in which one polymer has greater water solubility than another polymer and / or in which one polymer has greater mechanical strength than another polymer. Also suitable are blends of polymers with different weight average molecular weights, for example a blend of PVA or a copolymer thereof with a weight average molecular weight of 10,000-40,000, preferably about 20,000, and of PVA or a copolymer of the itself, with a weight average molecular weight of 100,000 to 300,000, preferably about 150,000.

Also suitable in the present invention are polymer mixture compositions, for example those comprising mixtures of hydrolytically degradable and water-soluble polymers such as polylactide and poly (vinyl alcohol), obtained by mixing polylactide and poly (vinyl alcohol), in such a way typically comprising 1-35% by weight of polylactide and from 65% to 99% by weight of polyvinyl alcohol.

ES 2 328 680 T3

Preferred for use in the present invention are polymers that include polyvinyl acetate and are hydrolyzed from 60% to 98%, preferably hydrolyzed from 80% to 90%, to improve dissolution characteristics of the material.

The most preferred cold water soluble pouch materials are the PVA films known under the trade name Monosol M8630 and sold by Chris-Craft Industrial Products of Gary, Indiana, USA, and the corresponding PVA films. solubility and deformability characteristics. Other films suitable for use in the present invention include films known under the trade reference PT film or the K series of films supplied by Aicello or VF-HP film supplied by Kuraray.

The pouch material of the present invention may also comprise one or more additive ingredients. For example, it may be beneficial to add plasticizers, eg, glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Other additives include functional detergent additives to be supplied to the wash water, for example organic polymeric dispersants.

The bag can be prepared according to methods known in the art. The bag is typically prepared by first cutting a suitable size piece of bag-shaped material, preferably bag-shaped material. The pouch material can then be folded to form the required number and size of compartments and the edges sealed using any suitable technology, for example heat sealing, wet sealing or pressure sealing. Preferably, a source of sealing is contacted with the bagged material, heat or pressure is applied and the bagged material is sealed.

The bag-shaped material is typically introduced into a mold and a vacuum is applied so that the bag-shaped material sticks to the inner surface of the mold, thereby forming a vacuum space or niche in said bag-shaped material. bag. This is known as vacuum forming.

Another suitable method is thermoforming. Thermoforming typically involves the step of forming an open bag in a mold by applying heat, which allows the bag material to take the shape of the mold.

Typically, more than one piece of bag material is used to make the multi-compartment bags. For example, a first piece of bag-shaped material can be vacuum applied into the mold so that said bag-shaped material sticks to the inside walls of the mold. A second piece of bag-shaped material can then be positioned so as to at least partially overlap and preferably completely overlap the first piece of bag-shaped material. The first piece of bag material and the second piece of bag material are sealed together. The first piece of bag-shaped material and the second piece of bag-shaped material may be made of the same type of material or they may be made of different types of material.

In a preferred process, a piece of bag-shaped material is folded at least twice or at least three pieces of bag-shaped material are used or at least two pieces of bag-shaped material are used wherein at least one piece of bag-shaped material is folded at least once. The third piece of bag material, or a folded piece of bag material, creates a barrier layer which, when the bag is sealed, divides the internal volume of the bag into at least two or more compartments.

The bag can also be prepared by fitting a first piece of the bag-shaped material in a mold, for example, the first piece of film can be vacuum applied in the mold so that said film sticks to the inner walls of the mold. A composition, or component thereof, is typically poured into the mold. A pre-sealed compartment made of pouch material, eg containing a liquid composition, is then typically placed on the mold containing the composition, eg a solid composition, or a component thereof. The pre-sealed compartment preferably contains a composition or a component thereof. The pre-sealed compartment and said first piece of bag material can be sealed together to form the bag.

Examples

Abbreviations used in the examples

In the examples, the abbreviated component identifications have the following meanings:

Carbonate: Anhydrous sodium carbonate

STPP: Anhydrous sodium tripolyphosphate

Silicate: Amorphous sodium silicate (SiO₂: Na₂O = from 2: 1 to 4: 1)

ES 2 328 680 T3

<td>Alcosperse 240</td><td>: Sulfonated polymer available from Alco Chemical, 40-45% solids</td>

<td>Alcosperse 240-D</td><td>: Sulfonated polymer available from Alco Chemical, 95% solids</td>

<td>Percarbonate</td><td>: Sodium percarbonate of nominal formula 2Na₂CO₃, 3H₂OR₂</td>

<td>TAED</td><td>: Tetraacetylethylenediamine</td>

<td>Amylase</td><td>: α-amylase available from Novo Nordisk A / S</td>

<td>Protease</td><td>: Protease available from Novo Nordisk A / S</td>

<td>SLF18</td><td>: Low foaming surfactant marketed by BASF</td>

<td>LF404</td><td>: Low foaming surfactant marketed by BASF</td>

<td>c₁₄year</td><td>: Tetradecyl dimethylamine oxide</td>

<td>CieAO</td><td>: Hexadecyl dimethylamine oxide</td>

DPG: Dipropylene Glycol

In the following examples all levels are expressed in grams.

Examples 1 to 3

The compositions of Examples 1 to 3 are enclosed in a single compartment PVA pouch made of a film practically insoluble in cold water and soluble in hot water, BP26 as marketed by Aicello.

<img file="ES2328680T3_D0002.tif" />

ES 2 328 680 T3

Eight Libby beakers and a beaker containing 50 g of the soil described hereinafter are placed in a Bosch Siemens 6032 dishwasher with a capacity of 51 wash water. The water used has a hardness of 0.31 g / l (18 gpg) - 0.38 g / l (22 gpg) of calcium. Each of the illustrated bags is placed in the dispenser for delivery to the main wash and the dishwasher is run on its normal 65 ° C program. The washed glasses have an excellent shine.

Dirt

Ingredients

<td>Crisp, dry solid oil</td><td>300 g +/— 1 g</td>

<td>Scott oatmeal</td><td>100 g +/- 1 g</td>

<td>Stork margarine</td><td>150 g +/— 1 g</td>

<td>Confined medium sized egg yolk (separate the yolks and wash in urban cold water [medium hardness] before use).</td><td>300 g +/— 1 g</td>

<td>Thawed frozen Asda spinach (strain before use to remove excess water).</td><td>100 g +/- 1 g</td>

<td>UHT Asda whole milk</td><td>50 g +/— 1 g</td>

The dirt is prepared by mixing the above ingredients for 10 min.

Examples 4 to 8

The compositions of Examples 4 to 8 are made in the form of two-compartment PVA bags. The first compartment, which comprises the liquid composition, is practically insoluble in cold water and soluble in hot water and is made of a BP26 film such as that marketed by Aicello and the second compartment, which comprises the solid composition, is soluble in cold water and It is made from a Monosol M8630 film such as that sold by Chris-Craft Industrial Products.

(Table goes to next page)

ES 2 328 680 T3

<td>Example</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>

<td>Solid composition</td><td></td><td></td><td></td><td></td><td></td>

<td>STPP</td><td> 10,0</td><td> 10,0</td><td> 10, 0</td><td> 10,5</td><td> 9,5</td>

<td>Silicate</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td>OR i — 1</td>

<td>Carbonate</td><td> 2,0</td><td> 2,0</td><td> 2,0</td><td> 2,0</td><td> 2, 5</td>

<td>Alcosperse 240</td><td></td><td></td><td> 1,0</td><td> 1,0</td><td> 1,0</td>

<td>C₁₆ AO</td><td> 0,2</td><td></td><td></td><td></td><td></td>

<td>C14 AO</td><td></td><td></td><td></td><td></td><td></td>

<td>SLF18</td><td>O &lt;—1</td><td></td><td></td><td></td><td></td>

<td>LF404</td><td></td><td></td><td></td><td></td><td></td>

<td>PCO</td><td> 2,5</td><td> 2,5</td><td> 2,5</td><td> 2,5</td><td> 2,5</td>

<td>TAED</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td>

<td>Amylase</td><td> 0,4</td><td></td><td> 0,4</td><td> 0,4</td><td> 0,4</td>

<td>Protease</td><td> 0, 8</td><td> 0, 8</td><td> 0,8</td><td> 0,8</td><td> 0,8</td>

<td>Fragrance</td><td> 0,05</td><td> 0,05</td><td> 0, 05</td><td> 0, 05</td><td> 0,05</td>

<td>Total</td><td>18.15 g</td><td>16.6 g</td><td>19.15 g</td><td>19.65 g</td><td>19.15 g</td>

<td>Liquid composition</td><td></td><td></td><td></td><td></td><td></td>

<td>DPG</td><td> 0, 8</td><td> 0,5</td><td> 0,75</td><td> 0,75</td><td> 0,8</td>

<td>Cie AO</td><td></td><td></td><td> 0,2</td><td></td><td></td>

<td>C14 AO</td><td></td><td></td><td></td><td> 0,2</td><td></td>

<td>SLF18</td><td></td><td></td><td> 1,0</td><td>O i — I</td><td></td>

<td>LF404</td><td></td><td></td><td></td><td></td><td> 0,8</td>

<td>Alcosperse 240-D</td><td> 1,0</td><td> 1,0</td><td></td><td></td><td></td>

<td>Amylase</td><td></td><td> 0,4</td><td></td><td></td><td></td>

<td>Dye</td><td> 0,1</td><td> 0,1</td><td> 0,05</td><td> 0,05</td><td> 0,1</td>

<td>Total</td><td>1.9 g</td><td>2.0 g</td><td>2.0 g</td><td>2.0 g</td><td>1.7 g</td>

The dishwasher washing process of Examples 1 to 3 is repeated. The washed glasses have excellent gloss.

Examples 4 and 5 are presented for illustrative purposes only.

Examples 9 to 13

Two compartment bags practically insoluble in cold water and soluble in hot water (both compartments) are manufactured with a BP26 film comprising the compositions of Examples 4 to 8. The bags are used to wash the load described in Examples 1 to 3 The dishwasher washing process of Examples 1 to 3 is repeated but placing the bag in the cutlery basket. The washed glasses have an excellent shine.