HU218571B - Detergent composition - packaging system combination - Google Patents

Abstract

In the combination according to the invention, the detergent composition comprises at least one moisture-sensitive component of: - polyhydroxy fatty acid amide nonionic surfactants; - bleach activators which may be alkanoyloxybenzoylsulfonates, amide derivatives, benzoxazine derivatives, quaternary substituted compounds or mixtures thereof; - polymers which are polyamine N-oxides, N-vinyl pyrrolidone and N-vinylimidazole copolymers, polyvinyl oxazolidone and polyvinylimidazoline, polyaspartate, polyglutamate, maleic acid / acrylic acid / vinyl alcohol terpolymers, sulfonated polyethoxy / propoxy closure ester oligomers, or mixtures thereof; - peroxidase enzymes; - amylase enzymes; - ethylene diamine succinic acid chelating agents; -parfümkapszulák; or - mixtures thereof; wherein the composition has a equilibrium relative humidity of less than 30% at 35 ° C, and the packaging system consists of a plastic foil or a plastic / paper laminate, foldable, sealed, recharging bag having a vapor transfer rate of 1 to 15 g / m 2 / day. ŕ

Description

The present invention relates to a packaging system combination comprising a detergent composition comprising selected moisture sensitive additives which provides optimum moisture protection to the selected selected additives.

The interaction of moisture with additives used in detergent formulations during storage, particularly during long-term storage, has long been a known problem for detergent manufacturers. This interaction, on the one hand, takes place between water and certain additives and results in their degradation and / or loss of action and, on the other hand, between degradation products of moisture sensitive additives and other additives and also results in degradation and / or loss of effect. A number of processes have already been proposed in which special additives are used to protect the finished product from moisture or the additives already used are modified.

However, relatively little attention is paid to packaging systems containing detergent compositions in connection with the above problem.

The invention is based on the discovery that by using a particular packaging system and by carefully controlling the moisture content of the composition, many storage stability problems of the particularly moisture sensitive additives described herein can be solved.

Accordingly, the present invention relates to a packaging system combination comprising a controlled humidity containing detergent composition containing selected moisture sensitive additives, wherein the packaging system is characterized by a defined Moisture Vapur Transfer Rate (MVTR).

Detailed Description of the Invention:

The detergent composition

The term "detergent composition" as used herein refers to detergents, dishwasher detergents, and detergent compositions.

The compositions of the present invention are characterized by having an equilibrium relative humidity of less than 30% at 35 ° C.

The equilibrium relative humidity of the compositions of the present invention is determined by adding 300 g of product to a 1 liter container made of waterproof material and fitted with a closure. The lid is provided with a sealable opening through which a sampler is introduced into the interior of the container. Keep the container and its contents at 35 ° C for 24 hours until the temperature has equalized. A vapor pressure hygrometer (Hygrotest 6100, Old Fluor Mill, Queen Street, Emsworth, Hampshire, England) was used to measure the vapor pressure of the water above the product. While holding the tank at 35 ° C, the sampler is introduced through the opening and after 10 minutes, the vapor pressure, which is the result of two successive measurements, is measured to compensate for the water vapor pressure. Equilibrium water vapor pressure values are read directly on the unit.

The compositions of the present invention can be prepared by various methods so that the critical relative humidity at 35 ° C is not more than 30%.

For example, certain internal moisture components of detergent compositions, such as surfactant agglomerates or spray-dried components, may be dried or further dried prior to mixing; dried zeolite may also be used to prepare the surfactant; these are added to the spray-dried components as a dry additive or are added in the final pulverization step.

Other processes for drying the final product are also described in DE 40 31 910.

In some cases, the equilibrium relative humidity at 35 ° C may be maintained below 25%.

Description of selected moisture sensitive additives:

1. Polyhydroxy fatty acid amides

The preparation of polyhydroxy fatty acid amides can be accomplished by reacting a fatty acid ester with an N-alkyl polyhydroxyamine. A preferred amine for use in the present invention is a compound of the formula NH (R ₁ ) -CH ₂ - (CHOH) ₄ CH ₂ OH, and the preferred ester is a C 12 -C 20 fatty acid methyl ester. Most preferred is the reaction product of N-methylglucamine and C12-C20 fatty acid methyl ester.

The process used to prepare polyhydroxy fatty acid amides is described in WO 92/6073. In the process described herein, the preparation of polyhydroxy fatty acid amides is carried out in the presence of a solvent. For the purposes of the present invention, the product obtained by reacting N-methylglucamine with a C12-C20 methyl ester is very advantageous. It is also claimed that the preparation of the granular detergent composition is conveniently carried out in an alkoxylated solvent, in particular ethoxylated (EO 3-8) C 12 -C 14 alcohols. By this process, nonionic surfactant systems, such as N-methylglucamine and C12-C14 alcohols having an average of 3 ethoxylates per molecule, are advantageously used directly for the purposes of the invention.

WO 92/6160 discloses nonionic surfactant systems and granular detergent compositions prepared using them. The granular detergent composition described herein is prepared by fine dispersion using an Eirich RV01 blender using 10% by weight of N-methylglucamine and 10% by weight of nonionic surfactant.

Both publications disclose a nonionic surfactant system and a process for their preparation which are suitable for the purposes of the present invention.

The polyhydroxy fatty acid amide content of the compositions of the invention is from 0 to 40% by weight, preferably from 1 to 30% and more preferably from 1 to 20% by weight of the composition.

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2. Choline esters

Preferred choline ester derivatives are those compounds of formula I wherein R ¹ is a straight or branched alkyl or alkenyl group containing 5 to 30 carbon atoms; and X is an anion which makes the compound dispersible at least in water and can be halogen, methyl sulfate, sulfate and nitrate, preferably methyl sulfate or chlorine, bromine or iodine;

and derivatives of the above compounds wherein the ester group is replaced by an amide group.

Of these types of cationic surfactants, stearoylcholine ester quaternary ammonium halides (R ¹ is C 17 alkyl), palmitoylcholine ester quaternary ammonium halides (R ¹ is C 15 alkyl), myristoyl are particularly preferred. choline ester quaternary ammonium halides (R ¹ is C 13 alkyl), lauroylcholine ester ammonium halides (R ¹ is C 11 alkyl), and coconut and tallow choline ester quaternary ammonium halides ( R ¹ is C 15 -C 17 and C 19 -C 13 alkyl).

Other preferred cationic components of the choline ester compounds are those compounds of formula II or III wherein p is 0-20.

The choline derivative described above is prepared by direct esterification of cationic surfactants in the presence of a desired fatty acid of the desired chain length and dimethylaminoethanol in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide to give the desired cationic material.

The choline derivative cationic surfactants may also be prepared by reacting the long chain fatty acid of the desired chain length with 2-haloethanol in the presence of an acid catalyst. The reaction product is then quatemized. The trimethylamine thus formed is the desired cationic component.

Other choline ester derivatives useful for the purposes of the present invention include compounds of formulas IV, V, VI, VII, VIII, IX, X and XI, wherein t is 0 or 1;

y is from 1 to 20; and

R ¹ and X have the same meanings as defined above.

The choline ester content of the compositions of the invention is 0-50% by weight, preferably 1-30% by weight and more preferably 1-20% by weight.

bleach activators

Suitable bleach activators for use in the compositions of the present invention may be the following substances or mixtures thereof:

Alkanoyloxy benzene sulphonate

Suitable alkanoyloxybenzenesulfonates for use in the compositions of the present invention include those compounds of Formula XII wherein R'-C10-10 is C8-C12, preferably C8-C11; and

M is a suitable cation, for example an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being the most preferred.

Very preferred alkanoyloxybenzene sulfonates include nonanoyloxybenzene sulfonate, 3,5,5-trimethylhexanoyloxybenzene sulfonate, 2-ethylhexanoyloxybenzene sulfonate, octanoyloxybenzene sulfonate, decanoyl sulfonate. oxybenzenesulfonate, dodecanoyloxybenzenesulfonate and mixtures thereof.

Amido derivatives are bleach activators

Suitable amide derivative bleach activators for use in the compositions of the present invention include compounds of Formulas XIII, XIV, or mixtures thereof wherein

R ¹ is C 1 -C 14 alkyl, aryl or alkaryl;

R ² is C 1 -C 14 alkylene, arylene or alkarylene;

^R5 is hydrogen or C1-10 alkyl, aryl or alkaryl; and

L is essentially any leaving group.

The cleavage group can be any group which is cleaved from the bleach activator by nucleophilic attack on the perhydroxidanion bleach activator. This perhydrolysis reaction occurs when peroxycarboxylic acid is formed. The appropriate cleavage group should generally be able to withstand an electron-attracting effect and, in addition, be of such a stable group that the background reaction rate is negligible. This promotes the nucleophilic attack of the perhydroxidanion.

The L group must be sufficiently reactive in a reaction that occurs within an optimal time period (e.g., a wash cycle). However, if L is too reactive, the activator in the bleaching composition may be difficult to stabilize. These characteristics are generally similar to the conjugate band pKa of the cleavage group, but there are exceptions. Generally, cleavage groups exhibiting the above properties will have a conjugate band with a pKa of 4 to 13, preferably 6 to 11, and most preferably 8 to 11.

Among the bleach activators of the general formula described above, those in which L is a, b or c are preferred.

R ³ is C 1 -C 8 alkyl; and Y is -SO ₃ © M® or -CO ₂ ^e M®, where M® is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred.

Among the bleach activators of the general formula described above, the following compounds are preferred: (6-octanamido-caproyl) -oxybenzenesulfonate, (6-nonanamido-caproyl) -oxybenzenesulfonate, (6-decanamidocaproyl) -oxybenzenesulfonate and mixtures thereof, amines it is disclosed in U.S. Patent 4,634,551.

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Benzoxazine activators

Such a substance is, for example, the very preferred benzoxazine XV of U.S. Patent 4,966,723.

Acyl lactam activators

Such compounds are especially the acyl caprolactams XVI and XVII of the formula and acyl valerolactams of compounds wherein ^R6 is H or 1-12 carbon alkyl, aryl, alkoxyaryl or alkaryl group containing 6-18 carbon atoms, aryl or substituted phenyl. (See, for example, U.S. Pat. Nos. 08/064,562 and 08/082,270, which disclose substituted benzoyl lactam compounds.) Preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5, 5-trimethyl-hexanoyl-caprolactam, nonanoyl-caprolactam, decanoyl-caprolactam, undecenoyl-caprolactam, benzoyl-valerolactam, octanoyl-valerolactam, decanoyl-valerolactam, undecenoyl-valerolactam, nonanoyl-valerolactam, 3,5,5-trimethyl- valerolactam and mixtures thereof. See also acyl caprolactam compounds disclosed in U.S. Patent 4,545,784, including benzoyl caprolactam adsorbed on sodium perborate.

Quatemary Substituted Bleach Activators (QSBA)

Typically, the QSBAs described herein are compounds of formula E- [Z] _n -C (O) -L wherein E is "head"; Z is a "tag" group (n is 0 or 1, i.e. this group may be absent but its presence is generally preferred); and L denote the "leaving group". These compounds generally contain at least one quaternary substituted nitrogen group which is part of the E, Z or L group. More preferably, a single quaternary nitrogen atom is present which is in the E or Z group. Generally, L is a leaving group in which the pKa range of the corresponding carboxylic acid (HL) is generally 50-30, more preferably 10-20, depending on the hydrophilicity of the QSBA. See U.S. Pat. No. 4,283,301 for more information on the pKa of the leaving group.

Preferred QSBAs in the composition of the present invention are water soluble and, to a certain extent, are divided into surfactant micelles, in particular nonionic surfactant micelles.

U.S. Pat. No. 4,539,130 discloses cleavage groups and solubilizing tendencies of quaternary groups present in QSBA. Also described herein are QSBAs in which the quaternary group is in the leaving group.

British Patent No. 1,382,594 discloses a class of QSBA compounds that are useful for the purposes of the present invention. In these compounds, Z is a polymethylene or oligomethylene group, the labeling group is an aliphatic group, and the quaternary group is E. British Patent 4,818,426 discloses another class of QSBA compounds that are useful for the purposes of the present invention. These compounds are quaternary ammonium carbonate esters in which the group Z of the above compound is attached via a group E to a carbon atom but also via a linking oxygen atom to the carbonyl group. Therefore, these compounds are quaternary ammonium carbonate esters. Homologous compounds lacking oxygen in Z are also known; they are also well suited for the purposes of the invention. See, for example, U.S. Patent Nos. 5,093,406 and 4,904,406.

Further QSBAs are also disclosed in European Patent Nos. 552,812 A1 and 540,090 A2.

Particularly preferred QSBA compounds are those containing caprolactam and valerolactam cleavage groups.

The preparation of QSBAs useful for the purposes of the invention can be carried out according to the reaction equation [A].

Details of the production process:

Preparation of N- [4- (Triethylammoniomethyl) benzoyl] caprolactam chloride salt

Preparation of 4- (chloromethyl) benzoyl chloride

To a round-bottomed flask equipped with an addition funnel, a gas inlet and a magnetic stirrer were added 0.5 mol of 4-chloromethylbenzoic acid, toluene (1.0 molar acid / 350 ml) and hot stone under argon. To the flask was added dropwise 1 mol of sulfinyl chloride via the addition funnel. The addition funnel was then replaced with a reflux condenser, and the reaction mixture was heated under reflux of toluene under argon for 4 hours. The reaction mixture was cooled to room temperature. The solvent is then evaporated.

Preparation of 4- (chloromethyl) benzoyl caprolactam

To a 3-necked round bottom flask equipped with a mechanical stirrer, reflux condenser, addition funnel and gas inlet were added 0.5 mol of caprolactam, 0.75 mol of triethylamine under argon and 75% of the required amount of toluene (1.0 mol of caprolactam) was added. . The reaction mixture was heated to reflux temperature of toluene. The remaining toluene was suspended in 0.5 mol of 4- (chloromethyl) benzoyl chloride and slowly added to the reaction mixture. The reaction mixture was heated under reflux of toluene under argon for 4 hours, then cooled slightly and filtered. The filtered solids (triethylamine hydrochloride) were discarded and the filtrate was cooled until a precipitate formed. The product is filtered off with suction, washed and dried.

Preparation of N- [4- (Triethylammoniomethyl) benzoyl] caprolactam chloride salt

To a round-bottomed flask equipped with an addition funnel, gas inlet and magnetic stirrer were added 0.5 mol of 4- (chloromethyl) benzoyl-caprolactam and acetonitrile (1 mol of caprolactam / 1.5 L) under argon. To the flask was added 1 mole of triethylamine. The addition funnel was then replaced with a reflux condenser and the reaction mixture was refluxed with acetonitrile under an argon atmosphere.

EN 218 571 Β for 4 hours. The reaction mixture was cooled and the solvent was evaporated. An excess of acetone was added to the flask under magnetic stirring to prevent product precipitation. The mixture was heated at the reflux temperature of acetone for a short time and then cooled to room temperature. The product is filtered off with suction, washed and dried.

The above procedure may also be repeated by replacing caprolactam with valerolactam. The synthesis may also be carried out using trimethylamine instead of triethylamine. Any of these results in the corresponding cationic bleach activator.

While the QSBAs described above are very advantageous for the purposes of the invention, they are intended to be illustrative only and are not intended to limit the scope of the invention. Any QSBA known in the art can be used. For example, variants of the above structures in which E or Z is part of a heterocyclic group may also be employed; or wherein the leaving group L is bonded to either the E group or the Z group by a hydrolytically resistant covalent bond; in the latter case group L is a so-called "moored" detachment group. These may be compounds of formula XIX or XX in which the group L still "leaves" E (Z) _n C (O) by perhydrolysis to form a peracid compound such as compound XXI or XXII.

In another group of known QSBAs, the cleavage groups are attached to the E (Z) _n C (O) group via an oxygen atom, not a neutral nitrogen atom. Such is, for example, the ordinary OBS (oxybenzenesulfonate) cleavage group. These examples are illustrated by various literature sources, including the disclosure documents described above.

The bleach activators are preferably present in an amount of from 1 to 20% by weight, more preferably from 2 to 10% by weight and most preferably from 3 to 5% by weight of the composition.

Description of the polymers

Polymers useful in the compositions of the present invention include: polyamine N-oxide polymers having a molecular weight of about 10,000, N-vinylpyrrolidone-N-vinylimidazole copolymers, polyvinyl oxazolidones, polyvinyl oxazolidones, and the like. imidazoles), polyaspartates, polyglutamates, or mixtures thereof; Terpolymers of maleic acid / acyclic acid and vinyl alcohol having a molecular weight of 3,000 to 70,000, wherein the vinyl alcohol is present in an amount of 5 to 60% by weight; sulfonated polyethoxypropoxy end-capped ester oligomers and mixtures thereof. They are present in an amount of 0.01 to 20% by weight of the composition.

The esters described herein are simply oligomers comprising a substantially linear "backbone" and a closure moiety. The end cap is derived from sulfonated monohydroxy polyethoxy / propoxy monomers, in particular 2- (2-hydroxyethoxy) ethanesulfonate. By appropriately selecting the structural units that make up the ester backbone and using the appropriate amount of sulfonated barrier group, the materials so prepared have the desired soil release properties. The addition of a stabilizer to the oligomers reduces the crystallization of the oligomer during production and in the washing liquor, resulting in an improvement in the solubility / dispersion and soiling activity of the esters.

A preferred composition of the ester oligomer suitable for the purposes of the invention is as follows:

i) 1-2 moles of sulfonated polyethoxy / propoxy closure unit (MO.SfoCH ^^ CHAYCH.CH.OfoRO) in which

M is a salt-forming cation which may be sodium or tetraalkylammonium;

m is 0 or 1;

R is ethylene or propylene or mixtures thereof; and n is 0-2;

ii) 0.5 to 66 mol of the following unit: (a) oxyethyleneoxy unit; (b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units in the molar ratio (0.5: 1) to (10: 1); (c) a mixture of the materials of (a) or (b) with polyoxyethylene units having 2-4 degree of polymerization; provided that when the degree of polymerization of the polyoxyethylene oxy units is 2, the molar ratio of the polyoxyethylene oxy units to all groups ii) is (0: 1) to (0.33: 1) ), if the degree of polymerization of the polyoxyethylene oxy units is 3, the molar ratio of the polyoxyethylene oxy units to all groups (ii) (0: 1) to (0.22: 1), and if the degree of polymerization of the polyoxyethylene oxy units is 4, the molar ratio of the polyoxyethylene oxy units to all groups ii) is (0: 1) to (0.14: 1);

iii) from 1.5 to 40 moles of terephthalol units; and iv) 0-26 moles of a 5-sulfoisophthaloyl moiety of the formula - (O) C (C 3 -C 3) (SO ₃ M) - in which M is a salt-forming cation.

Description of oligomeric esters

The soil release compositions of the present invention are not resinous, high molecular weight, macromolecular or fibrous polyesters, but are relatively low molecular weight materials which are composed of oligomers rather than polymers. Unique esters of the present invention containing closure moieties include such esters having a molecular weight of 500-8000. Compared with these, glycol terephthalate fiber-forming polyesters have an average molecular weight of 15,000 or more; preferred esters of the invention containing essential units and 5-sulfoisophthalate units generally have a molecular weight of 500-5000. Accordingly, the soil release agents that can be used in the detergent compositions of the present invention are not called "polyesters" but are called "oligomeric esters", as opposed to the long chain polymers commonly used for fiber forming.

The geometry of the molecular structure

The esters used in the compositions of the invention are "substantially linear" in the sense that when more than two ester linking

HU 218 571 Β space, they do not essentially branch or cross-link. (Typically, the branched or cross-linked polyesters disclosed in U.S. Patent 4,554,328 are not predominant esters of the invention.) Although small amounts of cyclic esters formed in the side reactions of ester synthesis, they are non-essential constituents of the invention. . The amount of cyclic esters is preferably not more than 2% by weight of the composition; more preferably, these esters are completely absent from the formulation.

In contrast to the "substantially linear" materials described above, materials with specific side chains are unreactive in ester formation or transesterification reactions. For example, oxy-1,2-propyleneoxy units are not symmetrically substituted; their methyl groups are not conventionally considered to be "branched" in polymer technology (see Odian, Principles of Polymerization, Wiley, N. Y., 1981, pp. 18-19) and show inertness in ester-forming reactions. Other units used in the ester component of the soil release agents of the invention may also contain side chains which exhibit similar inactivity.

The molecular structure

Preferred ester structures according to the invention described above may be as follows:

(a) ester molecules of the formula XXIII containing two end-capping groups which contain essential moieties i), ii) and iii);

(b) an ester molecule having a single closure group of formula XXIV which is a) an ester molecule having a double lid group of formula XXIII containing i), ii) and iii) essential units;

(c) ester molecules of the formula XXV (hereinafter referred to as "hybrid ester molecule") containing two moieties which contain essential units (i), (ii) and (iii). Units (ii) are mixtures of oxyethyleneoxy and oxy-1,2-propyleneoxy units having a molar ratio of 2: 1 in the compound of formula XXV (the ratio above for ester preparations as a whole, if formulations i), ii) and iii. ) are composed of units, in contrast to the above individual ester molecules, very preferably on average (1: 1) to (0: 1)]; and

d) ester molecules of the formula XXVI having two covering groups which contain essential units i), ii), iii) and iv). If the compositions contain i), ii), iii) and iv), the molar ratio of the oxyethyleneoxy units to the oxy-1,2-propyleneoxy units in the composition as a whole is very advantageous (0.5: 1) - (1: 0).

Most preferred among the many soil release structures described above are compounds of formula XXVII wherein R is hydrogen or methyl and the molar ratio is 1.8: 1.

It is apparent from the ester molecule structures described herein that the desired composition and properties of the compositions of the invention are influenced not only by the arrangement of units within the molecule, but also by the composition of the ester mixture according to the invention. Accordingly, for a given number of monomer units and for a given ratio of units, the numbers represent the average number of monomer units in the oligomer component of the composition.

The ester frame structure

Oxyethyleneoxy and terephthaloyl units alternate in the backbone structure of the above-described ester components of the soil release agents of the present invention. The backbone structure may optionally be 5-sulfoisophthaloyl units, terephthaloyl units, oxyethyleneoxy units, or alternatively oxyethyleneoxy, oxypropyleneoxy and aryldicarbonyl and oxyalkyleneoxy units. containing polyoxyethyleneoxy units.

Closure groups of the ester frame structure

As used herein, the term "soil release agent ester components of the invention" refers to novel compounds having two and one end-protecting group and mixtures thereof, which also contain all non-backing group structures. However, in very preferred compositions, they are zero or very minimal. As used herein, the simple term "ester" refers to a mixture of sulfonated, coated and uncoated ester molecules prepared by any process.

Any ester molecule having a non-fully occluding, i.e. not two, occluding closure moiety in the compositions of the present invention should have terminating moieties which are "head" sulfonated with polyethoxy / propoxy closure moieties. These blocking groups are typically hydroxy or other groups which are distinguishable for the unit-forming reagent. For example, in structure (b) above, the hydrogen atom forms a hydroxy group with the chain-terminating group to which it is attached. Other such structures include, for example, - (O) CCl ₄ C (O) -OCH _} groups in the closing positions. However, the most preferred ester molecules for the purposes of the present invention, as described above, have two sulfonated closure moieties and no skeletal moieties in the closure position.

Symmetry of ester molecules

It is also noteworthy that in esters having oxy-1,2-propyleneoxy units, the methyl groups of the oxy-1,2-propyleneoxy units may alternate with the hydrogen atoms of the adjacent -CH ₂ - groups, and thus reduce the symmetry of the ester chain. Accordingly, the orientation of the oxy-1,2-propyleneoxy units is -OCH-frCH1CHpO or the opposite OCH2CH2CH? direction. The carbon atom of the oxy-1,2-propylene units to which the methyl groups are attached is asymmetric, i.e. chiral; they contain four non-equivalent chemical units.

In contrast to oxy-1,2-propyleneoxy units, no stabilizer is used for the purposes of the invention.

The oxy-1,2-alkyleneoxy units can be used as they lack the necessary non-symmetrical character. Crystallization of the oligomer is prevented during manufacture and after addition to the washer by the presence of asymmetric units and / or stabilizers. Therefore, stabilizers are used to prevent crystallization at the use of oxyethyleneoxy units or at a higher proportion of oxyethylene units relative to oxy-1,2-propyleneoxy units. Accordingly, the oligomeric compositions of the present invention comprise sulfonate-type hydrotropes, linear or branched alkylbenzene sulfonates, paraffin sulfonates, or mixtures thereof.

The esters can optionally be combined with various hydrophilicity enhancing and non-polyester materials. This association is usually created by a random connection. The optional units are preferably anionic hydrophilic compounds such as 5-sulfoisophthaloyl or the like. When these units are associated with the ester backbone structure, the backbone structure will generally be divided into two or more hydrophobic groups separated by one or more hydrophilic groups.

It should be noted that unless the structure of the ester polyester is substantially damaged, the non-charged aryldicarbonyl units of the present invention are not necessarily terephthalene. Accordingly, the esters of the invention may contain small amounts of uncharged isomeric dicarbonyl units such as isophthaloyl or the like.

Poly (oxyethylene) oxy Units

The polyoxyethylene oxy units optionally used in the ester components of the soil release agents of the present invention have a degree of polymerization of from 2 to 40 mol% based on the total amount of oxyalkylene oxy units present. Polyoxyethylene oxy units are preferably used when the backbone structure comprises 8 or more terephthaloyl units; however, esters containing 1.5 terephthaloyl units may contain all polyoxyethylene oxy units. The polyoxyethylene oxide units in esters containing predominantly 8 or more terephthaloyl units promote the dissolution of the soil release agent in the wash liquor.

The amount of polyoxyethyleneoxy units present in the skeleton is a function of the degree of polymerization, such as the degree of polymethylation of 2-oxyethyleneoxyethylene units (made from diethylene glycol) and the total oxyalkyleneoxy units in the skeleton structure 0-25 mol%. The degree of polymerization (oxyethylene) ₃ units (prepared from triethylene glycol) may represent 0-18 mol% of the total oxyalkyleneoxy units in the backbone. Oxyethylene ₄ units having degree of polymerization ₄ (prepared from tetraethylene glycol) may represent 0-12 mol% of the total oxyalkyleneoxy units in the backbone.

Closing cover groups

Closing groups for the soil release esters of the present invention are sulfonated ethoxy / propoxy groups. When the esters are dispersed in an aqueous medium, such as washing liquor, these barrier groups create anionic charged sites. Closure moieties facilitate transport in aqueous media and provide hydrophilic sites on the ester molecules.

The esters of the present invention do not exclude the use of acid forms, but are generally employed in the form of the sodium or other alkali metal salt or nitrogen-containing cation (particularly tetraalkylammonium) or in the aqueous medium. Closing groups include, for example, sodium isethionate, sodium 2- (2-hydroxyethoxy) ethanesulfonate, 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, sodium 5-hydroxy 4-methyl-3-oxa-pentanesulfonate, alpha- (3-sulfopropyl) -omega-hydroxy-poly (oxy-1,2-ethane-diyl) (average degree of ethoxylation 1-2), sodium-5-hydroxy-3 -oxa-hexanesulfonate and mixtures thereof.

The soil release agent of the present invention preferably contains from 1 to 2 moles of closure moiety per mole of ester. More preferably, these esters contain two closure groups; i.e., there are 2 moles of closure group present per mole of ester. With respect to the weight of the composition, it is clear that the ratio of the closure groups to the ester molecular weight decreases proportionally with increasing the molecular weight of the ester backbone.

Optional crystallization-reducing stabilizers:

The stabilizers used in the detergent compositions of the present invention must be water soluble or dispersible. Suitable stabilizers for the purposes of the present invention include sulfonate-type hydrotropes, linear or branched alkyl benzene sulfonates, paraffin sulfonates, and other C 4-20 thermally stable alkyl sulfonate compounds. Preferred stabilizers are, for example, sodium dodecylbenzene sulfonate, sodium toluenesulfonate, sodium xylene sulfonate and mixtures thereof. When larger amounts of stabilizer are used, mixtures of hydrotropes and / or other stabilizers are preferred over pure components because they provide better integration into the oligomer and reduce the possible crystallization of the stabilizer.

The amount of stabilizers must be kept to the lowest possible level so as to meet the original conditions for it, ie to reduce the crystallization of the soil release agent during manufacture, storage and addition to the washing machine. The composition of the present invention contains from 0.5 to 20% by weight of a stabilizer. More preferably, the soil release agent will contain enough stabilizer to reduce the crystallization of the oligomer during manufacture and when added to the wash. This amount is at least 3% by weight.

The addition of the stabilizer to the soil release agent can be accomplished by various methods. Preferably, the stabilizer is added to the oligomeric reagents during the initial phase, i.e., before complete oligomerization, so that the stabilizer is uniformly integrated into the oligomer. In another process, the molten preformed oligomer is first melted and then equilibrated to the molten oligomer.

EN 218 571 Β mix the stabilizer. Addition of an alkylbenzene sulfonate surfactant to the detergent compositions does not provide the stabilizing, crystallization-reducing effect of the stabilizer added as described above when dissolving the soil release agent in the wash.

Dye transfer inhibition polymer

Selected dye transfer inhibitors in the composition of the present invention include polyamine-NOXID polymers, N-vinylpyrrolidone-N-vinylimidazole copolymers, polyvinyl oxazolidones, polyvinyl imidazole and mixtures thereof.

These polymers are used in an amount of 0.001 to 10% by weight, preferably 0.01 to 2% by weight.

a) Polyamine-N-oxide polymers

Suitable polyamine N-oxide polymers for use in the present invention are compounds of formula XXVIII in which

P is a polymerizable unit in which the R-N-O groups may be attached to, are part of, or may be a combination of the two;

A is NC (O), C (O) O, C (O), -O-, -S-, edge;

x is 0 or 1; and

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or any combination thereof, in which the nitrogen atom of the N-O group is attached to or is part of these groups.

The N-O group may be a compound of formula XXIX or a group of formula XXX in which

R1, R2 and R3 are aliphatic, aromatic or combinations thereof;

x and / or y and / or z is 0 or 1; and the nitrogen atom of the N-O group is attached to or is part of these groups.

The N-O group (P) may be part of a polymerizable unit, or may be attached to the polymer backbone, or both. Suitable for the purposes of the present invention are polyamine N-oxides wherein the N-O group is part of a polymerizable unit containing N-oxides and R is an aliphatic, aromatic, alicyclic or heterocyclic group.

One of the groups of polyamine N-oxides mentioned above is a polyamine N-oxide wherein the nitrogen atom of the N-O groups is part of the R group. Preferred are polyamine N-oxides wherein R is a heterocyclic group such as pyridinyl, pyrrolyl, imidazolyl, pyrrolidinyl, piperidinyl, quinolinyl or acridinyl and derivatives thereof.

Another group of polyamine N-oxides mentioned above are polyamine N-oxides wherein the nitrogen atom of the N-O groups is attached to the R group.

Other suitable polyamine N-oxides are polyamine N-oxides wherein the N-O group is attached to the polymerizable moiety. Of these, polyamine N-oxides of the formula I in which R is aromatic, heterocyclic or alicyclic and wherein the nitrogen of the N-O functional group is part of the R group are preferred. This group includes polyamine oxides wherein R is a heterocyclic group such as pyridinyl, pyrrolyl, imidazolyl and derivatives thereof.

Another group of preferred polyamine N-oxides is the polyamine N-oxide of formula I wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the N-O functional groups is attached to the R group. These include polyamine oxides wherein R is an aromatic group such as phenyl.

For the purposes of the present invention, any polymer backbone which enables the resulting amino oxide polymer to be aqueous and has a dye transfer inhibitory action is suitable. Typical examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate backbones and mixtures thereof.

Typical amine to amine N-oxide polymers suitable for the purposes of the present invention have a typical amine: amine to N-oxide ratio of from 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymers may be varied by suitable copolymerization or by appropriate degree of Noxidation. The ratio of amine: amine to N-oxide is preferably from (2: 3) to (1: 1,000,000), more preferably from (1: 4) to (1: 1,000,000), and most preferably from (1: 7) to (-) 1: 1,000,000). In fact, the polymers of the invention may be random copolymers in which one monomer type is an amine N-oxide and the other is an amine N-oxide or other monomer. The amine oxide unit of the polyamine N-oxides of the invention has a pKa of less than 10, preferably less than 7 and more preferably less than 6.

Polyamine oxides can be prepared by polymerization of almost any degree of polymerization. The degree of polymerization provided that the desired water solubility and dye transfer inhibitory effect can be obtained is not critical.

The average molecular weight is 500-1,000,000, preferably 1,000-50,000, more preferably 2000-30,000, and most preferably 3000-20,000.

b) N-Vinylpyrrolidone-N-vinylimidazole copolymers

The average molecular weight of the N-vinylpyrrolidone and N-vinylimidazole polymers suitable for the purposes of the present invention is 5,000-1,000,000, preferably 20,000-200,000.

Very useful in the detergent compositions of the invention are N-vinylpyrrolidone-N-vinylimidazole copolymers having an average molecular weight of 5,000-50,000, preferably 8,000-30,000 and more preferably 10,000-20,000.

Determination of the average molecular weight is performed by the light scattering method described in Barth, H.G. and Mays, J.W. Chemical Analysis, Vol. 113, Modem Methods of Polymer Characterization.

The very preferred N-vinylpyrrolidone-N-vinylimidazole copolymers have an average molecular weight

HU 218 571 Β

5,000-50,000, preferably 8,000-30,000, and more preferably 10,000-20,000.

Nvinylpyrrolidone-N-vinylimidazole copolymers having a typical average molecular weight range exhibit excellent dye transfer inhibitory properties while not affecting the cleaning performance of the detergent compositions prepared by their use.

The molar ratio of N-vinylimidazole to N-vinylpyrrolidone in the N-vinylpyrrolidone-N-vinylimidazole copolymers of the invention is 1-0.2, preferably 0.8-0.3 and more preferably 0.6-0.4.

(c) Poly (vinyl oxazolidone)

The detergent compositions of the present invention may also contain polyvinyl oxazolidone as a polymeric dye transfer inhibitor. They have an average molecular weight of 2500-400,000, preferably 5000-200,000, more preferably 5000-50,000 and most preferably 5000-15,000.

(d) Poly (vinylimidazole)

The detergent compositions of the present invention may also contain polyvinylimidazole as a polymeric dye transfer inhibitor. They have an average molecular weight of 2500-400,000, preferably 5000-200,000, more preferably 5000-50,000 and most preferably 5000-15,000.

Peroxidase enzymes

The peroxidase enzymes are used in combination with an oxygen source such as percarbonate, perborate, persulfate or hydrogen peroxide. They are used for "solution bleaching", that is, to prevent the transfer of dye between different materials during washing. Peroxidases are known substances and include horseradish peroxidase, ligninase, halogen peroxidases such as chlorine and bromine peroxidase. Peroxidase-containing detergent compositions are described, for example, in WO 89/099813 and WO 91/05839.

The amount of peroxidase, if used, should be such that its activity is in the range of 0.10-1.00 PODU / ml wash (PODU = Peroxyl / ase Unit).

Peroxidase is typically used as a detergent component and is present in an amount of 0.01-100 mg enzyme, preferably 0.04-0.1 mg enzyme per liter of detergent.

Amylase enzymes

The compositions of the invention may also contain an amylase enzyme. Suitable amylases include, for example, special amylases from B. licheniformis, which are described in more detail in GB-1 296 839. Preferred are, for example, Rapidase from International Bio-Synthetics, Inc. and Termamyl from Novo Industries.

Other suitable amylases include fungi such as Fungamyl from Novo Nordisk A / S.

The amount of amylase should be from 0.01% to 1.5% by weight of the detergent composition. When using a bacterial amylase, such as Termamyl commercial product, the amount of amylase should be such that the activity range is typically 1-500 KNU / 100 g detergent composition (KNU = Kilo Novo Unit).

When a fungal amylase, such as Fungamyl commercial product, is used, the amount of amylase should be such that the activity range is typically 1-5000 FAU / 100g of Fungal Alpha / Immunase Unit.

EDDS chelating agent

The chelating agent is ethylene diamine disuccinate (EDDS), particularly the [S, S isomers], which are described in more detail in U.S. Patent 4,704,233.

Typical amounts of EDDS used are 0.1 to 10% by weight, preferably 0.12 to 5% by weight of the composition.

Parfiimkapszulák

The granular perfume capsules according to the invention are present in an amount of 0.001 to 10% by weight, preferably 0.1 to 3% by weight, based on the composition.

Perfume capsules contain a perfume dispersed in certain carriers.

The term "perfume" as used herein is intended to refer to any fragrance or odor suppressant. The vapor pressure of such materials at room temperature is greater than atmospheric pressure. The perfume or deodorant used in the compositions of the present invention may generally be liquid at room temperature but may also be solid, such as known odor suppressants. A variety of known chemicals can be used as perfumes, including aldehydes, ketones or esters. Perfume materials are generally naturally occurring vegetable and animal oils and extracts containing mixtures of various chemical components; these substances can also be used in the compositions of the invention. The composition of the perfume used in the compositions of the present invention may be a compound of very simple or natural and synthetic chemicals which may produce any desired odor.

The compositions of the present invention may also contain substances commonly used as perfumes. They are mixed with a liquid former, such as a solvent, or, if the perfume does not sublimate or decompose on exposure to heat, simply melted and then combined with the granules.

The compositions of the invention may also contain odor-suppressing agents. In the remainder of this description, these materials are referred to as "perfumes", but they do not have a characteristic odor in themselves, but reduce unpleasant odors. U.S. Pat. No. 3,102,101 discloses suitable odor suppressants.

A variety of capsules can be used to achieve the perfume effect at different times during the cleaning or conditioning process. Less protection for perfumes used in washing / conditioning procedures, a

EN 218 571 Β greater protection is required in the drying process or subsequent surface treatment.

One type of encapsulation of various encapsulated materials is microencapsulation. In these formulations, the perfume forms a capsule core encased in a material such as a polymer. U.S. Patent Nos. 4,145,184 and 4,234,627 disclose a hard coating material that substantially prevents diffusion of perfume. The perfume is conveyed by the microcapsule to the fabric, and the release of the perfume on the fabric is made possible by the microcapsule cracking during the treatment of the fabric.

In another method, the perfume is protected during the wash cycle and released at a higher temperature of the dryer. In the process described in U.S. Patent 4,096,072, fabric conditioners are passed to the fabric during the washing and drying cycle. The transfer is in the form of a particulate material containing hydrogenated castor oil and a fatty quaternary ammonium salt. Perfume may be associated with these granules.

In the process described in U.S. Patent No. 4,152,272, the perfume is associated with wax granules to preserve the perfume during storage in a dry composition and to increase the deposition of granules on the fabric with the cationic surfactant accompanying it. The perfume then diffuses through the wax granules into the fabric under high temperature drying conditions.

The protection may be increased by appropriate selection of the ratio of the encapsulating material to the amount of perfume and encapsulating or agglomerating material.

The encapsulating material used to make the perfume particles of the present invention depends to some extent on the perfume used. Some perfumes require more protection than others, so the encapsulating material must be selected accordingly.

Generally, perfume particle encapsulating materials may be water-soluble or water-insoluble.

Examples of water insoluble materials are polyethylene, polyamide, polystyrene, polyisoprene, polycarbonate, polyester, polyacrylate, vinyl polymer, polyurethane or mixtures thereof.

Suitable water-soluble substances include, for example, methylcellulose, maltodextrin and gelatin. Such coatings are used in an amount of 1 to 25% by weight based on the weight of the particulate material.

A particularly useful example of a water-soluble encapsulating material is that described in British Patent No. 1,464,616, containing polysaccharide and polyhydroxy compounds.

Further examples of water-soluble or dispersible encapsulating materials are dextrins derived from non-gelatinized starch acid esters of substituted dicarboxylic acids described in U.S. Patent 3,455,838. These acid ester dextrins are preferably prepared from starches such as waxy corn, waxy millet, sago, tapioca and potato starch. Typical examples of such materials are National Starch, N-Lok, Narlex (ST and ST2) and Capsul E. These products contain pregelatinised waxy corn starch and optionally glucose. The starch is modified by monofunctional substituted groups, such as octenyl succinic anhydride.

Water-soluble materials are particularly preferred when the perfume is to be combined with a dry granular or powder product. This water-soluble capsule protects the perfume from other ingredients in conventional detergents such as bleach, enzymes and clay during storage.

In order to increase the protection of perfumes used in liquid products, it is desirable to perform perfusion encapsulation with pH-sensitive materials. These are materials that act as coatings in one pH range and leave the particles in another pH range. Such material is used, for example, to encapsulate perfume in a liquid fabric softener composition having a pH of about 3. If such a composition is added to a laundry having a pH greater than 6, the coating may peel off. Such encapsulation allows the perfume in liquid formulations to be protected over a long period of time, i.e. not easily diffused from the granule in the liquid medium. The diffused pellets of the detached coating may be diffused when the pellets are contacted with a different pH medium.

The perfume may also be encapsulated in a material which renders the granules more compatible with the treated surface, such as the surface of the fabric treated in the washing process. Such materials facilitate the delivery of granules to the fabric and maximize the release of perfume directly onto the fabric surface. These materials are generally water-insoluble cationic materials. Examples of such materials are the cationic compounds listed in U.S. Patent 3,686,025 (including imidazolinium). These are well known materials and include, for example, quaternary ammonium salts containing at least one, preferably two, C 10-20 alkyl substituent groups; alkylimidazolinium salts in which at least one alkyl group contains a C8-C25 chain; and C12-20 pyridinium salts.

Other encapsulating materials which are well compatible with textiles include those described in U.S. Patent 4,234,627.

Encapsulated perfume particles can be prepared by mixing the perfume with the encapsulating material. Mixing is accomplished by subjecting the emulsions comprising the encapsulating material and the perfume to a spray-drying process. The particle size of the material formed in the spray-drying tower may also be modified. The modification requires special processing steps, such as granules10

An additional tower agglomeration step (such as a fluidized bed operation) and / or processing steps in which the surface properties of the capsules are modified are incorporated to increase the size. For example, hydrophobic silica dust is used to reduce the hygroscopicity of the capsules.

One particularly preferred encapsulation process is emulsification by spray drying followed by silica dusting in the final step. The formation of the emulsion is carried out as follows:

a) The starch is dispersed in water at a temperature of 1: 2 by weight at room temperature. The starch is preferably pregelatinized to form the emulsion at this temperature. As a result, perfume loss will be minimal. The starch must have a low viscosity in order to obtain high starch concentration and perfume uptake in the water.

b) The perfume oil is then added to the above mixture (0.8-1.05): 1: 2 by weight, and the mixture is emulsified with a high shear mixer. The shear force must produce oil droplets below 1 pm and the emulsion must be stable in this form for at least 20 minutes (the starch serves to stabilize the once mechanically produced emulsion).

c) The mixture is spray-dried in a counter-current tower equipped with a rotating atomizer. The drying air inlet temperature is 150-200 ° C. This type of spray drying allows for minimal loss of perfume and a high drying rate. The granules have a particle size of 50-150 µm.

d) The dry capsules thus obtained may contain up to 5% by weight of non-encapsulated oil on the surface of the granulate. Optionally, up to about 2% by weight of hydrophobic silica may be added to the capsules in a belt mixer.

Other suitable perfume capsules may also be perfumes dispersed in certain carriers. Clay or zeolite described in European Patent No. 535,942 may also be used as such carrier. They have a nominal pore size of at least 0.6 nm and thus the perfume is absorbed in the pores of the zeolite particles. The particles are then embedded in or coated with a mixture of a water-soluble liquid polyol or diol and a solid polyol containing more than 3 hydroxyl groups.

It may also be desirable to add a perfume that does not have capsule protection. Such a perfume makes the composition itself aesthetically pleasing. When you open the package containing the product and add the product to the water, this fragrance is immediately perceptible.

This perfume is combined with a liquid formulation or sprayed onto a dry product using a conventional device such as a stirrer.

The detergent additive of the present invention can be associated with a variety of formulations, including detergent and rinse aid formulations, which allow perfume to reach the fabric.

The packaging system:

The packaging system used for the packaging of detergent compositions of the present invention is characterized by a Moisture Vapor Transfer Rate (MVTR) of 1-15 g / m ² / day and a bag of foldable soldered refillable plastic foil or plastic / paper laminate.

The wet vapor transmission rate is measured by a known method, such as that described in ASTM E-96-53T for measuring the water vapor permeability of the raw materials, and by the TAPPI T464 m-45 standard for measuring the high vapor permeability and moisture content of the raw materials.

Testing of the compositions of the present invention is the so-called procontest, which is performed on a Permatran-W TWIN apparatus.

Description of the procedure:

Equipment used:

- aluminum test cups with lids (10.16 and 15.34 cm in diameter);

- 1 template (for sample cutting);

- 2 templates (for wax application);

- electric hob;

- laboratory furnace with temperature control (accuracy of +1 ° C);

- cabinet with humidity control (accuracy: ± 2% relative humidity);

- microcrystalline wax (trade name Mobel Oil Wax 2305 or equivalent);

- Calcium chloride, anhydrous, granular, particle size: 1.7 mm;

- kerosene;

- electric dish with thermostat for melting the wax;

- cutting table;

- scissors or circular cutting knives; and

- Laboratory balance (eg Mettler K-7, Mikrowa type FW-31-6), accurate to ± 0.05 g.

Production of materials

Specimens are cut from the packaging material to be tested, such as laminated polyethylene bags. As a control, a test piece cut from a uniform protective sheet made of a known MVTR protective material (for example, bitumen laminated fabric or wax laminated sheet) is used.

The investigation procedure

1. Heat the wax in the electric vessel to 90-110 ° C. The test dishes are heated in the oven or on the hot plate at about 90 ° C for 1/2 hour. Remove only one cup at a time from the furnace and fill the cups with calcium chloride up to 2/3 of the height of the ring and carefully add kerosene to the tapered edge of the template. The template contact area of the template 2 is wiped dry. The template 2 is placed on the sample and centered on the rim of the cup. Melted wax is poured into a circular space formed by the tapered edge of the template 2 and the rim of the cup. As the wax solidifies, the 2 templates are turned off with a slight twisting motion11

HU 218 571 Β. The cup assembly is weighed to the nearest 0.05 g before being placed in the assay atmosphere. The cups were then stored at 35 ° C and 80% relative humidity.

2. The cups are kept in the humid chamber for 2 days and weighed every 24 hours. The measurement is continued until three successive measurements result in a constant weight gain (maximum difference 0.25 g). Measurements are taken immediately after removal from the wet chamber and covered with an aluminum cover when removed from the chamber.

In each case, the weight measurement result is recorded and the daily weight gain for each cup is calculated. The MVTR is recorded in g / m ^2/24 hours and calculated as follows:

(a) in the case of an effective area of 6,6,6 cm ² (10,16 cm diameter cup):

3600 x - g / m ^2/24 hours; y

(b) in the case where the effective area of the sample is 133 cm ² (15,34 cm diameter cup):

Χ 1800 - g / m ^2/24 hours; y in the formulas: x = total weight gain [g], y = time [h];

both are calculated on the basis of the measurement results for 3 consecutive periods with constant daily weight gain.

The packaging system useful in the present invention has an MVTR of from 1 to 15 g / m ² / day, preferably 5 g / m ² / day.

Commercial units of the packaging system of the invention are bags / sacks which are used as refill bags.

Refill bags are easy-to-fold containers that are designed to minimize the amount of polluting plastics that they become when they become waste.

The use of refill bags can be accomplished by transferring their contents into a permanent packaging such as a plastic or metal can or a carton used by the consumer to store detergent products.

In such cases, the refill bag cannot be resealed.

The bags according to the invention may be pillow bags or knitted bags; each of these, and in particular the tied bags, shall be designed so that their upper space is reduced in size or has no upper space; they may be made from raw materials or from preformed and / or folded materials; and may be sealed by various means, such as heating or gluing / gluing, adhesive tapes.

The bags / sacks of the present invention may be made from films, including single-layer materials, including coextruded or laminated materials; such films being plastic films or combinations of paper and plastic; plastic and paper laminates are preferred. Polyolefins are typically used as plastics. Plastics and paper may be new or recycled; printing of the films according to the invention may be carried out by various methods, for example by light printing or flexo or offset printing.

Also included within the scope of the invention are films which are made moisture-proof by coextrusion or by coating or resin coating of resins.

Commercial units according to the invention may also be of cardboard / box / barrel made of corrugated or laminated material or combinations thereof; each material may be new or recycled.

The above cardboard / box / barrel means may be coated with a layer of material, typically a metal or plastic layer, to form the desired MVTR.

The above carton / box / barrel means may be printed as above and / or coated with materials such as varnishes to provide proper barrier properties.

Optional additives

The formulations of the present invention may contain additives other than the one or more selected additives described above, such as those described below.

In addition to the bleach activators described above, the present invention provides compositions comprising a non-enzymatic bleach; however, granular laundry detergent compositions which do not contain bleach may be desirable, particularly for textiles requiring special treatment; therefore, the present invention also provides such compositions without bleach.

Preferred moisture sensitive materials for compositions without such bleach include choline ester polyaspartate, polyglutamate, maleic acid / acrylic acid / vinyl alcohol terpolymers, sulfonated polyethoxy / propoxy barrier ester oligomers, peroxidase enzymes, and mixtures thereof.

Fehérltőszer

The bleaching agent, when used, can be an inorganic perso such as perborate, persulfate, percarbonate or a preformed organic peracid or perimidic acid such as Ν, Ν-phthaloylaminoperoxycaproic acid, 2-carboxyphthaloylaminoperoxycaproic acid, N, N-phthaloylamino peroxivaleric acid, peroxyadipic acid nonylamide, 1,12-diperoxidodecanedioic acid, peroxybenzoic acid and ring-substituted peroxybenzoic acid, monoperoxyphthalic acid (magnesium salt hydrate), and diperoxylic acid.

The detergent containing the bleaching agent of the present invention typically has a bleach content of from 1 to 40% by weight, preferably from 3 to 30% by weight, and more preferably from 5 to 25% by weight.

The perborate bleach is generally a sodium salt which is present in the form of monohydrate or tetrahydrate.

The average particle size of the percarbonate bleach, generally in the form of the sodium salt, is in the range of 250 to 900, preferably 500 to 700. Sodium percarbonate is an additive having the formula: 2Na ₂ CO ₃ .3H ₂ O ₂ .

HU 218 571 Β

To improve the storage stability of the percarbonate, for example, an additional mixed salt coating comprising alkali metal sulfate and carbonate may be used. Such coatings and coating processes are described in British Patent No. 1,446,799. The weight ratio of the mixed salt coating material to percarbonate is (1: 2000) to (1: 4), preferably (1:99) to (1: 9) and more preferably (1:49) to (1:19). The mixed salt is preferably sodium sulfate and sodium carbonate and preferably Na ₂ SO ₄ -n-Na ₂ CO ₃ wherein n is from 0.1 to 3, preferably 0.3 to 1.0, and more preferably 0 , from 2 to 0.5.

Other suitable coatings include sodium silicate or magnesium silicate containing SiO ₂ : Na ₂ O (1.6: 1) by weight (2.8: 1).

Commercially available carbonate / sulfate coated percarbonate may also contain small amounts of a heavy metal sequestering agent, such as EDTA, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), or an aminophosphate component that is incorporated during manufacture.

Preferred heavy metal sequestering agents include organic phosphonates and aminoalkylene poly (alkylene phosphonates), such as alkali metal ethane-1-hydroxyphosphonates, nitrilotrimethylene phosphonates, ethylenediaminetetramethylenes, diethylenetriamine penta-phosphonates.

Surfactants

Preferred detergents according to the invention may also contain a surfactant component which may be:

Alkyl sulfate surfactant

Used in compositions of the invention are alkyl sulfate surfactants include a ROSO ₃ M acids or their water-soluble salts of formula I, wherein R is from 10 to 24 carbon atoms, a hydrocarbon group, preferably an alkyl or hydroxyalkyl group containing from 10 to 20 carbon atoms in the alkyl moiety, more preferably C 12 -C 18 alkyl or hydroxyalkyl, and M represents a hydrogen atom or a cation such as an alkali metal cation (e.g. sodium, potassium or lithium) or an ammonium or substituted ammonium group (e.g. methyl, dimethyl and trimethylammonium). cation as well as quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Preferred alkyl chains at lower wash temperatures (e.g., below about 50 ° C) typically have from 12 to 16 carbon atoms, and at higher wash temperatures (e.g., above about 50 ° C), preferred alkyl chains typically have from 16 to 18 carbon atoms.

Alkylalkoxylated sulfate surfactants

Alkyl alkoxylated sulfate surfactants for use in the compositions of the present invention include acids (R (A) _m SO ₃ M) or water-soluble salts thereof wherein R is an unsubstituted C 10 -C 24 alkyl or

A hydroxyalkyl group containing from 10 to 24 carbon atoms, preferably a C 12-20 alkyl or hydroxyalkyl group, and more preferably a C 12-18 alkyl or hydroxyalkyl group; A is an ethoxy or propoxy moiety; m is greater than 0, typically 0.5-6, preferably 0.5-5; and M represents a hydrogen atom or a cation such as a metal cation (e.g. sodium, potassium, lithium, calcium or magnesium) or an ammonium or substituted ammonium cation. Also included are alkyl ethoxylated and alkyl propoxylated sulfates. Examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, diethylamine, triethylamine and mixtures thereof. Examples of such surfactants include C 12 -C 18 alkyl polyethoxylate (1,0) sulfate, C 12 -C 18 E (1,0) M, C 12 -C 18 alkyl polyethoxylate (2,25) sulfate, C 12 -C 18 E. (2,25) M, C 12 -C 18 alkyl polyethoxylate (3) sulfate, C 12 -C 18 E (3) M and C 12 -C 18 alkyl polyethoxylate (4) sulfate, C 12 -C 18 E (4) M wherein M is preferably sodium or potassium.

Other Anionic Surfactants The detergent anionic surfactants for use in the detergent compositions of the present invention may also be the following or used alone: soap salts, including, for example, sodium, potassium, ammonium, or substituted ammonium salts, such as mono-, di-, or trietanolsók; Sulfonated polycarboxylic acids prepared by sulfonation of C9-C20 linear alkyl benzene sulfonates, C8-C22 primary or secondary alkane sulfonates, C8-C24 olefin sulfonates, pyrrolized derivatives of alkaline earth citrates, e.g. polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C14-C16 methyl ester sulfonates; alkyl glycerol; fattyoleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionate, N-acyl taurate, alkyl succinate and sulfosuccinate, sulfo monosuccinate especially C12-C18 saturated and unsaturated monoesters), sulfosuccinate diesters (especially C6-C14 saturated and unsaturated diesters), acyl sarcosinates, alkyl polysaccharide sulfates such as non-alkyl polyglucoside sulfated compounds, described below), branched-chain alkyl alkyl sulfates, alkyl polyethoxycarboxylates, such as those of the formula RO (CH ₂ CH ₂ O) _k CH ₂ COO® M®, wherein R is C 8 -C 22 alkyl, k is an integer from 0 to 10, and M is a cation forming a soluble salt. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resins in or derived from tall oil 13 may be used.

EN 218 571 Β blind and hydrogenated resin acids. Further examples are found in "Surface Active Agents and Detergents" (Vol. II by Schwartz, Perry and Berch). Many such surfactants are also disclosed in U.S. Patent 3,929,678.

Preferred surfactants for use in the compositions of the invention include alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.

The anionic surfactant content of the detergents of the present invention, when used, is typically from 1 to 40% by weight, preferably from 3 to 20% by weight.

Nonionic surfactants

The detergents of the present invention preferably also contain a nonionic surfactant.

Any nonionic surfactant may be used in the compositions of the invention, but two of these groups are particularly preferred. One group includes alkoxylated (primarily ethoxylated) alcohols, the other group includes nonionic surfactants consisting of amide derivatives of fatty acid esters and N-alkyl polyhydroxyamines. Amide derivatives of esters and amines are referred to herein as polyhydroxy fatty acid amides. Mixtures containing one or more nonionic surfactants containing at least one alkoxylated alcohol and polyhydroxy fatty acid amide surfactant are particularly suitable for use in the compositions of the present invention.

Suitable surfactants include condensation products of alkylene oxide groups (hydrophilic in nature) and organic hydrophobic compounds, which may be aliphatic or aromatic. The length of the polyoxyalkylene groups fused to a particular hydrophobic moiety can be varied to form water-soluble compounds in which the hydrophilic and hydrophobic moieties are desirably balanced.

Particularly useful nonionic surfactants in the compositions of the present invention are poly (ethylene oxide) condensates of alkyl phenols, such as straight or branched alkyl phenol condensation products containing from 6 to 16 carbon atoms, which are 4 to 1 mole of alkyl phenol. They contain 25 moles of ethylene oxide.

Preferred nonionic surfactants are the water-soluble condensation products of straight or branched aliphatic C 8 -C 22 aliphatic alcohols containing up to 25 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having from 9 to 15 carbon atoms containing from 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol and ethylene oxide. Most preferred are the condensation products of alcohols having 12 to 15 carbon atoms containing an average of 3 moles of ethylene oxide per mole of alcohol.

Nonionic surfactant components of surfactant systems also useful in the compositions of the present invention include alkyl polysaccharides described in U.S. Patent 4,565,647, having a hydrophobic group of from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide. for example, a polyglycoside hydrophilic moiety has from 1.3 to 10, preferably from 1.3 to 3 and more preferably from 1.3 to 2.7 saccharide units. Any C5-C6 reducing saccharide such as glycosyl groups (optionally containing hydrophobic groups attached at the 2-, 3-, 4-, etc. positions and thus forming a glucose or galactose opposite to a glycoside or galactoside) can be used. For example, the intersaccharide linkages are between one of the positions of the additional saccharide moieties and the 2-, 3-, 4- and / or 6-positions of the previous saccharide moiety.

Preferred alkyl polyglycosides are compounds of formula XXXI wherein R ² is alkyl or alkylphenyl, hydroxyalkyl or hydroxyalkylphenyl containing from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably from 1.3 to 3 and more preferably from 1.3 to 2.7. Glycosyl is preferably derived from glucose. In preparing such compounds, the alcohol or alkyl polyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form the glycoside (linked in the 1-position). Further glycosyl units may be linked between their 1-position and the 2-, 3-, 4- and / or 6-positions, preferably 2-positions, of the preceding glycosyl units.

Other surfactants

The detergent compositions of the present invention may also contain cationic, ampholytic, dual ionic and semi-polar surfactants as surfactant components, as well as non-ionic surfactants other than those described above, including the semi-polar nonionic amine oxides described below.

The detergent cationic surfactant component of the detergents of the present invention uses compounds having long chain hydrocarbon groups. Examples of such cationic surfactants are ammonium surfactants, such as alkyldi- and trimethylammonium compounds, and compounds of formula XXXII wherein R ² is alkyl or C 8 -C 18 alkyl-benzyl-alkyl. group; R ³ is independently selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 and mixtures thereof; R ⁴ is independently selected from C1-4 alkyl, C1-4 hydroxyalkyl, or two R ⁴ group formed by joining a benzyl or -CH2COH-CHOHCOR <> CHOHCH ₂ OH wherein R ⁶ is any hexose or hexose polymer having a molecular weight of less than 1000 and, when y is not 0, is hydrogen; R ⁵ is as defined for R ⁴ , or is an alkyl chain having up to 18 total carbon atoms in R ² and R ⁵ ; and y is independently O

HU 218 571 Β

Up to 15; and X is any compatible anion.

Other cationic surfactants useful in the compositions of the present invention are also described in U.S. Patent No. 4,228,044.

The cationic surfactant content of the detergent compositions of the present invention, when used, is typically from 0% to 25% by weight, preferably from 3% to 15% by weight.

Ampholytic surfactants are also useful in the detergents of the present invention. In a broad sense, these are aliphatic derivatives of secondary or tertiary amines or heterocyclic secondary or tertiary amines containing straight or branched alkyl groups. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8 to 18 carbon atoms, and at least one anionic water soluble group, such as a carboxy, sulfonate or sulfate group. Ampholytic surfactant is described, for example, in U.S. Patent No. 3,929,678.

The detergent compositions of the present invention typically have an ampholytic surfactant content of from 0% to 15% by weight, preferably from 1% to 10% by weight, when used.

Dual ionic surfactants are also useful in the detergents of the present invention. In a broad sense, these are aliphatic secondary or tertiary amine heterocyclic secondary or tertiary amine derivatives or quaternary ammonium derivatives or quaternary phosphonium or tertiary sulfonium compounds. Such a dual ionic surfactant is also described, for example, in U.S. Patent No. 3,929,678.

The dual ionic surfactant content of the detergent compositions of the present invention, when used, is typically from 0% to 15% by weight, preferably from 1% to 10% by weight.

Semi-polar nonionic surfactants are non-ionic surfactants which are special surfactants which may be water-soluble amino oxides containing one C 10 -C 18 alkyl group and two C 1 -C 3 alkyl groups or hydroxyalkyl groups; or water soluble phosphine oxides containing one C 10 -C 18 alkyl group and two C 1 -C 3 alkyl groups or hydroxyalkyl groups.

Semi-polar nonionic detersive surfactants include amine oxide surfactants of formula XXXIII.

Detergent Builders

The detergents of the present invention contain a detergent builder. This is preferably a non-phosphate detergent builder, but phosphate-containing types are also within the scope of the invention. These include, for example, alkali metal carbonates, hydrogencarbonates, silicates, alumina silicates, carboxylates, and mixtures thereof. The detergent builder content of the granular detergents of the present invention is from 1 to 80% by weight, preferably from 20 to 60% by weight of the composition, and from 1 to 30% by weight of the liquid detergent.

Suitable silicates are those having a SiO ₂ : NaO ₂ molar ratio of 1.6 to 3.4, and so-called amorphous silicates having a SiO ₂ : NaO ₂ molar ratio of 2.0 to 2.8 are preferred.

Within the family of silicates, crystalline layered sodium silicates of Formula XXXIV, wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20 are very preferred. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514; processes for their preparation are described in DE-A-3417649 and DE-A-3742043. In a compound of the above general formula suitable for the purposes of the invention, x is 2, 3 or 4, preferably 2. More preferably, M is sodium and y is 0. Such a compound is preferably Na ₂ Si ₂ O ₅ . These materials are sold under the trade names NaSK.S-5, NaSK.S-7, NaSKS-11 and NaSKS-6 by Hoechst AG FRG. Most preferred is NaSK.S-5 under the trade name Na ₂ Si ₂ O ₅ . Crystalline layered silicates are combined as dry mixed solids or solid agglomerates with other materials.

Although many aluminosilicate ion exchange agents can be used in the compositions of the present invention, it is preferred to have a uniform cellular aluminosilicate zeolite of formula XXXV wherein a and y are at least 6, a: y molar ratio is 1.0 to 0.4, and It ranges from 10 to 264. Amorphous hydrated aluminum silicate materials useful in the present invention are compounds XXXVI wherein M is sodium or potassium, ammonium or substituted ammonium, z is 0.5 to 2, and y is 1. The ion exchange capacity of such materials is at least 50 mg calcium -carbonate equivalent hardness / Ι g anhydrous aluminum silicate. The particle size is preferably from 0.01 to 10 µm.

Aluminum silicate ion-exchange building materials suitable for the purposes of the present invention are hydrated and contain 10-28% by weight of water for crystalline material and potentially even greater amounts for water for amorphous material. The highly preferred crystalline aluminosilicate ion exchange materials contain 18-22% by weight of water in their crystal structure. Another characteristic of crystalline aluminum silicates is that they have a particle diameter of 0.1 to 10 µm. Amorphous materials are often smaller, e.g., with a lower size limit of less than 0.01 µm. Preferred particle diameters of the ion-exchange materials are from 0.2 to 4 µm. The term "particle diameter" as used herein refers to the average particle diameter of a given ion exchange material measured by conventional analytical techniques, such as microscopy using a scanning electron microscope.

Aluminum silicate ion exchange materials suitable for the purposes of the present invention are commercial products. They are

Substances may have a crystalline or amorphous structure and may be of synthetic or natural origin. A process for the production of aluminum silicate ion exchange materials is described in U.S. Patent No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials suitable for the purposes of the present invention are commercially available as Zeolit A, Zeolit X and MAP. The latter is described in EPA Publication No. 384,070. Of the crystalline aluminosilicate ion exchange materials, particular preference is given to Zeolite A of formula XXXVII wherein x is from 20 to 30 µm, in particular about 27 µm, and generally has a particle size of less than 5 µm.

Suitable carboxylate-type building materials containing a carboxylate group include lactic acid, glycolic acid and their ether derivatives as described in Belgian Patent Nos. 831,369, 821,369, and 821,370. Polycarboxylates containing two carboxylate groups include the water soluble salts of succinic acid, malonic acid, ethylene dioxydiacetic acid, maleic acid, diglycolic acid, boric acid, tartric acid and fumaric acid, and in German Patent Nos. 2,446,686 and 2,446,687; The ether carboxylates described in United States Patent 257, and in addition the sulfinyl carboxylates described in Belgian Patent 840,623. Polycarboxylates containing three carboxylate groups include water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as carboxymethyloxysuccinates disclosed in British Patent No. 1,379,241; oxy-polycarboxylates, such as the 2-oxa-1,3,3-propane tricarboxylates described in British Patent 1,387,447.

Polycarboxylates containing four carboxylate groups include the oxydisuccinates described in British Patent No. 1,261,8291 as well as 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. 2,3-propane tetracarboxylates. Polycarboxylates containing a sulfo substituent include sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422, and U.S. Patent Nos. 3,936,448, and sulfonated pyrrolized pyridized derivatives disclosed in British Patent 1,082,179. citrates and polycarboxylates having a phosphate substituent as described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane cis, cis, cis tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis, dicarboxylates, 2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexanehexacarboxylates and carboxymethyl derivatives of polyhydroxy alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and phthalic acid derivatives as described in British Patent No. 1,425,343.

Other additives, if appropriate

Other additives commonly used in detergent compositions may also be used in the compositions of the invention. Examples include: other bleach activators, other chelating agents, other enzymes, anti-sludge agents, textile softeners, in particular textile softeners, and dyes, fillers, optical brighteners, pH adjusting agents, non-structural alkaline sources, enzyme stabilizers, solvents and perfumes.

Other bleach activators

Particularly preferred as an additional bleach component of the compositions of the present invention are the Ν, Ν, Ν ', Ν'-tetraacylated compounds of formula XXXVIII wherein x is 0 or an integer from 1 to 6.

Examples of such compounds are tetraacetylmethylenediamine (TAMD), where x = 1, tetraacetyl ethylenediamine (TAED), where x = 2, and tetraacetylhexylene diamine (TAHD), where x = 6. Such compounds and analogs thereof are described, for example, in GB-A-907 356. The most preferred peroxyacid bleach activator component as an additional bleach component is TAED.

A further preferred group of peroxyacid bleach components are amide substituted compounds of the formulas XXXIX and XL wherein R ¹ is C 1-14 aryl or alkaryl, R ² is C 1-14 alkylene, arylene and alkarylene, and R ⁵ is C 1 -C 10 hydrogen or an alkyl, aryl or alkaryl group, and L can be substantially any leaving group. Preferably R ^{1 is C} 6 -C 12, and R ^{2 is} preferably C 4 -C 8. R * can be straight or branched alkyl, substituted aryl or alkylaryl having a branched chain substituent, or both, and may be derived from either synthetic or natural sources, such as tallow fat. The R ² group can be a number of analogous structure. The substituent may be an alkyl or aryl group, a halogen, a nitrogen or a sulfur atom, or other typical organic substituent group or compound. ^R5 is preferably hydrogen or methyl. R ¹ and R ⁵ may together contain up to 18 carbon atoms. Amide-substituted bleach activator compounds of this type are disclosed in EP-A-0170386.

Other chelating agents

The detergent compositions of the present invention may also contain iron and / or manganese chelating agents other than EDDS. Such chelating agents include aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, as described below. Without any particular theoretical discussion, these can be said to be advantageous because they form soluble chelates with iron and manganese and are thus removed from the washing liquor.

Such optional chelating agents include: ethylenediaminetetraacetate16.

EN 218 571 Β cases, N-hydroxyethyl ethylenediamine tetraacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetramine hexaacetates, diethylene triamine pentaacetates and ethanol diglycines, their alkali metal and ammonium salts, ammonium salts thereof and mixtures thereof.

Amino phosphonates may also be used as chelating agents in the composition of the present invention, provided that at least a small amount of phosphorus is allowed in the detergent composition. Such materials include ethylenediamine tetrakis (methylphosphonate) (also known as DEQUEST). These aminophosphonates preferably contain up to 6 carbon atoms of alkyl or alkenyl.

Polyfunctionally substituted aromatic chelating agents may also be used in the compositions of the present invention. (See U.S. Patent No. 3,812,044.) Of this type of compound, the preferred acid form is the dihydroxydisulfobenzene derivative, such as 1,2-dihydroxy-3,5-disulfobenzene.

Other enzymes

The detergent compositions of the present invention may contain enzymatic agents other than peroxidase and amylase. Examples of such enzymatic agents are proteases, lipases, cellulases and mixtures thereof. Suitable lipase enzymes are, for example, Lipolase from Novo Industries A / S (Denmark), and lipases (Novo Nordisk) such as Lipolase 165 KLU (KLU = Kilo Lipolase) are also suitable. í / nit).

Commercially available protease enzymes are preferred, including Novo Industries A / S (Denmark), Alcalase and Savinase (Commercial), and International Bio-Synthetics, Inc. (Netherlands), Maxatase (e.g. Savinase 13 KNPU). (KNPU = Ájlo Novo Pmtase í / nit).

Other proteases include Protease A and Protease B as disclosed in European Patent Publication No. 130,756.

A preferred method of preparing the detergents of the present invention

In a preferred process for the preparation of detergents of the present invention, in particular where a high density formulation is desired, some or all of the surfactant component of the finished product is incorporated as a separate particulate material; these granules may be in the form of flakes, granules, noodles, ribbons or other forms, but preferably granules. In the most preferred manufacturing process, the powders (e.g., aluminum silicate or carbonate) are agglomerated with a very active surfactant paste and the particle size is kept within the defined range. In such a process, one or more agglomerators, e.g. Paderbom 1, Elsenerstrasse 7-9, Pf. 2050, Germany. Most preferred are high shear mixers such as Lodige CB.

The amount of highly active surfactant is 50-95% by weight, preferably 70-85% by weight, based on the total surfactant used. The surfactant system may be anionic, nonionic, cationic, amphoteric, double ionic or mixtures thereof. Pumping of the paste into the agglomerator is carried out at such a high temperature that the pumpable viscosity is maintained but the anionic surfactant used is not yet decomposed. Typical operating temperatures are 50-80 ° C.

A particularly preferred embodiment of the process for preparing the particulate surfactant from a very active surfactant paste is described in European Patent 510,746.

The free flowing particulate materials may be prepared by the process described above and then mixed with the other detergent components to form the final detergent composition. This mixing may be carried out by any suitable apparatus. Liquid detergents, such as nonionic surfactant and perfume, are sprayed onto the surface of one or more ingredients of the granulate or into the finished composition.

Examples

Granular detergent compositions of the present invention are prepared from the following ingredients.

Spreadsheet

Examples 1 2 3 4 5 6 7 8 component (crowd%) Linear alkyl sulfonate 7 0 0 0 0 0 0 0 Tallow alkyl sulfate 3 0 0 0 0 0 0 0 Alkyl sulfate 0 9 6 9 12 12 9 6 Alkyl ethoxylate sulfate 0.2 2 1 2 2 3 3 3 Kókuszkolin ester 0 0 0 0 0 0 0 0 Alkyl ethoxylate (5-7 times ethoxylated) 4 5 10 6 4 7 8 12

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Table (continued)

Examples 1 2 3 4 5 6 7 8 component (%, By weight) Alkyl N-methyl glucose 0 2 3 3 1 3.5 3.5 3.5 perborate 22 0 0 0 0 0 0 0 percarbonate 0 22 19 22 24 0 0 0 (6-octanamido-caproyl) oxy sulfonate 0 5 0 0 0 0 0 0 Benzoyl caprolactam 0 0 2 5 0 0 0 0 N- [4- (triethylsilyl ammonio-ylmethyl) - benzoyl chloride salt kaprolaktámj 0 0 0 0 4 0 0 0 Ν, Ν, Ν, Ν-ethylene Tetraacetyl diamine 5 0 2 5 0 0 0 0 S, S-Ethylene-disuccinic acid 0 0 0.5 0.5 0.5 0 0 0 Peroxidase 1 PODU / g 0 0.4 0 0.3 0.1 0.2 0 0.1 Termamyl 60 KNU / g 0.6 0.3 0 0.2 0.5 0.8 0.2 0.2 Fungamyl 1600 FAU / g 0 0,125 0.2 0.2 0.2 0 0.3 0.3 Lipolase 165 KLU / g 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Cellulase 1000 CEVU / g 0.1 0.2 0.3 0 0.3 0.2 0.2 0.2 Endoglucanase 5000 CEVU / g 0 0.1 0.1 0 0.1 0.1 0.1 0.1 Protease (Savinase) 13 KNPU / g 0.4 0.5 0.7 0.7 0.5 0.7 0.7 0.7 Aluminum Silicate (Zeolite A) 21 13 15 15 18 19 21 23 Layered silicate 0 12 11 11 9 9 11 7 Sodium citrate 6 5 4 4 3 11 9 8 N atrium carbonate 16 8 7 7 7 11 11 9 Sodium silicate 3 0 0 0 0 4 6 8 Sulfate 4 0.6 0.6 0.6 0.6 0 0 0 Soil release polymer (oligomer ester) 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.2 Polyvinyl N-oxide (VATO) 0.3 0 0 0.5 0.2 0.2 0.4 0.3 Poly (vinylpyrrolidone / vinylimidazole) PVPVI copolymer 0 0.05 0 0 0.2 0 0.5 0.1 Terpolymer of maleic acid / acrylic acid / vinyl alcohol 0 0 3 4 0 3 0 0 polyaspartate 0 0 0 0 0 0 4 2 perfume Capsules 0 0 0.2 0 0 0 0 0.4 Minor amounts of other ingredients 100% supplemental quantity

When the compositions according to the invention are filled into plastic bags having a vapor transmission rate of MVTR = 5 g / m ² / day, for example laminated polyethylene bags or plastic containers having a MVTR of 0.5 g / m ² / day and sealed. The laundry compositions so packaged exhibit excellent stability even after storage for 4 weeks at 35 ° C in an 80% RH environment. The equilibrium relative humidity (eRH) at 35 ° C after storage for 4 weeks ranges from 10% to 28%. 60

Claims (7)

PATENT CLAIMS A combination packaging system comprising a granular detergent composition, wherein the detergent composition comprises at least one of a moisture-sensitive component of: - polyhydroxy fatty acid amide non-ionic surfactants, - Bleach activators of alkanoyloxybenzoyl sulfonates, amido derivatives, benzoxazine derivatives18 They may be compounds, quaternary substituted compounds, or mixtures thereof; - polymers consisting of polyamine N-oxides, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl oxazolidones and polyvinylimidazolines, polyaspartate, polyglutamate, maleic acid / acrylic acid / vinyl alcohol terpolymers, sulfonated polyethoxy / propoxy barrier ester oligomers, or mixtures thereof; - peroxidase enzymes; - amylase enzymes; ethylenediamine succinic acid chelating agents; perfume capsules; obsession - mixtures thereof; characterized in that the detergent composition has an equilibrium relative humidity of less than 30% at 35 ° C and the packaging system is comprised of a plastic film or plastic / paper laminate, foldable, sealed refill bag having a moisture vapor transmission rate of 1-15 g / m ² / day. Combination according to claim 1, characterized in that the detergent composition is a laundry detergent composition comprising a surfactant and a detergent builder. Combination according to claim 2, characterized in that the composition has a bulk density greater than 650 g / l. Combination according to claim 3, characterized in that at least part of the surfactant in the composition is in the form of an agglomerate or an extrudate. 5. A combination according to any one of claims 1 to 3, characterized in that the composition comprises a peroxygen or peroxyacid bleach. 6. A combination according to any one of claims 1 to 5, characterized in that the composition is bleach-free and the moisture-sensitive ingredient - a choline ester cationic surfactant, - a polymer which may be a polyaspartate, a polyglutamate, a terpolymer of maleic / acrylic acid / vinyl alcohol, a sulphonated polyethoxy / propoxy barrier ester oligomer, or a peroxidase enzyme - mixtures thereof. 7. A combination according to any one of claims 1 to 3, characterized in that the plastic is a polyolefin.