WO2001046379A1

WO2001046379A1 - Slightly water-permeable packaged detergent or cleanser

Info

Publication number: WO2001046379A1
Application number: PCT/EP2000/012580
Authority: WO
Inventors: Dirk Oberdorf; Wolfgang Barthel
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-12-21
Filing date: 2000-12-12
Publication date: 2001-06-28
Also published as: DE19961663A1

Abstract

The invention relates to a combination comprised of a particle-shaped detergent or cleanser which has an active oxygen content and which is provided with a packaging system that contains the detergent or cleanser. Said packaging system has a water-vapor permeability rate ranging from 20 g/m2/day to 100 g/m2/day at a temperature of 23° C and a relative humidity of 85 %. The inventive combination enables the compound that yields active oxygen to be stabilized in particle-shaped detergents or cleansers, and the content of the compound that yields active oxygen can be maintained over a period corresponding to the average storage time periods for agents of this type.

Description

Detergent or cleaning agent packed with little water permeability

The present invention relates to a combination of an active oxygen-containing washing or cleaning agent with a packaging material containing the same, which has a low water permeability.

Detergents and cleaning agents which contain active oxygen-providing compounds alone or as a bleaching system in the form of a combination of an inorganic peroxide or perhydrate with a bleach activator have been known for a long time. The most frequently used bleaching components or oxidizing agents containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates. As bleach activators, there are generally used compounds which split off carboxylic acids or percarboxylic acids under hydrolysis or perhydrolysis conditions. Since the release of hydrogen peroxide from the peroxygen compound, which is only intended to take place under the mostly aqueous conditions of use of the agents, can also take place during the production and, in particular, storage of such agents, as a result of which the availability of the peroxygen compound for the actual intended use decreases, has been going on for a long time Wanted for the stabilization of these peroxygen compounds, which should prevent the loss of active oxygen during storage. The problem of inadequate storage stability is particularly difficult to solve for percarbonate-containing bleaching systems, since this perhydrate is extremely susceptible to hydrolysis and is even rapidly decomposed by normal atmospheric humidity. To remedy this, it has been proposed, for example, to coat the percarbonate with inorganic salts such as borates, sulfates and / or silicates or organic substances such as nonionic surfactants or fatty acids. As a further solution, a bleaching agent composition is described in German patent application DE 31 41 745, for example, which contains an inorganic peroxide, in particular sodium percarbonate, which is effective for bleaching fabrics, and 0.01% to 5% by weight of enzyme and at least 0.1 Wt .-% to 20 wt .-% of an anhydrous salt from the series contains anhydrous sodium citrate, anhydrous magnesium sulfate, anhydrous calcium chloride and anhydrous zinc sulfate.

European patent application EP 0 407 045 describes a stabilized sodium percarbonate composition which, in addition to sodium percarbonate, contains 2.5% by weight to 35% by weight of at least one compound from the group consisting of urea, urea derivatives, acetates and amino acids with no more than contains seven carbon atoms or their salts, triazine compounds and guanidine compounds as stabilizers.

A combination of a granular percarbonate-containing detergent composition and a packaging system with a water vapor permeability rate in the range from 1 g / m / day to below 20 g / m / day is known from European patent EP 0 634 484 B1, which means that when the agent is stored, active oxygen Losses from the percarbonate should be avoided.

International patent application WO 98/40464 describes a combination of at least one tablet of compressed particulate detergent, which is stored for at least 24 hours in a packaging system with a moisture permeability rate of less than 20 g / m / day.

In particular, packaging, such as cardboard packaging, which is equipped with a barrier layer and which has a water vapor permeability rate below 20 g / m ² / day, is difficult to produce. On the other hand, packaging with a water vapor permeability rate of less than 10 g / mJ day is generally not required for the commercially available detergents or cleaning agents containing active oxygen, in particular percarbonate. The barrier layers generally consist of polyethylene or a hot melt material (hot melt) which are applied to the cardboard in a thickness of 20 to 30 g / m 2, as a rule by means of a complex extrusion process. The materials coated in this way have the disadvantage that they cannot be easily recycled. A material with a barrier layer made of polyethylene cannot be easily recycled with other waste paper and must be processed separately. A so-called hot melt coating must be treated as special waste and cannot be recycled.

The present invention was accordingly based on the object of providing a packaging system for detergents and cleaning agents containing active oxygen, which on the one hand has a water vapor permeability rate which ensures the stability of per-compounds in particulate detergents and cleaning agents over long average storage periods, but which also special economic requirements in the manufacture of the packaging materials to be used for the particulate agents are taken into account.

Surprisingly, it has been found that active oxygen-providing compounds in particulate detergents and cleaning agents stabilize and maintain the content of these compounds over a period corresponding to average storage periods for such agents when packaging materials with a

9 9

Water vapor permeability rate from 20 g / m / day to 100 g / m / day.

The invention therefore relates to the combination of an active oxygen-containing detergent and cleaning agent with a packaging system containing the same, which at 23 ° C. and 85% rel. Moist one

9

Has water vapor permeability rate of 20 g / m / day to 100 g / m / day.

The packaging material of the combination of detergent or cleaning agent containing active oxygen and packaging material has a water vapor permeability rate

9 9 from over 20 g / m / day to less than 100 g / m / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, whereby according to DIN 53122 only relatively small deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The water vapor permeability rate of a given packaging system or material can be determined using other standard methods and is also, for example, in ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in TAPPI Standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of common methods is based on the water absorption of anhydrous calcium chloride. which is stored in a container in the appropriate water vapor atmosphere. the container being closed at the top with the material to be tested. The water vapor permeability rate WDDR can be deduced from the size of the surface of the container which is closed with the material to be tested (permeation surface), the weight increase in calcium chloride and the exposure time

24 - 10000 xr ₂ i

WDDR = [g 'fri! 24 hours\

A y

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity". is 85% at 23 ° C when measuring the water vapor transmission rate in the context of the present invention. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 πr air at 17 ° C is saturated with 14.4 g of water vapor; at a temperature of 11 ° C, saturation is already present with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air at 17 ° C contains 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) -100 = 83%. If this air is cooled, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 ° C), which means that with further cooling, a precipitate is formed in the form of mist (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture. The relative equilibrium humidity of 85% at 23 ° C can be set, for example, in laboratory chambers with moisture control to approximately +/- 2% RH depending on the device type. Even over saturated solutions of certain salts form in closed Systems at a given temperature consist of constant and well-defined relative air humidities, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the soil and which can be used to determine the water vapor permeability of the packaging material.

The combinations of active oxygen-containing detergents or cleaning agents and packaging system according to the invention can of course in turn be packaged in secondary packaging, for example cardboard boxes or trays, with no further requirements being placed on the secondary packaging. The secondary packaging is therefore possible, but not necessary.

In the context of the present invention preferred packaging systems have at 23 ° C and 85% rel. Humidity has a water vapor transmission rate in the range of 20

9 9 9 ^" * g / mJ day to 100 g / m / day, in particular from 20 g / m / day to 30 g / m ^~ / day.

The packaging system of the combination according to the invention, which may consist of a plurality of packaging materials, can consist of a wide variety of materials and take on any external shape, the water vapor permeability rates given relating to the entire packaging system in the case of a packaging system consisting of several different packaging materials. For economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention, the packaging material or the packaging system consists of a sack, pouch or folding box made of single-layer paper or cardboard. These can be designed in a wide variety of ways, for example as an inflated bag without a central seam or as a bag with a central seam, which are sealed by heat (hot melt), adhesives or adhesive tapes. Single-layer bag or sack materials are the known papers, which can optionally be coated. Combinations which are particularly preferred in the context of the present invention contain, as packaging, a sack or bag made of cellulose which is coated with a plastic dispersion, as a result of which the cellulose is given the desired water vapor permeability. Preferably, cellulose (paper) films (is that so?) With a thickness of 20 μm to 200 μm, preferably from 40 μm to 150 μm and in particular from 90 μm to 130 μm, are used.

The pulp is preferably coated using suitable aqueous polymer dispersions. The polymer dispersions can be applied in a manner known per se, e.g. B: directly in the paper machine or in a conventional coating process. Copolymers are preferably used as plastic dispersions, which consist of a balanced ratio of hydrophilic and hydrophobic groups, setting the desired barrier properties.

Such detergents or cleaning agents contain 5% by weight to 40% by weight, in particular 7.5% by weight to 30% by weight, of active oxygen-containing compounds, with agents intended for use as bleach-enhancing agents Additive in addition to conventional washing or cleaning agents are provided. Levels tend to be at the upper limit of the range, for example from 20% by weight to 40% by weight. Suitable compounds are percarbonates, alkali perborate mono- or tetrahydrate, with sodium being the preferred alkali metal. In addition or in particular as an alternative, known peroxycarboxylic acids, for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present. In addition, the addition of small amounts of known bleach stabilizers such as, for example, phosphates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate can also be useful. Sodium percarbonate is particularly preferred as the active oxygen-providing compound. It can be produced by known methods and packaged or stabilized and / or coated in granular form. For reasons of stability, it is preferably used in the form of a granulate which, with the aid of alkaline earth metal sulfate, alkali metal sulfate, alkali metal silicate, alkaline earth metal halide, alkali metal halide, alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal phosphate, alkali metal borate, alkali metal perborate, boric acid, partially hydrated aluminosilicate, carbonic acid, carbonic acid Polymers made from unsaturated carboxylic and / or dicarboxylic acids, or mixtures thereof, or is encased. In a preferred embodiment, it has a physiology index (MI), as defined in EP 0 451 893, of less than 0.06.

Depending on their intended use, the detergents or cleaning agents of the combination according to the invention can contain further customary ingredients of detergents and cleaning agents in varying amounts. Regardless of the intended use of the agent, it is preferred that it has a relative equilibrium moisture content of less than 30% at 35 ° C. The relative equilibrium moisture content of the detergent or cleaning agent can be determined using standard methods, with the following procedure being chosen within the scope of the present investigations: A water-impermeable 1 liter vessel with a lid, which has a closable opening for introducing samples, was used filled with a total of 300 g of the agent and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of the vessel and substance. The water vapor pressure in the space above the molded bodies can then be determined using a hygrometer (for example Hygrotest 6100, Testoterm Ltd .. England). The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above-mentioned hygrometer allows a direct display of the recorded values in% relative humidity.

The detergents and cleaning agents, which can be present as granules, powdered or tablet-shaped solids or as other shaped bodies, in particular as largely spherical extrudates, can, in addition to the bleach-boosting active ingredient mentioned, in principle contain all known ingredients customary in such agents. The packaged agents according to the invention can in particular builder substances, surface-active surfactants, additional Persau substance compounds, Per-oxygen activators, sequestering agents, enzymes. Contain electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators and colorants and fragrances. A cleansing agent for hard surfaces packed according to the invention can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof. Abrasives are preferably not contained in the cleaning agents above 20% by weight, in particular from 5% by weight to 15% by weight.

The agents can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic ones. zwitterionic and amphoteric surfactants come into question. Such surfactants are contained in detergents packed according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas cleaning agents for hard surfaces normally have smaller proportions, the means amounts up to 20% by weight, in particular up to 10% by weight and preferably in the range from 0.5% by weight to 5% by weight. In detergents for use in machine dishwashing processes, extremely low-foaming surfactant compounds are normally used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. The surfactants of the sulfonate type are preferably C ₉ -C ₃ -alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₂ -C ₈ -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or Tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, may also be present in small amounts, preferably in amounts not above about 2 to 3% by weight. In particular, alkyl sulfofatty acid esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 1 -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C ₈ oxo alcohols and those half esters secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C * ₂ -Ci ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C ₄ -Ci5 alkyl sulfates are particularly preferred from a washing-technical point of view. 2,3-Alkyl sulfates, which are produced, for example, in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C -C ₂ ι- alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl branched C -Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι ₂ -Cι ₈ -Fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally used in washing and cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. preferred Sulfosuccinates contain C ₈ to C ₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside) are also suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Soaps, for example in amounts of 0.2% by weight to 5% by weight, are particularly suitable as further anionic surfactants. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, for example coconut oil, are particularly suitable. Palm kernel or tallow fatty acids, derived soap mixtures. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Anionic surfactants are contained in detergents packed according to the invention preferably in amounts of 1% by weight to 30% by weight and in particular in amounts of 5% by weight to 25% by weight.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position can be or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, -C 1 -C alcohols with 3 EO or 4 EO. C -Cn alcohols with 7 EO, ₃ - cis alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C, ₂ -C, ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, like mixtures of -C ₄ -C alcohol with 3 EO and -C ₂ -C ₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. The nonionic surfactants also include alkyl glycosides of the general formula RO (G), in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which as an analytically determinable variable can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical 3 to 10 carbon atoms and 3 to 10 hydroxyl groups: R ²

R'-CO-N- [Z] (I)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ⁴ -OR ⁵

(II)

R ³ -CO-N- [Z]

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue. [Z] is also preferred here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose. Get mannose or xylose. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds which have two hydrophilic groups per molecule. These groups are usually separated from each other by a so-called "spacer". This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean "dimeric" but also "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized by their bi- and multifunctionality. The end group-sealed surfactants mentioned have good wetting properties and are low-foaming. so that they are particularly suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used.

A detergent packed according to the invention preferably contains at least one water-soluble and or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphinophosphonic acid), l, l-diphosphonic acid, as well as polymeric (poly) carboxylic acids, in particular the polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers obtained from these by oxidation of polysaccharides or dextrins, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. As water-soluble organic builder substances it is also possible to use polymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and or an esterified vinyl alcohol or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. his. Such polymers generally have a relative molecular mass between 1,000 and 200,000. Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances, in particular for the production of liquid agents, can be used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight.

Particularly suitable water-soluble inorganic builder materials are alkali silicates and polymeric alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding Potassium salts or mixtures of sodium and potassium salts. The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali alumosilicates, in amounts of normally up to 50% by weight, preferably not more than 40% by weight and in particular from 5% by weight to 35% by weight. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA), are preferred , Amounts close to the above upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates that can be used as builders preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. Crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x + 1} ^" H ₂ O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Crystalline phyllosilicates which come under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred, with β-sodium disilicate for example according to the Method can be obtained, which is described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can. Practically anhydrous crystalline alkali silicates of the general formula mentioned above, in which x is a number from 1.9 to 2.1, can also be used, produced from amorphous alkali silicates. In a further preferred embodiment of such agents, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention. In a preferred embodiment of agents according to the invention, a granular compound of alkali silicate and alkaiicarbonate is used, as is commercially available, for example, under the name Nabion® 15. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

Such builder substances are preferably contained in amounts according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.

In principle, all builders commonly used in agents for machine dishwashing, for example the alkali metal phosphates mentioned above, can be used as water-soluble builder components in cleaners for hard surfaces packed according to the invention. Their amounts can range from up to about 60% by weight, in particular 5% by weight to 40% by weight, based on the total composition. In addition to polyphosphonates and phosphonate alkyl carboxylates, other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin of the type of polycarboxylates listed above, which act as co-builders in particular in hard water regions, and naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, α-hydroxy- propionic acid and gluconic acid. The preferred organic builder components include the salts of citric acid, especially sodium citrate. Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH ultimately set in the cleaning agents according to the invention, the acids corresponding to the co-builder salts mentioned can also be present.

To increase the bleaching action of the per-compound contained according to the invention, customary transition metal complexes known as bleach activators and / or conventional bleach activators, that is to say compounds which contain perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, which are optionally substituted under perhydrolysis conditions. Result in atoms. Suitable are the conventional bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzovl groups. Multi-aeylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), aeylated glycolurils are preferred. especially tetraacetylglycoluril (TAGU). aeylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), aeylated phenylsulfonates, in particular nonanoyl- or isononanoyloxybenzenesulfonate, aeylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate -Diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and aeylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. In a preferred embodiment of the use according to the invention, such a compound which releases peroxocarboxylic acid under perhydrolysis conditions is used simultaneously with the bleach-enhancing complex compound. In a preferred embodiment of agents packed according to the invention, 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight, of such a compound which releases peroxocarboxylic acid under perhydrolysis conditions is present. In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt. Ruthenium or molybdenum carbonyl complexes. the manganese, iron described in German patent application DE 196 05 688. Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 41 1, which in the German patent application DE 44 16 438 manganese, copper and cobalt complexes described, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, which are known from European Patent specification EP 0 392 592 known manganese, iron, cobalt and copper complexes, the cobalt complexes known from international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 and / or those in the European patent specification EP 0 443 651 or the European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent. The enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and or Savinase®, amylases such as Termamyl®. Amylase-LT®, Maxamyl®, Duramyl®, Purafect® OxAm, cellulases such as Celluzyme®. Carezyme®, KAC® and or the cellulases and / or lipases known from international patent applications WO 96/34108 and WO 96/34092 such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in washing and cleaning agents packed according to the invention, preferably in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, enzymes stabilized against oxidative degradation being particularly preferably used.

Color transfer inhibitors which are suitable for use in agents according to the invention, in particular those for washing textiles, include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular of the textile fiber suspended in the liquor and thus to support the co-builder. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch products other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used , The agents intended for use in textile washing can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which replace the Moφholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine washing and cleaning processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₈ -C ₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins. Waxes. Microcrystalline waxes and their mixtures with silanized silica or bis fatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The preparation of particulate agents according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, the per-compound, in particular percarbonate, and other thermally sensitive ingredients optionally being added separately later. A method known from European Patent EP 0 486 592 and having an extrusion step is preferred for producing powders according to the invention with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1. They are in principle known in packaging materials with a water Vapor permeability rate from over 20 g / m ² / day to less than 100 g / m ² / day and can be stored in these without significant loss of active ingredient over long periods.

Examples

A commercial heavy-duty detergent (Persil ^® , commercial product from the applicant, in powder form) was filled in a packaging system with a defined water vapor thickness and stored over a period of 12 weeks.

Veφackungssystem:

Example 1: WDD 79 g / m / day, cardboard coated with a copolymer dispersion; Example 2: WDD 65 g / m / day cardboard coated with a copolymer dispersion; Example 3: WDD 28 g / m ² / day cardboard coated with a polyethylene film;

After a storage period of 0, 4, 8 and 12 weeks, the active oxygen content (AO) was determined in each case. Changes in bulk behavior and in the grain spectrum are also examined.

Example 2

Storage time / weeks 0 4 8 12

AO 1.7 1.8 1.8 1.8

Bulk density 0.555 0.560 0.562 0.569

(G / ml)

Grain spectrum,

> 1.6 mm 1.7 1.0 1, 5 1.5

> 0.8 mm 14.9 13.9 13.7 13.2

> 0.4 mm 37.7 38.2! 38.0 38.4

> 0.2 mm 29.6 29.4 30.1 31.4

> 0.1 mm 14.3 16.1 16.1 15.3

<0.1 mm 1.7 1.3! 0.6 0.3

Trickle behavior hesitating hesitating hesitating hesitating fluent fluent in batches in batches

; fluent fluent

1

The storage tests show that the active oxygen content of the investigated combination of active oxygen-containing agent and packaging system according to the invention with a defined water vapor permeability remains constant over a period of 12 weeks.

The other powder properties, which can change during a longer storage period, remain almost unchanged.

Claims

claims

1. Combination of an active oxygen-containing particulate washing and cleaning agent with a packaging system containing this, which at 23 ° C and 85% rel. Moisture has a water vapor permeability rate of 20 g / m ² / day to 100 g / m ² / day.

2. Combination according to claim 1, characterized in that the water vapor permeability rate is in the range between 20 and 30 g / m / day.

3. Combination according to one of claims 1 or 2, characterized in that the packaging system consists of a sack or bag made of coated paper or plastic.

4. Combination according to one of claims 1 to 3, characterized in that the packaging system is coated with a copolymer dispersion.

5. Combination according to one of claims 1 to 4, characterized in that the washing or cleaning agent has a relative equilibrium moisture content of less than 30% at 35 ° C.

6. Combination according to one of claims 1 to 5, characterized in that the active oxygen-providing compound is sodium percarbonate.

7. Combination according to one of claims 1 to 6, characterized in that the detergent contains 5 wt .-% to 50 wt .-%, in particular 8 wt .-% to 30 wt .-%, surfactants.

8. Combination according to one of claims 1 to 7, characterized in that the detergent contains 1 wt .-% to 30 wt .-% and in particular 5 wt .-% to 25 wt .-% anionic surfactants.

9. Combination according to one of claims 1 to 8, characterized in that the Contains cleaning agents for hard surfaces up to 20% by weight, in particular up to 10% by weight and particularly preferably 0.5% by weight to 5% by weight of surfactants.

10. Combination according to one of claims 1 to 9, characterized in that the agent organic builder substances in amounts up to 40 wt .-%. contains in particular up to 25% by weight and preferably from 1% by weight to 8% by weight.

11. Combination according to one of claims 1 to 10, characterized in that the agent contains up to 60% by weight, in particular 5% by weight to 40% by weight, of alkali metal phosphate.

12. Combination according to one of claims 1 to 11, characterized in that the composition contains 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight, of compounds which split off peroxocarboxylic acid under perhydrolysis conditions.

13. Combination according to one of claims 1 to 12, characterized in that the agent bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, in an amount up to 1 wt. -%. contains in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight.