CZ134797A3 - Process of washing clothes by making use of a solid bleaching detergent dosage method - Google Patents

Abstract

There is provided a method of washing laundry in a domestic washing machine in which a means is provided for dispensing an effective amount of a solid detergent composition to the drum of the washing machine before the commencement of the wash wherein the detergent composition contains a bleach system capable of providing organic peroxyacid bleach to a laundry wash solution and non-three-dimensional phyllosilicate mineral compound, said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said mineral compound being in close physical proximity within said composition.

Description

This invention relates to a method of washing laundry in an automatic washing machine in the home or in industry and particularly ί ^ ^ 1 ^ $ ό ογ ₅ »· ος) the washing process when the solid detergent is dosed, and especially -rg.

which comprises in close contact with a whitening agent capable of providing a bleach of the type organic wash solution, and also comprises a high density system which is a peroxyacid to a non-three-dimensional phyllosicate mineral compound. The detergent is dispensed directly into the wash solution.

BACKGROUND OF THE INVENTION

Successful removal of bleachable stains or stains such as stains from tea, fruit juice and vegetables from stained textiles is a challenge for bleachers to use in laundry washing. Traditionally, bleaching agents such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids, have been used to remove such bleachable stains. Organic peroxyacids are often obtained in situ by perhydrolysis between hydrogen peroxide and an organic peroxyacid precursor. In addition, organic peroxyacids may be included in the compositions as tablet bleaching components.

t

An increase in the use of organic peroxyacid precursors has been made possible by the use of a lower textile washing temperature, along with an increase in the proportion of colored fabrics in the conventional laundry wash volume.

It has been found in the art that the stain removal effect is achieved in a laundry process by allowing the formation of a localized transient high concentration of certain detergents, including fillers and surfactants, at the beginning of the wash cycle. J. Bland, in an article published in Manufacturing Chemist, November 1989, pp. 41-46, describes these achievements in much more detail. High transient concentrations increase for several reasons. The detergents themselves have very low solubility, this solubility can be increased by the presence of other materials such as viscous surfactant phases, or

may increase by mixing overhead in the immediate vicinity of detergent substances, which may not be sufficient to deliver the dissolved detergent.

DAvA is preferred in such a manner as to permit the formation of a localized transient high concentration and to allow the use of a metering method which delivers the detergent directly into the wash solution. One suitable method allows the use of a dispensing device. The dispensing device is typically filled with an effective amount of detergent and then loaded into the drum of an automatic washing machine before starting the wash cycle. At the beginning of the wash cycle, the detergent is progressively released as a result of agitation of the device which rotates with the drum, and thus the detergent in the washing water device is contacted.

The formation of localized high concentrations of certain detergent substances is successful, but it is associated with the problem of producing localized high concentrations of bleaching substances, mainly organic peroxyacids, and thereby deteriorating the colors of fabrics and maters that are exposed to localized high concentrations of bleach. Overfilling the machine with textiles and slow water supply to the drum can increase localized high bleach concentrations. Another problem that may be involved is the localized blotchy discoloration of dyes on fabrics. In particular, eating dyes are both stained and stained.

Where peroxyacid precursors form a component of the composition, the potential problem increases, especially if the laundry detergent contains high concentrations (e.g., > 3% by weight) of the organic peroxyacid precursor and / or when sodium percarbonate is used as the hydrogen peroxide source in rapidly soluble form.

The Applicants have found that the problem of speckled damage is particularly problematic in peroxyacid precursors, from which henzoic acid or non-cationically substituted derivatives or cationic peroxyacids are released by perhydrolysis as peroxyolysis. The benzooxazine-type precursor has also been found to exacerbate this problem.

The development of high-density products and their dosing with a dosing device, which is placed in the drum of the washing machine together with the filling of the laundry, only serves to restore these problems. There is now a need for a laundry washing process wherein organic peroxyacids are released into the wash solution in a manner that minimizes and preferably eliminates dyeing of fabrics and materials during dissolution and perhydrolysis in the wash liquid while still acceptably removing bleachable soils and stains from fabrics.

Previous work includes a number of examples of peroxyacid precursors that are coated or form agglomerates so as to increase their storage stability and / or affect their behavior in solution.

EP-A-0070474 discloses granular organic peroxyacid precursors prepared by spray drying a pumpable aqueous dispersion containing an N-acyl or O-acyl compound together with at least one water-soluble cellulose ether, starch or starch derivative in an activator = coating ratio of 98 = 2 to 90 = 10.

GB-A-1507312 describes the coating of precursors of organic peracids with a mixture of alkali salts of Cs-22 fatty acids with corresponding fatty acids. GB-A-1381121 discloses coating with a molten mixture of inter alia C14-1S fatty acids to protect solid precursors of organic peroxyacids. GB-A-1441416 discloses a simple method that utilizes a mixture of C12-14 fatty acids and ¢ 10-20 aliphatic alcohols. EP-A-0375241 discloses a stabilized organic peroxyacid precursor extrudate in which alkyl peroxycarboxylic acid precursors are mixed with a binder selected from anionic or non-ionic surfactants, film-forming fatty acid polymers or mixtures of such binders. .

EP-A-0356700 discloses compositions comprising organic peroxyacid precursors, a water-soluble film-forming polymer and 2-5% C3-6 polyvalent carboxylic acid or hydroxycarboxylic acid to enhance stability and facilitate dispersion / solubility i. Carboxylic acid, preferably citric acid is dry blended with the organic peroxyacid precursor and then granulated with the aid of the film-forming polymer. Citric acid is used to increase the dissolution rate of the organic peroxyacid precursor granules.

EP-A-0382464 discloses a method for coating or encapsulating solid particles comprising bleaching compounds and organic peroxyacid precursors. In this method, a (coating) melt of the coating material is formed in which the particles form a dispersed phase, the melt solidifies and then crushed into a free-flowing material in which the particles are cast in a continuous phase. Various coating materials are described herein, and certain materials such as polyacrylic acid and cellulose acetate phthalate are said to be useful when the pH-dependent release of the coated material is useful.

General emphasis is now placed in the art on protecting organic peroxyacid precursors against unfavorable storage conditions and relatively little attention is paid to the dissolution characteristics of the coated or agglomerated materials used. If the coating and / or agglomeration is carried out with poorly soluble materials such as fatty acids, this affects the resulting perhydrolysis rate of the organic peroxyacid precursors, here the perhydrolysis rate is lower than that of the unprotected precursors. In another use in the context of an aglonerated compound, where faster soluble materials such as citric acid are used, an objectively faster solution of organic peroxyacid precursors is formed. In both examples, when the detergent composition is started with an alkaline hydrogen peroxide solution, the problem of particularly high localized concentrations of organic peroxyacid bleach is not solved.

EP-A-0.028.432 discloses granules which contain laundry detergents containing from 5 to 80% organic precursors 5 to 60% water-soluble silicate and from 5 to 40% nonionic binders in a solid laundry detergent composition. A water-soluble silicate compound, a preferred example of which is smectite clay, is mixed with an organic peroxyacid precursor and then bound with a nonionic surfactant. This combination is said to rapidly form peroxycarboxylic anions when added to a source of hydrogen peroxide.

EP-A-0.028.432 does not disclose any use of the dispensing device in the washing method or any problem relating thereto.

JP5-7296 addresses the basic problem of lightening fabric colors, but does not specify the problem of blotchy discoloration. Described herein is a composition wherein the water-soluble mineral compound, the organic peroxyacid precursor and the bleaching compound are initiated together to form the perhydrolysis and dissolve the peroxyacid composition from a mineral compound to compound ratio of 1 = 99 to 90 = 10, with preferably the water-soluble mineral is selected from activated clays, kaolin, bentonite, precursors and bleaching from 20 = 80 to 65 = 35. made of cucumber, diatomaceous earth and perlite.

This composition is said to stop light without inhibiting the whitening effect. JP5-729O does not disclose any use which relates to the use of a dispensing device in a laundry process or any problem relating thereto.

WO 92/13798 discloses the use of acidic materials having specific characteristics as coating materials for organic peroxyacid precursors to suspend the onset of perhydrolysis during the initial product dissolution / dispersion stages in an aqueous prewashing liquid.

Applicants have found that the problem of fabric damage that has been observed in which a detergent has been dispensed into a laundry solution through a dispensing device can be reduced by adding defined values of mineral clay to a well blended organic peroxyacid bleach composition which forms a bleaching system. It has been found that the inclusion of the mineral's ability to remove the composition does not compromise the stability of the bleach component and, in particular, the bleached discoloration in the laundry process, does not significantly compromise bleachable stains in clay and also in the product upon storage. While it is essential that the mineral clay and the organic peroxyacid or precursor thereof be in close contact, it is not necessary that the bleaching component be coated with clay. Such coatings are less preferred due to the complexity of production and higher costs.

All documents cited in the description are referenced in the relevant sections.

SUMMARY OF THE INVENTION

The present invention provides a method of washing laundry in a domestic or industrial washing machine which is based on a method of dispensing an effective amount of a solid laundry detergent comprising peroxyacid bleaching agent directly into the drum of the washing machine prior to commencement of washing. into a washing liquid and wherein said peroxyacid bleaching agent comprises:

(a) a bleaching system capable of providing an organic peroxyacid bleach to the wash solution, and wherein the bleaching system is selected from (i) a hydrogen peroxide source in combination with an organic peroxyacid precursor (ii) a tableted organic peroxyacid another and any mixtures thereof; and (b) a non-three-dimensional phyllosic acid mineral compound wherein the organic peroxyacid precursor or tableted organic peroxyacid and said non-three-dimensional phyllosiclate compound are in said composition in close physical proximity.

Preferably, the organic peroxyacid precursor or tableted organic peroxyacid and the non-three-dimensional phyllosiclate compound are in intimate contact, most preferably in the composition in a well-mixed mixture.

Preferably, the laundry detergent composition comprises peroxyacid bleaching compositions in bulk form, more preferably in granular form, and an organic peroxyacid precursor or tableted organic peroxyacid and a non-three-dimensional phyllosiclate compound are present in the same particulate component.

Preferably, the granular detergent has a high bulk density, more preferably it has a bulk density of at least 600g / liter.

In a preferred aspect, a dispensing method is employed in which the dispensing device is filled with solid detergent and the dispensing device is placed in the drum of the washing machine before the start of the wash.

In another preferred view, dosing is provided in the form of a solid laundry detergent such as tablets and such a tablet is placed in the drum of the washing machine before the start of the washing.

The non-three-dimensional phyllosic mineral compound is preferably mineral clay or crystalline layered silica.

Preferably, the mineral clay is smectite clay.

The weight ratio of the non-three-dimensional phyllosic acid compound to the organic peroxyacid precursor or tableted organic peroxyacid is preferably from 1-6 to 1 = 99.

DETAILED DESCRIPTION OF THE INVENTION

Washing method

Laundry methods disclosed herein typically include treating dirty laundry with an aqueous washing solution in a washing machine in which an effective amount of the detergent composition of the present invention is dissolved or dispensed. The detergent is added to the wash solution as described above. By an effective amount of detergent is meant from 40 to 300 g of product which is dissolved or dispensed in washing water of a volume of 5 to 65 liters, which are typical product doses and typical volumes of washing solution commonly used in laundry washing in a washing machine.

In a basic view, the dispensing method used in the washing method of the present invention is such that an effective amount of detergents is added directly to the drum of the washing machine before the start of the washing cycle. This dosing method allows the release of detergents into the wash liquid, especially during the initial wash phases, especially during the first two minutes of wash.

In another aspect, this method of dosing is guaranteed by a dosing device. The dosing device is filled with detergent and used to dispense the product directly into the drum of the washing machine. The bulk capacity of this device should thus be a sufficient amount of detergents to be washed.

Next, the washing machine is filled with laundry and the detergent dispensing device is placed directly in the drum. At the beginning of the washing cycle, water is supplied to the drum and the drum rotates periodically. The shape of the dispensing device should be such as to allow filling with dry detergent, but to allow product release during the wash cycle as a function of agitation as the drum rotates, and also as a result of contact of the device with the wash water.

In order to allow the release of detergents during washing, the device must contain a plurality of openings through which the product will pass.

able to contain commonly used in

The fluid may be permeable to the outside and which will allow the detergent to provide a high level of equipment made of a material that is liquid but impermeable to the solid product to release the dissolved product. Preferably, it is released rapidly at the beginning of the wash cycle and thus of the transient localized product concentration in the washing machine drum at this stage of the wash. It is preferred that the dispensers are reusable and are designed in such a way that the integrity of the container is maintained both in a dry state and during the wash cycle. Particularly preferred for use in the present invention are the dosing devices described in the following patents ¹

GB-B-2,157,717; GB-B-2,157,718; EP-A-O2O1376; EP-A-O288345; and EP-A-0288346. in Manufacturi ng specifically described

In the article by J. Bland, published by Chemist, November 1989, pp. 41-46, there is also a preferred device for use for a flexible wrapping ring that granulated laundry articles of the type commonly known as a "granulette" . Another preferred dispensing device for use in the present invention is described in PCT Patent Application No. WO 94/11562.

Particularly preferred are dispensing devices as described in European Patent Applications No. 0343069 fc 0343070. A later application discloses a device which consists in the form of a bag which is stretched onto an auxiliary serving as a mouth, the mouth is adapted to allow sufficient product into the bag. for one wash cycle in this washing method. A portion of the wash medium flows through the mouth into the pouch, dissolves the product, and the solution then passes through the outside of the mouth into the wash medium. The sub-ring is arranged to prevent the exit of the moist and undissolved product. The radially expanding walls, in the aforementioned circular arrangement, typically include those that extend from the center or comprise a simpler structure wherein the walls have a helical shape.

Further, a flexible container such as a bag or bag is used as the dispensing device. The bag is a fibrous construction that is coated with a waterproof protective material to retain the contents. Such a device is described in European Patent Application Publication No. 0018678. Further, the dispensing device is made of a water-insoluble synthetic material and is provided with an end seal or cap adapted to rupture in an aqueous medium. Such devices are described in European Patent Applications Nos. 0011500, 0011501, 011502 and 0011968. Such closures that rupture in water comprise a water-soluble adhesive and a seal at one end of the bag which is formed by a waterproof film such as polyethylene or polypropylene.

In another aspect, the dosage is carried out by the compact detergent itself, which is in the form of tablets. The tablets are then dispensed directly into the drum of the washing machine before the start of the washing cycle. Their compact form allows an increase in localized high levels of bleaching agents during dissolution of the tablets in the wash water during the first stages of the wash cycle.

Organic peroxyacid bleaching system

An essential characteristic of the present invention is an organic peroxyacid bleach system. A preferred bleach system embodiment comprises a hydrogen peroxide source and an organic peroxyacid precursor. The organic peroxyacid is formed in situ by reaction of the precursor with a source of hydrogen peroxide. Preferred are hydrogen peroxide sources, which include inorganic perhydrate bleaches. In an alternative preferred embodiment, the tableted organic peroxyacid is mixed directly into the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a tableted organic peroxyacid are also contemplated.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally added to the composition in the form of alkali metal salts, preferably sodium salts in the values of from 1 to 40% by weight, more preferably from 2 to 30% by weight, and most preferably from 5 to 25% by weight.

Examples of inorganic perhydrate salts include perborate, percarbonate, phosphate, persulfate and persilicate salts. Inorganic perhydrate salts are commonly alkali metal salts. The inorganic perhydrate salts may be used as a crystalline solid without additional protection. For certain perhydrate salts, in a preferred embodiment of the granular compositions, a material coated form is used which provides better storage stability of these perhydrate salts in the granular product.

ΙΟ

Sodium perborate and tannate may be in the form of a non-hydrate of the formula NaBO 2 H 2 O 2 or tetrahydrate of NaBO 2 H 5 O 3 and 3 H 5 O. Alkali metal percarbonates, especially sodium percarbonate, are preferred for use in the compositions of the present invention. Sodium percarbonate is an addition compound having the formula that corresponds to the composition of 2NaaCO3-3H2Q2 and is commonly available as a crystalline solid. Sodium percarbonate, as an addition compound with hydrogen peroxide, has the ability to release hydrogen peroxide quite rapidly upon dissolution and thus increases the tendency to produce a localized high concentration of bleach. Percarbonate is most preferred in the coated form in the compositions, which form is more stable in the product.

A suitable coating material that guarantees product stability includes a mixed salt of water-soluble alkali metal sulfate and alkali metal carbonate. Such coatings together with the Coating Method have already been described in GB-1,466,799, issued to Interox on March 9, 1977. The weight ratio of the mixed salt of the coating material to the percarbonate is within the range of < from 1 = 200 to 1 = 4, more preferably from 1 = 99 to 1 = 9, and most preferably from 1 = 49 to 1 = 19. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the basic formula NaaSO-α. n. Na 2 CO 3, wherein n is from 0.1 to 3, preferably from 0.3 to 1.0, and preferably from just 0.2 to 0.5.

Other coatings which preferably include silicate (alone or with borate salts or boric acid or other inorganic substances), waxes, oils and fatty soaps are preferably used in the present invention.

Potassium monoperoxosulfate is another perhydrate salt used in these detergents.

Peroxyacid precursor

Peroxyacid precursors are compounds that react perhydrolytically with hydrogen peroxide to provide the peroxyacid. Basically, peroxyacid precursors can be represented as where L is a leaving group and X is basically a Functional group from which perhydrolysis produces a peroxyacid ·

O ií

X-C-OOH

Peroxyacid precursors are preferably added to the detergent compositions at levels of from 0.5 to 20% by weight, more preferably from 3 to 15% by weight, and most preferably from 5 to 10% by weight.

However, the tendency to form localized high concentrations of peroxyacid is greater if the detergent composition comprises more than 3% by weight, more preferably more than 5% by weight, of the peroxyacid precursor.

Suitable peroxyacid precursors typically contain one or more N- or O-acyl groups, such precursors being selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of suitable materials from these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-O17O386.

Applicants have found that speckled damage is mainly associated with peroxyacid precursors which, by perhydrolysis, give a peroxyacid which is (i) perbenzoic acid or a non-cationically substituted derivative thereof, or (ii) a cationic peroxyacid

Benzoxazine precursors have also been found to be sensitive to this problem.

Outgoing groups

The leaving groups, hereinafter referred to as the L groups, must be reactive in the perhydrolytic reaction and must succumb to it in an optimal period of time (eg in a wash cycle). However, if the L group is so reactive, this activator will be difficult to stabilize when used in a bleaching composition.

The L group of the preferred group is selected from the group consisting of · *

Y

R ³

-O-CH = C-CH = CH ₂ -O-CH = C-CH = CH ₂

O ¹¹ ₁ -Ο-c — R ¹

O

II ch ₂ -c

JnR ⁴

II o

-N.

'in

And ' ^c ''C

II o

NR ⁴

R ³ = O-C = CHR ⁴ ;

O

II

-N-S-CH-R ⁴

I-II R ³ O and mixtures thereof, wherein R * is an alkyl, aryl or alkaryl group consisting of 1 to 14 carbon atoms, R ³ is an alkyl chain consisting of 1 to 8 carbon atoms, R ⁴ is hydrogen or R ³ and Y is hydrogen or a group that promotes dissolution. Any of R ¹ , R ^3, and R ⁴ may be substantially substituted with any functional group including, for example, alkyl.

alkoxy, halogen, amine, nitrosyl, amido and ammonium promote dissolution, are -N ⁺ (R ³ ) 4X-, and O <-N (R ³ ) 3

-CO ^{2 '} M ⁺ , wherein R ³ is alkyl of up to 4 carbon atoms, M is hydroxy, a group.

Preferably, the groups which -SO _{3 '} M ⁺ , -CO ₂ -M ⁺ , -SO ₄ -M *, and most preferably are -SO 3 M *, and a chain containing from 1 cation which guarantees the solubility of the bleach activator and X is the anion which guarantees solubility of the bleach activator.

Preferably, the alkali metal C, ammonium or substituted ammonium cation is preferred, the sodium and potassium cations being preferred, X being a halide, hydroxide, methyl sulfate or acetate.

Perbenzoic acid precursor

The perbenzoic acid precursor provides perbenzoic acid by perhydrolysis of the acid.

Suitable precursors of O-acylated perbenzoic acid include substituted or unsubstituted benzoyloxybenzene sulfonates and include, for example, benzoyloxybenzene sulfonate:

O

_SO3 are also suitable benzoylated products of sorbitol, glucose, and all sugars benzoylating agents, including for example:

Ac =

And what

OBz

OAc

COCH 3, Bz = benzoyl

The precursors of the perbenzoic acid compounds of the ioid type include N-benzoyl acid.

N-benzoyl-succinimide, tetrabenzoyl-ethylene-amine substituted urea. Other suitable perbenzoic imidazole type precursors include

N-benzoylimidazole and N-benzoylbenzimidazole and other perbenzoic acid precursors, N-benzoylpyrrolidone, benzoylpyroglutamic acid.

Other benzoyl diacyl peroxide precursors having the formula:

which contain an N acyl group include dibenzoyltaurine and perbenzoic acid include benzoyltetraacylperoxides and compounds,

COOH

Phthalic anhydride is another suitable perbenzoic acid precursor for this use

Suitable N-acyl lactam precursors of perbenzoic acid have the formula ^:

O

II

- CH2 --CH2

R ^b, -C-N-CHH-fCHjln wherein n is from O to 8, preferably from O to 2, and ^R6 is a benzoyl group.

Perbenzoic acid derivatives precursors

Perbenzoic acid derivatives precursors provide perbenzoic acid substituted by perhydrolysis.

Suitable precursors of perbenzoic acid derivatives include any of the perbenzoic acid precursors described herein, in which the benzoyl group is substituted with any non-charged (e.g., non-cationic) functional group such as alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl and the like. amide group.

A preferred class of substituted perbenzoic acid precursors are substituted amides of the following structural formula.

R ¹ - N - C - R ^{2 l (}

R ⁵ O

R ¹ —C — N — R ² —C - L or

II

Wherein R ¹ is an aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an arylene or acarylene group having from 1 to 14 carbon atoms and R ® is hydrogen or an alkyl, aryl or alkaryl group having from 1 to 14 carbon atoms 10 carbon atoms and L is basically any leaving group. R ¹ preferably contains from 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ is aryl, substituted aryl or alkylaryl which may be branched or substituted or both substituted and branched and is obtained both from synthetic sources and from natural sources including, for example, tallow. Analogous structural variations are permissible for R ^2nd Substitution includes substitutions with alkyl, aryl, halogen, nitrogen, sulfur, and other typical groups of substituents or organic compounds. R ⁵ is preferably hydrogen or methyl. R * and R ⁵ can not have more than 18 carbon atoms. Substituted aeide compounds as bleach activators of this type are described in EP-A-0170386.

Cationic Peroxyacid Precursors in

The cationic peroxyacid precursors produce a cationic peroxyacid by perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting a portion of the peroxyacid in a suitable peracid precursor with a positively charged functional group such as an ammonium or alkylammonium group, preferably ethyl or methyl ammonium. Cationic peroxyacid precursors are typically present in solid laundry compositions as salts with a suitable anion, such as a halide ion.

The peroxyacid precursor which is substituted is perbenzoic acid or a derivative and a precursor of a compound which, alternatively, the peroxyacid precursor is an alkylperoxycarboxylic acid or a precursor thus cationically externally substituted as described above. an acid amide precursor which is substituted with an alkylperoxy acid as described below.

Catalyst peroxyacid injectors precursors are described in US Patents 4,904,406, 4,751,015, 4,988,451, 4,397,757, 5,269,962, 5, 127, 852, 5,093,022, 5, 106,528, in UK 1,382,594, EP 475,512, 458,396 and 284,292 and JP. 87-318,332.

Examples of preferred cationic peroxyacid precursors are disclosed in UK Patent Application No. 9407944.9 and US Patent Applications Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any alkyl or benzoyloxybenzene sulfonates that are substituted with an ammonium or alkylammonium group, N-acylated caprolactams, and monobenzoyltetraacetylglucosobenzoyl peroxides.

The preffered cationically activated benzoyloxybenzene sulfonate is 4- (trimethylammonium) methyl benzoyloxybenzene sulfonate =

The preformed catalyzed and non-alkyloxybenzene has the formula:

substituted sulfonate

Preformed precursors of cationic N-acylated caproactatts include methylenebenzoylcaprolactams, in particular methylenebenzoylcaprolactam ^: trialkylammonium triethylammonium trimethylammonium peroxyacids

Another preferred class of N-acylated caprolactam-type cationic peroxyacid precursors includes trialkylammonium methylenalkylcaprolactams, in particular trimethylammonium methylenebenzoylcaprolactam:

wherein n is from 0 to 12.

Preference is further given to a cationic peroxyacid precursor, which is the sodium chloride of 2- (N, N, trimethylammonium) ethyl 4-sulfophenyl carbonate.

Alkyl peroxycarboxylic acid precursors

Alkyl peroxycarboxylic acid precursors form by perhydrolysis of peroxycarboxylic acid. Preference is given to precursors of the type which give peracetic acid by perhydrolysis.

Preferred imide type alkylperoxycarboxylic acid precursors include NN, N, -tetraacetyl alkylenediamines in which the alkylene group contains from 1 to 6 carbon atoms, and especially include those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms . Tetraacetyl ethylenediamine (TAED >) is particularly preferred.

Other preferred alkylperoxyacid precursors include

Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium oxybenzenesulfonate (ABS) and pentaacetylglucose.

Alkyl peroxyacid-substituted amides precursors

Suitable are alkylperoxy acids, precursors and amines having the following substituted basic formula = cII o

C fl

O

C

II • RR ⁵ O or wherein R ¹ is an alkyl group having 1 to 14 carbon atoms, R ² is an alkylene group containing 1 to 14 carbon atoms, and R ⁵ is hydrogen or an alkyl group containing 1 to 10 carbon atoms and L is basically any leaving group. R ¹ preferably contains from 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R * has either a linear or branched alkyl chain which either contains or does not contain a substitution and is obtained from synthetic or natural sources, including, for example, tallow. Analogous structural variations are permissible for R ^2nd Substitution includes substitution with alkyl, halogen, nitrogen. sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably hydrogen or methyl. R ¹ and R ⁵ may not contain a total of more than 18 carbon atoms. Bleached activators of the substituted amide type of this type are described in EP-A-O1770386.

Precursor benzooxazine organic peroxyacids

Also suitable are the benzoxazine-type precursors described, for example, in EP-A-332,294 and EP-A-482,807, in particular those having the formula:

and also include substituted benzoxazines of the type:

R 5 where R 1 is alkyl, alkaryl, aryl, arylalkyl and wherein R 5, R 3, R 4 and R 5 are the same or different substituents selected from hydrogen, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COORs ( R 5 is hydrogen or alkyl) and carbonyl groups.

Particular preference is given to benzoxazine-type precursors ^:

Tableted organic peroxyacids

The organic peroxyacid bleaching system may contain either in addition to or alternatively to the organic peroxyacid precursor a tableted organic peroxyacid, typically at levels of from 1 to 15% by weight, more preferably from 1 to 10% by weight of the composition.

A preferred class is substituted amides of the following basic formula =

00H or

G —OOH

R ⁵ O wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene, alkarylene group containing from 1 to 14 carbon atoms, and R 8 is hydrogen or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. R ¹ preferably contains from 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ contains a linear or branched alkyl chain, substituted with an aryl or alkaryl, which contains either branched or substituted, or both, and is obtained from both synthetic and natural sources, including, for example, tallow. Analogous structural variations are possible for R and ^{the second} Substitution includes substitution with alkyl, aryl, halogen, nitrogen, sulfur and other typical groups of substituents or organic compounds. R ⁵ is preferably hydrogen or methyl. R ¹ and R ⁵ may not contain more than 18 carbon atoms in total. Amides substituted with organic peroxyacids are described in EP-A-O17O386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanoic acid and diperoxybexadecanoic acid. Mono and di-peranedioic acid, 1,11-monoperundecanedioic acid and 1,11-di-perundecanedioic acid and N-phthalenamino-noperoxycaproic are also suitable for use herein.

Non-three-dimensional phyllosiclate mineral compound

Detergent compositions for use in the present invention comprise a non-three-dimensional phyllosiclate mineral compound. In the main view, the non-three-dimensional phyllosic mineral compound and the organic peroxyacid precursor are in close physical proximity, more preferably in intimate contact and most preferably in a well mixed mixture in said composition.

The non-three-dimensional phyllosic acid mineral compound is preferably present in an amount such that the weight ratio of the non-three-dimensional phyllosic acid mineral compound to the organic peroxyacid precursor or said tableted organic peroxyacid is in the bleaching composition from 1 = 1 to 1 = 99, s. preferably from 1 = 3 to 1 = 49, and even more preferably from 1: 1 to 1:19,

By non-three-dimensional phyllosilicate mineral compound is meant here a silicate mineral compound in which the flat plates (two-dimensional) are mainly formed by sharing three of the four oxygen atoms in each tetrahedron silicate with adjacent tetrahedrons. This definition excludes those silicates having a larger complex of three-dimensional silicates interconnected in the structure, and occasionally referred to as framevork minerals. Here, non-three-dimensional phyllosilate mineral compounds are preferred, which include clay mineral compounds and crystalline layered silicates. For clarity, we note that the term non-three-dimensional phyllosiclate mineral compound, as used herein, excludes sodium aluminosilicate zeolites as fillers, but may be included in the compositions of the invention as optional fillers.

The non-three-dimensional phyllosic mineral compound is preferably present as a component of agglomerated particles comprising an organic peroxyacid precursor or a tableted organic peroxyacid and optionally other detergent compounds that include polymeric organic binders.

Here, the clay mineral compound (abbreviated clay) is understood to mean an aqueous phyllosilicate, which typically has a two- or three-layer crystalline structure. Further description of clays can be found in Kirk-Othmer, Encyclopaedia of Chemical Technology, 4th Edition, Volume 6, p. 381, published by John Wiley and Sons.

The clay is preferably a seectite clay.

Smectite clays are described in U.S. Patent Nos. 3,862,058,

Nos. 3,948,790, 3,954,632 and 4,062,647 and European Patent Nos. EP-A-299,575 and EP-A-313, 146 all under the auspices of Procter and Gamble Coapany.

The term smectite clays herein includes both clays having alumina present in the silicate lattice and clays having magnesium oxide present in the silicate lattice. Typical smectite clays include compounds having the basic formula Al 2 SiS 2 O 5> 2 (OH> 2.η H2O and compounds having the basic formula Mg 3 (Si 2 G 5) z (OH> 2.n HaO.) Smectite clays tend to assume an expandable three-layer structure.

Specific examples of suitable smectite clays include those selected from the classes of montmorillonites, hectonites, volchonskoites, nontronites, saponites and sauconites, and in particular those having an alkali or alkaline earth ion present in the crystal lattice. Sodium and calcium montmorillonites are particularly preferred.

Suitable smectite clays are sold by suppliers including English China Clays, Laviosa, Fordamin, Georgia Kaolin and Colin Stewart Minerals.

Preference is given to the smectite clay sold under the trade names Hhite Bentonite STP from Fordamine and Detercal P7 from Laviosa Chemical Mineria SPA.

The clays for this use may be acid treated by scrubbing with any suitable mineral or organic acid. Such clays increase the acidic pH when dissolved in distilled water. Commonly commercially available &quot; soured clay &quot; is sold under the trade name Tonssi P from Sud Chemie AG.

By substituting small ions such as protons, sodium, potassium, magnesium and calcium ions, certain organic molecules, including those with positively charged functional groups, can be incorporated into the crystalline lattice of smectite clay

The crystalline lattice structure of the mineral clay compounds in the preferred embodiment has a cationic fabric softening substance therein. Such substituted clays are called "hydrophobically activated clays". Cationic fabric softening agents are typically present in a weight ratio of cationic fabric softener to clay of from 1 = 200 to 1 = 10, preferably from 1 = 100 to 1 = 20. Suitable cationic fabric softening agents include the water-soluble tertiary amines or the double chain amide materials described in GB-A-1 514 276 and EP-B-0 011 340.

A preferred commercially available hydrophobically activated clay is bentonite clay which contains 40% by weight of dimethyl di-tallow-quaternary ammonium salt and is sold under the tradename Claytone EM English China Clays International.

Preferred crystalline layered silicates have the general formula =

NaMSixO2x + i. y HaO where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0164514 and methods for their preparation are described in DE- A-3417649 and DE-A-3742043. In the basic formula above, x is preferably 2, 3 or 4 and is preferably 2. The most preferred material is delta-NaaSizCte, which is obtained from Hoechst AG as NaSKS-6.

The crystalline layered silicate material is preferably present in the granular laundry detergent as a free-flowing mixture with a solid water-soluble ionizable material. The solid water-soluble ionizable material is selected from organic acid, organic and inorganic acid, and mixtures thereof.

Additional detergent ingredients

The detergent compositions of the present invention also contain additional ingredients. The exact nature of these additional ingredients and their content in the composition depends on the physical form of the composition and not the exact nature of the washing operation in which it is used.

The compositions of the present invention preferably comprise one or more additional ingredients selected from surfactants, fillers, organic polymeric compounds, additional enzymes, suds suppressors, calcium soap dispensers, soil suspending agents, anti-fouling agents and corrosion inhibitors.

Tenzid

Preferably, the detergent compositions of the present invention comprise an additional surfactant component selected from anionic, cationic, nonionic anpholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

The surfactant is typically present at a level of from 0.1 to 60% by weight. Still further, a surfactant content of from 1 to 35% by weight is preferred, and a content of from 1 to 20% by weight is most preferred.

A typical list of anionic, nonionic, ampholytic and zwitterionic classes of these surfactants is given in U.S. Patent 3,929,678 issued to Lauglin and Heuring on September 30, 1975. Further examples are provided in Surface Active Agents and Detergents (Volume I and II by Schvartz, Perry and Berch) . A list of suitable cationic surfactants is given in USP 4,259,217, issued to Murphy on March 31, 1981.

Ampholytic, amphoteric and zwitterionic surfactants, where present, are basically used in combination with one or more anionic and / or nonionic surfactants.

Anionic surfactant

In principle, any anionic surfactants for cleaning purposes can be used in these compositions. The compositions include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, as well as mono-, di-, triethanolamine salts) of anionic sulfates, sulfonates, carboxylates, and sarcosinates of surfactants.

Other anionic surfactants include 2-hydroxyethanesulfonates such as acyl 2-hydroxyethanesulfonate, N-acyl taurates, fatty acid amides with methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12 -18 monoesters, and especially diesters of sulfosuccinates). diesters), N-acyl sarcosinates. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated funa and resin acids and hydrogenated resin acids which are contained in or derived from tallow.

Anionic sulfate type surfactant

Anionic sulfate surfactants suitable for use herein include linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, Cetacyl N- (C 1-4 alkyl) and -N- (C 1-2 hydroxyalkyl sulfates) glucamine sulfates alkyl polysaccharides such as alkylpolyglucoside sulfates (nonionic unsulfated compounds are described herein).

The alkyl ethoxysulfate surfactants are preferably selected from the group consisting of C 6-6 alkyl sulfates which are ethoxylated from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C 6-6 alkyl sulfate which is ethoxylated from 0.5 to 20, preferably from 0.5 to 5 moles of ethylene oxide per molecule.

Anionic sulfonate surfactant

Surfactants of the anionic sulfonate type, such as alkylbenzene sulfonates, or seconds of polycarboxylic acid alkyl glycerol sulfonates, which are suitable for use include salts of C5-20 linear alkyl ester sulfonates, Ce-22 primary alkane sulfonates, Ce-24 olefin sulfonates, acids, acyl salts oleyl glycerol sulfonates and any mixtures thereof.

Anionic carboxylate surfactant

Anionic carboxylate-type surfactants suitable for use herein include alkyl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (alkylcarboxylates), particularly certain secondary soaps as described herein.

Preferred for this use are the alkyl ethoxycarboxylates, which include carboxylates of the formula:

RO (CH 2 CH 2 O) x CH 2 COO-M *, wherein R is a C 6-6 alkyl group, x ranges from 0 to 10, the ethoxylate distribution is on a weight basis. The amount of material where x is 0 is less than 20% and the amount of material where x is greater than 7 is less than 25%. The average value of x is from 4 to 10 if the average R is C13 or less and the average value of x is from 3 to 10 if the average R is greater than C13. M is a cation, preferably selected from alkali metal, ammonium and mono-cations, most preferably armonium and onts and their di-, a mixture of alkylethoxycarboxylates, alkaline earths, and triethanolarnonium from sodium, potassium, magnesium ions. Preferred wherein R is a C 12-18 alkyl group.

Alkylpolyethoxypolycarboxylate surfactants which are suitable for use herein have the formula:

RO-CHR ¹ -CHR ² -O) _X -R ³ wherein R is Ce_is alkyl group, x is 1 to 25, R ¹ and R ² are selected from the group consisting of hydrogen, a radical of acetic acid, succinic acid and hydroxy succinate and mixtures thereof. At least one R ¹ or R ² group is a succinic or hydroxysuccinic acid radical. R ³ is selected from the group consisting of hydrogen, a substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof.

The tensi d of an an onactive second soap1

Preferred soap type surfactants are secondary soap type surfactants which contain a carboxyl unit attached to a secondary carbon atom. The secondary carbon may be in a cyclic structure such as p-octylbenzoic acid or alkyl-substituted cyclohexylcarboxylates. Preferably, the secondary soap surfactants contain no ether bonds, ester bonds and no hydroxyl groups.

Preferably, no nitrogen atom is present in the main functional group (amphithic moiety). Secondary soap surfactants typically contain a total of 11-15 carbon atoms, although slightly more (e.g. up to 16) can be tolerated, e.g. with p-octylbenzoic acid.

Some of the preferred secondary soap surfactants are characterized by the following basic structures:

A. A highly preferred class of secondary soaps are secondary carboxyl materials of the formula

R ³ CH (R ⁴ ) COOM where R ³ is CH 3 (CH 2) x and R ⁴ is CH 3 (CH 2) y where y is 0 or an integer from 1 to 4, x is an integer from 4 to 10 and the sum (x + y) is 6-10, preferably 7-9, and most preferably 8.

B. Another preferred class of secondary soaps comprises carboxylic compounds wherein the carboxyl unit is attached to a hydrocarbon ring, e.g., secondary soaps of the formula:

Wherein R ⁵ is a C 1-10 group, preferably a C ^5-6 alkyl or alkenyl group, and R ⁶ is a cyclic structure such as benzene, cyclopentane and cyclohexane. (Note R® may be in the relative position ortho, meta or para to the carboxyl on the cycle.)

C. Another preferred class of secondary soaps includes secondary carboxyl compounds of formula =

Cto (CHR) k - (CH 2> m - (CHR) _n - CH (COOM) (CHR) o - (CH 2) r - (CHR) q - CH 3 wherein each R is C 1-8 alkyl, k, n, o , q are integers ranging from 0 to 8, and have values such that the total number of carbon atoms (including carboxyl) is in the range of 10 to 18.

In each of the above formulas A, B, and C, M is any suitable, especially water-soluble, paired ion.

Particularly preferred for this use are water-soluble secondary soap surfactants selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid,

2-propyl-1-nonanoic, 2-butyl-1-octane and 2-pentyl-1-heptane.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the sarcosinates and the alkali metal of the formula

R-CON (R ¹ ) CH ² COOM wherein R is a C 1-7 linear or branched alkyl or alkenyl group, R ¹ is a C 1-4 alkyl group and an M alkali metal ion. Myristyl and oleoyl methyl sarcosinates are preferred in the form of its sodium salts.

Not even onogenic tension i d

In principle, any anionic surfactant for cleaning purposes can be used in these compositions. Non-limiting examples of classes of useful non-ionic surfactants are given below.

Non-ionic surfactant of the polyhydroxy-fatty acid amide type

The polyhydroxy fatty acid amides which are suitable for use herein have the structural formula:

R ² -COUR ¹ Z wherein R ¹ is hydrogen, C 1-4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferred is C 1-4 alkyl, more preferred C 1 or C 2 alkyl, and most preferred is C 1 alkyl (e.g. methyl) . R ² is C 3íuhlovodík, preferably a linear Cs-Ig alkyl or alkenyl, more preferably a linear Cg-iy alkyl or alkenyl, and most preferred is a linear Cu-J7 alkyl or alkenyl, or mixture thereof, and Y is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and at least 3 hydroxyls directly bonded to the chain or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar by a reductive amination reaction, more preferably Z is glycityl.

Nonionic condensates of alkyl phenols

Suitable condensates are polyethylene, polypropylene and polybutylene oxide with alkylphenols. In principle, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group of 6 to 8 carbon atoms in a linear or branched chain with alkylene oxide.

Non-ionic surfactant of ethoxylated alcohol type

The alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for this use.

The alkyl chain of the aliphatic alcohol is either linear or branched, primary or secondary and contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Ethoxylated / propoxylated fatty alcohol surfactant

Ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated / propoxylated fatty alcohols are suitable for use herein, especially when water-soluble. Preferably, the ethoxylated fatty alcohols are C 10 -et ethoxylated fatty alcohols having an ethoxylation degree of from 3 to 50, most preferably C 8-18 is ethoxylated fatty alcohols having an degree of ethoxylation of from 3 to 40. Preferably the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, ethoxylation degree from 3 to 30 and propoxylation degree from 1 to 10.

Beionegennl EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic material, which is formed by condensation of propylene oxide with propylene glycol, are also suitable for this use. The hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and eliminates water solubility. Examples of compounds of this type include certain commercially available Pluronic ™ surfactants sold by BASF.

Nonionic EO condensation products with propylene / diamine adducts

The condensation products of ethylene oxide with the product formed by the reaction of propylene oxide and ethylenediamine are also suitable for this use. The hydrophobic portion in these products is the reaction product of ethylenediamine with an excess of propylene oxide, and has a molecular weight of from 2,500 to 3,000 basically. Examples of this type of non-ionic surfactant include certain commercially available Tetronic ™ compounds sold by BASF.

Nonionic surfactant of alkylpolysaccharide type

Suitable alkyl polysaccharides for this use are described in US Patent 4,565,647, Llenado, issued January 21, 1986. These alkyl polysaccharides have a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide, e.g., polyglycoside. The hydrophilic group comprises from 1.3 to 10, preferably from 1.3 to 3, and most preferably from 1 to 10

1.3 to 2.7 carbohydrate units. Any reducing sugar containing 5 or 6 carbon atoms, e.g., glucose, galactose, and galactosyl groups substituted with glucose groups, is used. (Optionally, glucose or galactose is attached to the hydrophobic moiety at the 2-, 3-, 4-, etc. position as opposed to the glucoside or galactoside.)

between one position of the next sugar unit and the position and / or 6 of the preceding sugar unit.

Preferred are alkyl polyglycosides of the formula '

R ² OC Cn H2n O) t (glycosyl) x wherein R ² is selected from the group alkyl-phenyl, hydroxyalkyl, and mixtures thereof, the group containing from 10 to 18, preferably 12 to 14 carbon atoms, n is 2 or 3, t is from 0 to 10, preferably 0 and x is from

1.3 to 8, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose.

2-, 3-, 4 consists of alkyl in which alkyl

Non-ionic fatty acid amide type surfactant

The fatty acid amide surfactants which are suitable for use herein are the amides of the formula R ⁶ CON 1 R ¹⁴ wherein R ⁶ is an alkyl group having from 7 to 21, preferably from 9 to 17 carbon atoms and each R ⁷ is selected from a group consisting of hydrogen, C 1-4 alkyl, C 1-4 hydroxyalkyl, and - (C 2 H 4 O> xH, where x is from 1 to 3.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkylamphocarboxylic acids.

A suitable example of an alkylamphodicarboxylic acid suitable for use herein is Miranol (TM) C2M Conc., Manufactured by Mira1, Inc, Dayton, NJ.

Amine oxide surfactant

Useful amine oxides herein include compounds of the formula R ³ (OR ⁴ ) x N ° (R ¹ ) 2 wherein R ³ is selected from alkyl, hydroxyalkyl, acylamidopropoyl, and an alkylphenyl group or mixtures thereof. These groups contain from 8 to 26 carbon atoms. preferably from 8 to 18 carbon abottos. R ⁴ is an alkylene or hydroxyalkylene group having from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3. Each R ⁵ is an alkyl or hydroxyalkyl group, which has from 1 to 3, preferably from 1 to 2, carbon atoms or a polyethylene oxide group having from 1 to 3, preferably 1, an ethylene oxide group. The R ⁵ groups can be attached to another R ⁶ group via an oxygen or nitrogen atom and can form a cyclic structure.

The amine oxide surfactants, in particular alkyldimethylamine oxides and alkoxyethylhydroxyethyl amine oxides. materials are dimethyloctylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, including

Cio - is Cs - is such

Examples are diethyldecylamine oxide, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminoxime, dimethyldodecylaminomethylamide, dimethyldodecylaminomethylamide, dimethyldodecylaminomethyldimethylamide. Preferred are C 10-18 alkyldimethylamine oxide and C 10-18 acylamidocyldimethylamine oxide.

Both theses i d

The double surfactants are also added to the detergent compositions of the present invention. These surfactants are generally described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultain surfactants are examples of zwitterionic surfactants for this application.

Betaine surfactant

The betaines for use herein are compounds of formula R (R '> 2N * R ² COO where R is a C 6-18 hydrocarbon group, preferably a C 10-6 alkyl group or a C 10-6 acylamidoalkyl group, R ¹ is typically C 1-3 alkyl, preferably methyl. R ³ is a C 1-8 hydrocarbon group, preferably a C 1-3 alkylene group, more preferably a C 1-2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine, hexadecyldimethyl betaine.

C12-14 acylanidopropyl betaine, C8-14 acylamidohexyldiethyl betaine, 4 [C1-4-acylmethylamidodiethylammonium-1-carboxybutane, C1-6-acylamidodimethyl betaine, C12-16 acylamidopentanediethyl betaine, C12-16 acylmethylamidodimethyl. Preferred are C12-C18 dimethylammonio bexanoate and C10-18 acylaidopropane (or ethane) dimethyl (or diethyl) betaine. A betaine surfactant complex is also suitable.

Sultain surfactant

Sultains useful herein are compounds of the formula:

(R (R ¹ ) ² N ⁺ R ² SO ₃ wherein R is a C 6-18 hydrocarbon group, preferably a C 10-6 alkyl group, more preferably a C 12-13 alkyl group. R ¹ is typically C 1-3 alkyl, preferably methyl and R ² is a C 1-4 hydrocarbon group, preferably a C 1-3 alkylene or preferably a hydroxyalkylene group.

Ampholytic surfactant

Ampholytic surfactants are also added to the detergent compositions herein. These surfactants are generally described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical is either linear or branched.

Kat ionactive surfactants

Cationic surfactants are also used in the detergent compositions herein. Suitable cationic surfactants include quaternary ammonium surfactants which are selected from mono C 6-10, preferably C 6-10 N-alkyl or alkenylammonium surfactants, wherein the remaining N-positions are occupied by methyl, hydroxyethyl or hydroxypropyl groups.

Water-soluble filler

The detergent compositions of the present invention preferably comprise a water-soluble filler, which is typically present at a level of from 1 to 80% by weight, preferably from 10 to 70% by weight, and more preferably from 20 to 60% by weight of the composition.

Suitable water-soluble fillers include water-soluble monomeric polycarboxylates or acid forms thereof, bomo or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acids contain at least two carboxyl radicals separated from no more than two carbon atoms and their carbonates, bicarbonates, borates, borates, borates, , silicates and mixtures of the compounds described above.

Carboxylate and polycarboxylate builders are either of the cligomeric or monomeric type, although monomeric carboxylates are preferred for cost and effect reasons.

Suitable carboxylates that contain one carboxy group include the water-soluble salts of lactic acid, glycolic acid, and ether derivatives thereof. Polycarboxylates containing two carboxy groups include water-soluble malonic, ethylenedioxy) di-acetic, tartaric, tartronic and fumaric, as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble citrates, aconititrates and citraconates, as well as succinic acid derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactosuccinates described in British Patent No. 1,389,732, and the aminosuccinates described in U.S. Pat. and oxypolycarboxylate materials such as the 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent No. 1,261,829, 1,1,2, 2-ethanethetracarboxylates, antarboxylic, maleic, diglycol,

1,1,3,3-propantetracarboxylates and 1,1,2,3-propantetracarboxylates. Polycarboxylates containing sulfo substituents include sulfosuccinate derivatives as disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent Nos. 3,936,448 and sulfonated pyrolyzed citrates described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane, cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates,

2.3.4.5-tetrahydrofuran-cis, cis, cis-tetracarboxylates,

2,5-tetrahydrofuran-cis-dicarboxylates,

2,2,5,5- te tra. hydrofuran, tetracarboxylates,

The 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives are sorbitol, mannitol and xylitol. including phthalic acid, phthalic acid derivatives disclosed by polyhydroxy alcohols such as pyromic acid aromatic carboxylates, and British Patent No. 1,425,343.

Of the aforementioned polycarboxylates, hydroxycarboxylates having three carboxy groups per molecule are preferred, citrates being particularly preferred.

The starting acid or monomeric or olefinic polycarboxylate chelating agents or salts thereof, e.g. citric acid or mixtures thereof, or citrate / citric acid mixtures are also contemplated as useful fillers.

Borate builders, as well as components that contain borate-releasing material and that produce borate upon detergent storage or under wash conditions are also used, but are not preferred under wash conditions at less than 50 ° C, particularly at less than 40 ° C. Deň: 32 ° C.

Examples of carbonate fillers are alkali metal and alkaline earth metal carbonates, which include sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate as described in German Patent Application No. 2,321,001, issued November 15, 1973.

Specific examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, and sodium and potassium orthophosphates, sodium meth / phosphate, in which the degree of polymerization is in the range of 6 to 21, and phytic acid salts.

Suitable silicates include water-soluble sodium silicates having an S1O2 ratio ^; NasO from 1.0 to 2.8, silicones having a ratio of 1.6 to 2.0 are preferred. Silicates are also

2,4 and most preferably are in the form of anhydrous salts or hydrated salts. Most preferred is sodium silicate with an SiO2 Na2 O ratio of 2.0.

The silicates are preferably present in the detergent compositions of the present invention at levels of from 5 to 50% by weight of the composition, more preferably from 10 to 40% by weight.

Partially soluble or insoluble filler

The compositions of the present invention comprise partially insoluble, nonsoluble fillers, which are typically present at a level of from 1 to 80% by weight, preferably from 10 to 70% by weight, and most preferably from 20 to 60% by weight of the composition.

Examples of considerably water-insoluble fillers are sodium sulfide.

Suitable aluminosilicate zeolites have the unit cell ^formula: »and ₂ [(AlO ₂₎ z (SiO 2> yl XlfeO emanations which are at least 6, the molar ratio ZKY is from 1.0 to 0.5 and x is MyUserName 5, preferably from 7 The aluminosilicate materials are in their hydrated form and are preferably crystalline, containing from 10 to 28%, more preferably from 18 to 22% water in bound form.

Aluminosilicate zeolites are naturally occurring materials, but are preferably synthetically derivatized. Synthetic crystalline ion exchange materials are obtained under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. formula ^:

Naiat (AlOa) ia (SiO2) 123 -XH2O where x is from 20 to 30, mainly 27.

Zeoli t X has the formula:

AlO2 sieve> 86 (SiO2> tl2776H2O

Protective agent for heavy metal ions

Preferably, the detergent compositions of the present invention comprise a heavy metal preservative as an optional ingredient. Heavy metal preservative herein refers to components that serve as a chelating agent for heavy metal ions. These components may also chelate calcium or magnesium ions, but preferably exhibit selectivity in the binding of heavy metal ions such as iron, manganese, and copper.

Protecting reagents for even onty heavy of metals they are in basis present in values from O, 005 to 20%, p advantage 1 from O, 1 up to 10%, preferably i from 0, 25 up to 7,5% and most preferably i from 0.5 up to 5%

by weight of the composition.

Heavy metal ion protecting agents are acidic in nature and have, for example, a phosphonic or carboxylic acid functional group, which may be present in their acid form or as a complex / salt with a suitable paired cation such as an alkali metal ion, an ammonium or substituted ammonium ion, or any mixtures thereof. Preferably, the salts / complexes are water-soluble. The molar ratio of the paired cation to the protecting agent for heavy metal ions is preferably at least 1 = 1.

Suitable preservatives for heavy metal ions for use herein include organic phosphonates (such as aminoalkylene polyalkylene phosphonates), alkali metal methane-1-hydroxydiphosphonates and nitrilotrimethylene phosphonates.

Preferred among the above are diethylenetriaminepenta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

Other suitable heavy metal ion preservatives for use herein include tritriotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminepentaacetic acid, ethylenediamine amine, antaric acid, ethylenediamine and amine. ig 1ukarová,

2-hydroxypropylenediamine disuccinate and any salts thereof.

Particularly preferred are ethylenediamine-N, N * -disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium and substituted ammonium salts or mixtures thereof. Preferred EDDS compounds are the free acid forms and the sodium or magnesium salts of EDDS or complexes thereof. Examples of such preferred EDDS sodium salts are NazEDDS and NaaEDDS. Examples of preferred magnesium EDDS complexes include MgEDDS and MgZEDDS.

Other suitable heavy metal ion preservatives for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid, as described in EP-A-317,542 and EP-A-399, 133.

Iminodioacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid-α-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid are also suitable for use herein. These acids are described in EP-A-516,102. β-alanine-N, N-diacetic acid, aspartic acid-N, di-acetic acid, aspartic acid-α-B-nonoacetic acid and iminodisuccinic acid as described in EP-A-5O9,382 are also useful as protective agents for use herein.

EP-A-476,257 discloses suitable amino group-based preservatives. EP-A-510,331 discloses suitable collagen, keratin or casein-derived preservatives. EP-A-528,859 discloses an alkyliminodiacetic acid as a suitable preservative. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable.

Glycidamide-N, N'-di-antaric acid (GADS), ethylenediamine-N, N'-diglucic acid (EDDG) and 2-hydroxypropylenediamine-Ν, N'-disuccinic acid (HPDDS) are also suitable.

Bleaching catalyst

The compositions optionally comprise a bleach catalyst which contains a transition metal.

One suitable type of bleach catalysts is a catalytic system consisting of a heavy metal cation with a defined catalytic bleaching activity such as copper, iron or manganese cations. Further, they comprise a metal cation which has little or no catalytic whitening activity, such as zinc or aluminum cations, and a preservative having defined stability constants for the catalytic and cation metal cation ion. In particular, ethylenediaminetetraacetic acid, ethylenediaminetetraethylenephosphonic acid) and their water-soluble salts are used as such preservatives. Such catalysts are disclosed in US Patent 4,430,243.

Other types of bleach catalysts include manganese-based complexes as described in US Patents 5,246,621 and 5,244,594. Examples of such preferred catalysts include

Mn ^IV 2 (u-0) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- <PFd> 2, Mn ^III 2 (u-0) i (u-OAc) 2, 1,4 7-trimethyl-1,4,7-triazacyclononane) 2- (ClO 4) 2, Mn ^IV 4 (µO) 6 (1,4,7-triazacyclononane) 4- (CIO 4) 2,

Mn ^{li: r} Mn ^IV 4 (µ-O) 1 (µ-OAc) 2 '<1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (ClO 4) 2 and mixtures thereof.

Others are described in European Patent Application No. 549,272. Other suitable ligands for this use include 1,5,9-trimethyl-1,5,9-triazacyclododecane,

2-methyl-1,4,7-triazacyclononane,

1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

For an example of suitable bleach catalysts see US Patent 4,246,612 and US Patent 5,227,084. Also US Patent 5,194,416 discloses mononuclear manganese complexes such as Mn 1,4,7-triazacyclononane (OCH3) 3 (PFe).

Still other types of bleach catalysts are described in US Patent 5,114,606 and are water-soluble manganese and / or manganese complexes with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive digestions. C-OH groups. Preferred ligands are sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, 1actose and other mixtures thereof.

US Patent 5,114,611 discloses a catalyst comprising transition metal complexes including Mn, Co, Fe or Cu with non- (macro) -cyclic ligands. These ligands have the formula ^:

R ² R ³ 1 ll

RB — R where R ¹ ,! ³ .!? ³ and R ⁴ are each selected from hydrogen, substituted alkyl or aryl groups such as R ¹ -N = CR ² and R ³ -C = NR ⁴ and form five or six membered cycles. These cycles are further substituted. B is a bridging group selected from O, S, CR ⁵ ! ⁶ , NR ⁷ and C = O, wherein R ⁵ , R ⁶ and R ⁷ are each either hydrogen, alkyl or aryl groups that include substituted and unsubstituted groups. Preferred ligands are pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole cycles. Optionally, the cycles may be substituted with such substituents as alkyl, aryl, alkoxy, halogen and nitro. Particularly preferred is 2,2'-bis-pyridylamine as a ligand. Preferred are bleach catalysts, which include Co, Cu, Mn, and Fe complexes with bispyrimidylmethane and bispyrimidylamine. Highly preferred catalysts include Co (2,2'-bispyrimidylamine) Cl 2, di (isothiocyanato) bispyridylanine cobalt (II) chlorates and trispyrididylamine cobalt (II), Co (2,2-bispyridylamine) 2 <> 2ClO 4, bis chlorate - (2,2-bispyridylamine) of copper (II) and trisidi-2-pyrididinylamine) of iron (II) and mixtures thereof.

Other examples include binuclear manganese complexes with tetra-N-dentate and bi-N-dentate as ligands. These complexes include N4Íln ¹¹¹ (UO) 2Íln ^IV N 4) ⁺ and [BipyzMn ¹¹¹ (u-0> 2mn ^Iv bipy2] - (ClO4) 3Other bleach catalysts are described in European Patent Application publication number 408,131 (cobalt complex catalysts), European Patent Application Publication Nos. 384,503 and 306,089 (Metal-Porphyrin Catalysts), U.S. Patent No. 4,728,455 (Manganese / Multidentate Ligand Catalysts), U.S. Patent No. 4,711,748, and European Patent Application Publication Nos. US 4,601,845 (aluminosilicate carrier with manganese, zinc or magnesium salts), in US

4,626,373 (manganese / 1 igand catalyst), in US 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelating catalyst), Canadian 866,191 (salts containing transition metals), US 4,430,243 (chelating agents with manganese cations and non- 4,728,455 (manganese gluconate catalysts).

The bleach catalyst is typically used in a catalytically effective amount in the compositions and methods described herein. By catalytically effective amount is meant an amount sufficient under comparable test conditions to increase bleaching and to remove the desired spot or spots from the target substance. The test conditions will vary depending on the type of wash used and the user's practice. Some users use very hot water, others use hot to cold water. However, the catalytic action of the bleach catalyst should be effective even under such requirements, the content of the catalyst used in fully formulated detergents and bleaching compositions is adjusted accordingly. In practice, the catalyst content cannot be defined, and the compositions and methods herein are adapted to provide at least one part of active catalyst per ten million parts of aqueous wash solutions, preferably to provide from about 1 ppm to about 200 ppm of catalyst in the wash solution. To illustrate this point below, a 3 micromolar manganese catalyst solution is effective at 40 ° C and pH 10 in a European washing method using a perborate and a bleach precursor.

An increase in concentration to 3-5 units is required under US washing conditions to achieve the same results.

Enzyme

Another preferred ingredient for use in laundry detergent compositions is one or more additional enzymes.

Preferred additional enzymatic materials include commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases, which are commonly admixed in laundry detergents. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include enzymes sold under the tradenames A1calase, Savinase, Primase, Durazy and Esperase from Novo Industries A / S (Denmark), enzymes sold under the tradenames Maxatase, Maxatal and Maxap from Gist-Brocades, enzymes sold by Genencor International and enzymes sold under the trade names Opticlean and Optimase by Solvay Enzymes. Protease enzymes are added to the compositions of the invention at levels of from 0.0001 to 4% by weight of the active enzyme.

Preferred amylases are, for example, et-amylases which are obtained from a special strain of Licheniformis B, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include those sold under the tradenames Rapidase from Gist-Brocades, Termamyl and BAN from Novo Industries A / S. Amylase enzymes are added to the composition of the present invention at values of from 0.0001 to 2% by weight of the active enzyme.

The lipolytic enzyme (lipase) is present at values of from 0.0001 to 2% by weight of the active enzyme, more preferably from 0.001 to 1% by weight, most preferably from 0.001 to 0.53% by weight.

The lipase is either bacterial or fungal in origin, for example, the lipase is produced by strains of Humicola sp., Thermomyces sp., Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases from chemical or genetic mutants of these strains are also used.

Preferred are lipsticks which are derived from Pseudomonas pseudoalcaligenes as described in European patent EP-B-0218272.

Other preferred lipases here are obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza as a host as described in European patent application EP-A-0258 068, which is commercially obtained from Novo Industries A / S, Bagsvaerd, Denmark under under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al., Issued March 7, 1989.

Organic polymer compound

Organic polymeric compounds are preferred as optional ingredients in the detergent compositions of the present invention and are preferably present as ingredients in bulk compositions where they serve as binder of bulk compositions in the composition. By organic polymeric compound is meant in principle any polymeric organic compound which is commonly used as a dispersing, soil re-settling and soil-suspending substance in laundry detergents and includes any highly molecular organic polymeric compounds described herein as flocculating substances clays.

The organic polymeric compounds are typically present in the detergent compositions of the present invention at levels of from 0.1 to 30%, preferably from 0.5 to 15%, and most preferably from 1 to 10% by weight.

Examples of organic polymeric compounds include water-soluble homo- and copolyric polycarboxylic acids or salts thereof, in which the polycarboxylic acid contains at least two carboxylic radicals, separated from each other by no more than two carbon atoms. Polymers of the second type are described in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 2000-5000 and their copolymers with maleic anhydride having a molecular weight of from 20,000 to 100,000, in particular from 40,000 to 80,000.

Other suitable organic polymeric compounds include acrylamide-acrylate copolymers having a molecular weight of from 3,000 to 100,000, and acrylate / fumarate copolymers having a molecular weight of from 2,000 to 80,000.

The polyaaino compounds useful herein include polyaaino aspartic acid derivatives as described in EP-A-305282, EP-A-305283 and EP-A-351629.

Also suitable are terpolymers which contain monomer units selected from maleic, acrylic, polyaspartamic acid and vinyl alcohol, and in particular those having an average molecular weight of from 5,000 to ΙΟ0,000.

Other organic polymeric compounds suitable for addition to the laundry detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other useful polymeric compounds are polyethylene glycols, especially polyethylene glycols having a molecular weight of from about 10,000 to about 10,000, more preferably from about 2,000 to about 8,000, and most preferably about 4,000.

A system that suppresses foaming

The detergent compositions of the invention, when formulated for use in automatic washing machines, preferably comprise a suds suppressor system. The system is present at a level of from 0.01 to 15%, preferably from 0.05 to 10%, and most preferably from 0.1 to 5% by weight.

Suitable suds suppressor systems for use herein include, in principle, any known antifoam compound including silicone antifoam compounds and 2-alkylalkanol antifoam compounds.

By the antifoam compound is meant herein any compound or mixture of compounds that reduces the foaming that results from a detergent solution, particularly when the solution is stirred.

Particularly preferred for this use are silicone antifoam compounds, which are defined herein as antifoam compounds that contain a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term silicone, as used herein and in the industry, includes various relatively high molecular weight polymers containing a polyoxane unit and a hydrocarbon group of various types. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having terminal trimethylsilyl units.

Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Patent 2,954,347, issued September 27, 1960 to Hayne ST. John. Monocarboxylic fatty acids and their salts, which are used as suds suppressors, typically have hydrocarbon chains of 10 to 24 carbon atoms and preferably of 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanoammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters with monovalent alcohols, aliphatic C 14-4 ketones (e.g., stearone), N-alkylated aminotriazines such as tri- and hexaalkylmelamines, or di - to tetraalkyldiamine chlorotriazines formed as reaction products of cyanuric chloride with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms, further propylene oxide, stearic acid bisamide and di-alkali aonostearyl diphosphate (eg sodium, potassium, lithium) ) and phosphate esters.

Suitable antifoam compounds for use herein are also ethylene oxide and propylene oxide copolymers, especially mixed ethoxylated / propoxylated fatty alcohols having a chain length of from 10 to 16 carbon atoms and an ethoxylation degree of from 3 to 30 and a propoxylation degree of from 1 to 10.

DE 40 21 265 describes suitable 2-alkyl alkanols as antifoam compounds for this use. The 2-alkyl alkanols suitable for use herein consist of a C 6-6 alkyl chain that carries a terminal hydroxyl group and that alkyl chain is substituted in that chain. Mixtures of 2-alkylalkanols are according to the invention.

A preferred suds suppressor system consists of = (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound which comprises a combination of (i) a polydimethylsiloxane of from 50 to 99%, preferably from 75 to 99% 95% by weight and the C 1-10 alkyl position are used in the (ii) silica compositions in a content of from 1 to 50%, preferably from 5 to 25% by weight, of the icon / silicon dioxide antifoam compound. % of silicon dioxide is added to the composition in a value of from 5 to 50%, preferably from 10 to 40% by weight.

(b) a dispersion compound which most preferably consists of a silicone glycol copolymer having a polyoxyalkylene content of 72 to 78% and an ethylene oxide to propylene oxide ratio of from 1: 0.9 to 1 = 1.1 and in the range of from 0.5 to 10%; preferably from 1 to 10% by weight, a preferred silicone-glycol copolymer of this type is DC0544, which is commercially available from DOW Corning under the trade name DCO544, (c) an inert liquid carrier, most preferably consisting of a C16-5 is ethoxylated alcohol with a degree of ethoxylation from 5 to 50, preferably from 8 to 15, in a content of from 5 to 80%, preferably from 10 to 70% by weight.

Particularly preferred for this use are suds suppressor systems which consist of a mixture of alkylated siloxanes of the type described above and solid silica.

The solid silica is either sublimed silica, precipitated silica or silica made from gel. A suitable silica has an average particle size of from 0.1 to 50 microns, preferably from 1 to 20 microns, and a surface area of at least 50 m ² / g. These silica particles exhibit hydrophobic properties when treated with dialkylsilyl groups and / or trialkylsilyl groups which are bonded directly to the silica or by means of a silicone resin. It is preferred to use silica particles which are hydrophobically treated with dimethyl and / or trimethylsilyl groups. Powdered antifoam compounds for use in the detergent compositions of the present invention are preferred. The compositions comprise an amount of silica such that the weight ratio of silica to silicone is in the range of 1 = 100 to 3 = 10, preferably 1: 50 to 1 = 7.

Other suitable suds suppressor systems are particularly represented by hydrophobic silane (most preferably trimethyl silane) silica having a particle size of from 10 nanometers to 20 nanometers and a specific surface area above 50 m ² / g, and which is very well mixed with dimethylsilicon. liquid.

having a molecular weight ranging from 500 to 200,000 and a weight ratio of silicone to silane silica is from 1 = 1 to 1 = 2.

foaming foams containing equine

Highly preferred is a particulate system as described in EP-A-0210731 and an antifoam compound and an organic carrier having a melting point of from 50 to 85 ° C. This organic carrier consists of a glycerol monoester and a fatty acid having a carbon chain from 12 to 20 carbon atoms. EP-A-O21O721 describes other preferred free-flowing suds suppressor systems wherein the organic carrier is a fatty acid or alcohol having a carbon chain of 12 to 20 carbon atoms or mixtures thereof and having a melting point of from 45 to 80 ° C.

Other highly preferred bulk suds suppressing systems are described in European Patent Application 91870007 to the Procter and Gamble Company. The present invention encompasses systems comprising a silicone antifoam compound, carrier, organic coating material and glycerol in a glycerol = silicone antifoam compound weight ratio of 1 = 2 to 3 = 1. Also, European Patent Application 91201342 discloses highly preferred free flow suds suppressing systems which contain a silicone antifoam compound, carrier, organic coating material and crystalline or amorphous aluminosilicate in a weight ratio of aluminosilicate = silicone antifoam compound from 1 = 3 to 3 = 1. Of the highly preferred carriers, a granular suds controlling agent such as starch is preferred in both of the above examples.

An example of a suds suppressor system suitable for use herein is a bulk agglomerated component which is produced by agglomeration and comprises in combination = (i) from 5 to 30%, preferably from 8 to 15% by weight of a silicone antifoam compound which (ii) from about 50% to about 90%, preferably from about 60% to about 80%, by weight of a carrier, preferably starch, (iii) from about 5% to about 50% by weight of said carrier; up to 30%, preferably from 10 to 20% by weight of the agglomerate binder, which is any compound or mixture thereof that is typically used as a binder for agglomerates, most preferably the agglomerate binder comprises a C 18-18 ethoxylated alcohol with an ethoxylation degree of from 50 to

And (iv) from 2 to 15%, preferably from 3 to 10% by weight of a C12-22 hydrogenated fatty acid.

Flaking agent for clays

The compositions of the invention comprise a flocculant for clays, which is preferably present at a level of from 0.005 to 10%, more preferably from 0.05 to 5%, and most preferably from 0.1 to 2% by weight.

The weight ratio of mineral clay to flocculant for clay is preferably from 300 = 1 to 1 = 1, more preferably from 80 = 1 to 10: 1, and most preferably from 60 = 1 to 20 = 1.

The clay flocculant serves to bond the clay particles in the wash solution until the clay particles settle on the fabric surface in the wash. This functional requirement is therefore different from the requirement for clay dispersing compounds that are commonly added to laundry detergents to help remove soiled soils from fabrics and allow them to be dispersed in the wash solution.

Preferred inoculants are organic polymeric materials having an average molecular weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000 and even more preferably from 200,000 to 2,000,000.

Suitable organic polymeric materials include hoaopolymers or copolymers which contain monomeric units selected from alkylene oxide, in particular ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone and ethyleniraine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are preferred.

European Patents Procter and Gamble Company Nos. EP-A-299,575 and EP-A-313,146 disclose organic flocculants for preferred lines in this application.

Inorganic flocculants for clays are also suitable herein, and typical examples are alum and lime.

Polymer dye transfer inhibitors

Detergents also contain from 0.01 to 10%, preferably from 0.05 to 0.5% by weight of polymeric dye transfer inhibitors.

The polymeric dye transfer inhibitors are preferably selected from polyamine N-oxides polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

and)

Polymers polyaain

N-oxide

Polymers of polyamine N-oxide. which are suitable for this use include units having the following structural formula = (I)

P

Ax!

R where P is the polymerization unit a

A is NC = O, O-CO, C = O, -S-, -N-, x is 0 or 1

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or any combination thereof, and wherein the nitrogen of the N-O group is attached to or is nitrated from the N-O group of its constituents.

The N-0 group is represented by the following basic structures:

O ▲

O

A (R ₁ ) X -N- (R ₂ ) y = Ν ^) χ ₍ ρ _{3) ζ} or wherein R ¹ , R ² and R ³ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or / aya / or z is 0 or 1 and wherein the nitrogen of the NO group is attached to these groups or wherein the nitrogen of the NO group forms part of these groups. The NO group is part of the polymerization unit (P) or is attached to the polymer backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerization unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of such polyamine N-oxides comprises a group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred are polyamine N-oxides in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of polyamine N-oxides comprises a group of polyamine N-oxides in which a polymerization unit is attached to the N-O group.

Preferred are the class of polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and wherein the nitrogen of the N-O functional group is part of that R group. Examples of classes of such polyamine N-oxides are polyamine N-oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.

Another preferred class of polyamine N-oxides are polyamine N-oxides having the general formula (I) and wherein R is an aromatic, heterocyclic or non-cyclic group, wherein the nitrogen of the N-O functionality is attached to this R group. Examples of such classes of polyamine oxides are polyamine oxides wherein R is an aromatic group such as phenyl.

A long polymer backbone is used such that the amine oxide polymer is water-soluble and has dye transfer inhibitor properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyacrylates, and mixtures thereof.

The amine N-oxide polymers of this invention typically have an amine to amine N-oxide ratio of from 10 = 1 to 1M OOO OOO. The amount of amine oxide groups present in the polyamine oxide polymer varies by the type of the respective copolymerization or the respective degree of N-oxidation. Preferably, the amine oxide ratio is from 2 = 3 to 1,000,000,000, more preferably from 1: 4 to 1: 1,000,000, and most preferably from 1: 7 to 1 ^: 1,000,000,000. The polymers of the present invention currently include random or block copolymers wherein one monomer type is an amine N-oxide and the other monomer type is also an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, and more preferably pKa < 6.

Polyamine N-oxides are obtained at almost any degree of polymerization. The degree of polymerization is not critical in providing the desired water solubility and dye suspending ability. Typically, the average molecular weight is in the range. 500 to 1,000,000, preferably 1,000 to 50,000, even more preferably 2,000 to 30,000, and most preferably 3,000 to 20,000.

b) N-vinylpyrrolidone and N-vinylimidazole copolymers

Preferred polymers for use herein include a polymer selected from copolymers of N-vinylimidazole and N-vinylpyrrolidone, the polymer having an average molecular weight in the range of 5,000 to 50,000, more preferably 8,000 to 30,000 and most preferably 10,000 to 20,000. For the ferred copolymers of N-vinylimidazole and N-vinyl pyrrolidone, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone has from 1 to 0.2, more preferably from 0.8 to 0.3, and most preferably from 0.6 to 0.4.

c) Polyvinylpyrrolidone

The detergent compositions herein also utilize polyvinylpyrrolidone (PVP) having an average molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trade names PVP K-15 (average molecular weight 10,000 OOO), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000). PVP K-15 is also obtained from ISP Corporation. Other suitable polyvinylpyrrolidones that are commercially available from BASF Cooperathion include Sokalan HP 165 and Sokalan HP 12.

Polyvinylpyrrolidone is added to the detergent compositions herein at levels of from 0.01 to 5% by weight. preferably from 0.05 to 3% by weight, even more preferably from 0.1 to 2% by weight. The amount of polyvinylpyrrolidone contained in the washable solution is preferably from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, preferably from 5 ppm to 100 ppm.

d) Polyvinyloxazolidone

The detergents herein also utilize polyvinyloxazolidones as polymeric dye transfer inhibitors. These polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 200,000, even more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000. The amount of polyvinyloxazolidones to be added to the detergent composition is from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, and more preferably from 0.1 to 2% by weight. The amount contained in the wash solution is typically from 0.5 to 250 ppm, preferably from 2.5 to 150 ppm, preferably from 5 to 100 ppm.

(e) Polyvinylimidazole

The detergent compositions herein also utilize polyvinylimidazole as a polymeric dye transfer inhibitor. These polyimidazoles preferably have an average molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.

The amount of polyvinylimidazole to be added to the detergent compositions is from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, more preferably from 0.1 to 2% by weight. The amount of polyvinylimidazole that is included in the wash solution is from 0.5 to 250 ppm, preferably from 2.5 to 150 ppm, more preferably from 5 to 100 ppm.

Optical brighteners

The detergent compositions herein also optionally comprise from 0.005 to 5% by weight of a certain type of hydrophilic optical brightener, which also serves as a dye transfer inhibitor. When used in the compositions, these compositions contain from 0.01 to 1% by weight of such optical brighteners.

Hydrophilic optical brighteners used herein have the structural formula:

wherein R1 is selected from NH-2-hydroxyethyl, R2 is N-2-hydroxyethyl-N-methylamino, anilino, N-2-bishydroxyethyl is selected from N-2-bishydroxyethyl, morpholino, chloro and amino and M is a cation, or potassium.

It is - 1 above

N-2-bishydroxyethyl and the brightener is which forms a salt such as sodium cation of the above formula M is a cation ion as then disodium

R1 is amino, R2 is sodium cationic acid salt

4,4'-bist (4-amino-6- (N-2-bishydroxyethyl) -s-triazin-2-yl-amine) -2,2'-stilbensulfonic acid, which is commercially marketed under the trade name Tinopal-UNPA -GX from Ciba-Geigy Corporation In these detergents, Tinopalu-UNPA-GX is preferred as a hydrophilic optical brightener

In the above formula, when R1 is not Nino, R2 is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium cation, the brightener is 4,4'-bis-4-amino-6- (N) disodium salt. -2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amine] -2,2'-stilbensulfonic acid. This particulate brightener is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

In the above formula, when R1 is not 1ino, R2 is morphine and M is sodium cation, the brightener is 4,4'-bis [(4-amino-6-morpholin-s-triazin-2-yl) -2-disodium salt. This bulk brightener is commercially marketed under the tradename Tinopal ASM-GX by Ciba-Geigy Corporation.

Cationic fabric softening agents

Cationic fabric softening agents are also added to the compositions of the present invention. These substances are present either as different components or as previously described, hydrophobically activated clays. Suitable cationic fabric softening agents include the water-soluble tertiary amines or the two long amide chain materials described in GB-A-514 276 and EP-B-O Oil 340.

Cationic fabric softening agents are typically added in total values of from 0.5 to 15% by weight, and typically from 1 to 5% by weight.

Other optional components

Other optional ingredients in the compositions of this invention are perfumes, colorants and filler salts, a preferred filler salt is sodium sulfate.

Formation of resources

The solid compositions of the present invention take various physical forms, including granular and tableted forms.

The granular compositions are mainly so-called high bulk density concentrate detergents which are adapted to be added to automatic washing machines by a dispensing device which is placed in the drum of the washing machine together with the soiled laundry. Concentrated granular laundry detergents are dispensed into the wash liquid by a dispensing device and are more susceptible to solubility problems than detergents which are added through the dispenser of the washing machine because, in the early stages of the wash cycle, the textile load prevents mixing in the immediate vicinity of the product. However, this can ensure success in producing high intermediate component concentrations. The formation of a high intermediate concentration of organic peroxyacid may, as noted above, lead to speckled dyeing of the fabrics.

The mean particle size of the components in the granular compositions of the invention is such that no more than 5% of the particles are larger than 1.7 mm in diameter and no more than 5% of the particles are smaller than 0.15 mm in diameter.

The term mean particle size, as defined herein, is calculated from the screen analysis of a sample for a number of fractions (typically 5 fractions) on a set of Tyler screens. The fraction weights thus obtained are plotted depending on the mesh size of the sieves. The mean particle size then corresponds to the mesh size through which passes 50% of the sample weight.

The bulk density of the present invention is g / l to 1200 g / l, and the bulk density of the granular laundry detergent composition is typically at least 600 g / l, more preferably from 650 to preferably 1000 to 1000 g / l.

is measured with a simple funnel device, eg the knife is put out of alignment.

which consists of a conical funnel which is fixed on a support and is provided with a flap valve at its narrowest point. The valve allows the contents to be emptied into an axially symmetrical cylindrical vessel located below the funnel. The funnel is 130 mm high and has internal diameters of the largest 130mm and the smallest 40 mm. It is positioned so that the lowest part is 140 mm above the top surface of the washer. Its nominal volume is 500 ml.

During the measurement, the funnel is manually filled with powder, the flap valve is opened and the powder is overfilled with the container. The filled frame container and excess powder are removed from the top end with a straight edge tool such as the filled container is then weighed and the weight value is then multiplied by two to give a bulk density in g / l. It is recommended to repeat the measurement.

Clay / organic peroxyacid particle precursor

Preferably, the organic peroxyacid precursor or tableted organic peroxyacid and the clay mineral compound are present in combination as free-flowing components, which preferably contain additional components which aid the cohesion of the particles and optimize their storage stability and flowability characteristics. Particularly preferred are additional components which promote good particle structure. These are binders which contain, for example, some of the organic polymeric compounds described above.

The flowable components are in any suitable form such as granules, flakes or noodles, but are preferably in the form of granules. The granules themselves are agglomerated in a bowl or drum in an in-line mixer or made by spray drying, which is formed by spraying an aqueous suspension of the ingredients in a stream of hot air where most of the water is removed.

Packaging of funds

Commercially available bleach formulations are packaged in a variety of suitable containers, including containers made of paper, cardboard, plastic materials and suitable laminates. Preference is given to an embodiment of the packaging as described in European application no.

93970141.4.

Abbreviations used in the Examples

In detergents, the abbreviations of the ingredients are as follows

meanings: XYAS Sodium C 1-6 alkyl sulfate 25EY: mainly C12-15 linear primary alcohol condensed with an average Y moles of ethylene oxide XYEZ: mainly Cix-iy linear primary alcohol condensed with an average Z mole of ethylene oxide XYEXS ' mainly sodium C 1-6 alkyl sulfate condensed with an average Z mole of ethylene oxide per mole mol. TEAA: C 1-6 alkyl N-glucamide Silicate; amorphous sodium silicate (SiO2 ^: Na2O ratio = 2.0) NaSKS-6 crystalline layered silicate of the formula β- NazSizCte

Carbonate: anhydrous sodium carbonate

MA / AA: 1 = 4 maleic / acrylic acid copolymer, average molecular weight 70,000

Zeoli t A hydrated sodium aluminosilicate of the formula

See Al2SO2O2) 12.27 H2O having a primary particle size ranging from 1 to 10 microns

Citrate trisodium citrate dihydrate Peruhliči tan anhydrous sodium percarbonate or sodium bleach coated with a sodium silicate coating (Si20: Na2O ratio = 2,1) in a percarbonate-sodium silicate 39 ^: 1 weight ratio TAED particles = tetraacetyl ethylenediamine particles formed by agglomeration of TAED with maleic / acrylic acid copolymer 14 having an average molecular weight of 70,000 in a TAED-copolymer ratio of 85 ^: 10 by weight. Subsequently, these agglomerates are coated with this copolymer in a weight ratio of the agomerate coating of 955 Proteása proteolytic enzyme that is sold under the trade name of Savino from Novo Industries A / S with an activity of 13 KNPU / g Amylase ^: amylolytic enzyme sold under brand name Termamyl 6OT from Novo Industries A / S with an activity of 1000 CEVU / g Lipása ^; a lipolytic enzyme sold under the trade name Lipolase from Novo Industries A / S with activity 165 KLU / g CMC: sodium carboxymethylcellulose HEDP 1,1-hydroxyethane phosphonic acid EDDS ethylenediamine-N, N'-disuccinic acid, [S, S1 i somer, in the form of sodium salt DETPMP ethylenetriamine penta (methylenephosphonic acid) acid ina) PVNO poly (4-vinylpyridine) -N-oxide copolymer vinylimidazole and vinylpyrrole don, which he has average molecular weight 10,000 OOO

Hli nka

Granular montmorillonite calcium suds suppressor

12% icon strength / silica, 18% 70% starch in granular form stearyl alcohol

Example 1 =

TAED / clay particles 1

The agglomerate of the following formulation was made in an Eirich mixer model RVO2 (trade name)% by weight

TAED 85 hl ^xx 5

MA / AA ^x 10

100 ^x Sokolan 45 (trade name) from BASF ^xx Bentonite (”) from Colin Stewart Minchem Ltd

TAED and clay were placed in an Eirich mixer and pre-mixed. The powder temperature was 25 ° C. An aqueous MA / AA binder solution having a temperature of 60 ° C was then added to the mixer over 30 seconds while stirring the Eirich blades and rotating the vessel. The resulting mass was then further stirred for 30 seconds. Stirring was stopped and the agglomerated product was removed from the Eirich mixer and further dried in a fluid bed dryer to a moisture content of 2%. The product was sieved and a material greater than 1180 microns and less than 250 microns was discarded.

TAED / clay particles 2

The above procedure was repeated except that the clay was replaced with an acid clay Tonsi1 P (tradename) sold by Sud Chemie AG) _of the same quantity.

TAED / clay particles 3

The agglomerate having the following composition was made by Eirich mission or model RVO2 (trade name)% by weight

TAED 80 clay ** 5 MA / AA * 1O * Sokolan 45 from BASF ^xx Bentonite from Colin Stewart Minchem Ltd

Bentonite and clay were placed in an Eirich mixer and premixed. The powder temperature was 25 ° C. The molten binder, which had a temperature of 60 ° C, was then added to the powder mixture over 30 seconds, while stirring with the Eirich blades and rotating the vessel. The resulting mass was then stirred for an additional 30 seconds. Stirring was stopped and the agloaerated product was removed from the Eirich mixer and further dried in a fluid bed dryer. The product was then screened and material greater than 1180 microns and less than 250 microns was discarded. The resulting aglonerate was then coated with MA / AA at an agglomerate coating value of 5 = 95.

The following granular detergents A, B, C, D and E for washing laundry at a density of 75Og / l have been prepared and the figures given are parts by weight, A and B are comparative compositions and C and E are compositions prepared in accordance with are used in a granulette dispensing apparatus for the laundry of the present invention ¹

AND (B) C D E 45AS / 25AS 9, 1 9, 1 9, 1 9, 1 9, 1 35AE3S 2, 3 2.3 2, 3 2, 3 2, 3 24E5 4,5 4, 5 4, 5 4, 5 4,5 TFAA 2, 0 2. O 2, O 2, 0 2, O Zeolite A 10. 2 10, 2 10, 2 10, 2 10.2

On SKS-6 / acid59

1 i on or throne (79:21) 10, 6 10, 6 10, 6 10, 6 10.6 Charcoal or tan 7, 6 7, 6 7.6 7, 6 7.6 TAED part i ce 5 6, 67 - - - TAED / clay part i ce 1 - - 6, 67 - - < TAED / clay part i ce 2 - - - 6, 67 - TAED / clay part 3 - - - - 6, 67 Squadron tan 22, 5 22, 5 22.5 22, 5 22.5 DETPMP 0, 8 0.8 O, 8 O, 8 O, 8 Proteása 0, 55 0, 55 O, 55 0, 55 0, 55 Li belt O, 15 0, 15 O, 15 O, 15 O, 15 Ce1u1osa 0. 28 O, 28 O, 28 O, 28 0, 28 Amylase 0, 27 0, 27 0.27 0.27 0, 27 Polycarboxylate 3, 1 3, 1 3, 1 3, 1 3, 1 * CMC 0.4 0, 4 0.4 0, 4 O, 4 PVNO 0, 03 O, 03 O, 03 O, 03 O, 03 Granulated substance foam suppressor 1.5 1.5 1.5 1.5 1.5

minor substances up to 100%

Comparative effect testing

Test Protocol 1 - Spotted bleach testing

Formulations A through E have been tested fully in the washing machine test. A 12 Miele washing machine (Model HM H698) was used and was set to a short wash cycle at 40 ° C for each formulation. Water of 12 ° Clark hardness (= 1.8 mmol Ca ²⁺ / liter) was used. The numbered textile samples were placed in a washing machine in pairs. Textile samples were made from garments that were obtained from High Street stores. Further details ^:

1 1 Sample number Type of garment Color ! Type text i 1 i e | 1 and 4 | 1 1 wool vest navy blue | 1 50/50 i wool / acres] j 2 and 3 men's shirt dark green 100% bav1na J 5 and 8 1 three | black J100% bav1na | 16 and 7 J i 1 Men's T-Shirt | black 1 j 10/90%! Cotton / polyester J J9 and 12 j T-shirt J black 100% cotton j 10 and 11 j e ans basket ile j blue 1100% bav1na J 13 & 16} T-shirt 1 I50 / 50% i 1 with a long one 1 1cotton / polyester 1 1 sleeve J black 1 1 J14 and 15 1 je ans | black 100% cotton | 17 and 20, men's | black 65/35% 1 1 trousers ! 1Polyester / Viscose j 18 and 19 | men's shirt jzelená 100% Cotton J 121 and 24 men's basket ile j dark green 100% cotton 22 and 23 i i 1 i 1 eginy 1 black and and I97 / 3% i j bav1na / 1kra 1 i 1

Each washer was filled with 1.9 kg (4 lbs) ballast laundry in the order of the following materials: textile sample, 100g formulation dispensed from a granulette dispensing device of the type described in EP-A-343,070 and commonly obtained under the trade name Ariel Ultra granulated laundry detergent i »>

and sold by The Procter and Gamble Company and the second textile sample was placed on top. The 30x30 cm samples were packed together in case the dispenser was caught during the first stages of detergent dissolution / dispersion. At the end of the cycle, samples were removed and air dried.

The samples were visually evaluated for discoloration of the fabric using a scale in which three color samples with different degrees of damage were used as standards to determine a 6-point scale in which 0 corresponds to "no coloring" and 5 corresponds to extreme discoloration. Three standards were used to define the midpoints between the different bleach descriptions

No discolouration very large discolouration and weak discoloration clearly discolored discoloration very discolored extreme discoloration

The samples were evaluated by two experts and their results were averaged.

Comparative test - blotch discoloration

Using the above test protocol, the resulting color damage after formulations A to E was compared. The following results were obtained:

% of samples having a degree of damage

Formulation 0 1 2 3 4 5 Total degree AND 67 17 8 8 0 O 0, 57 (B) 58 13 13 12 4 O O, 91 C 84 O 8 8 0 O O, 40 D 80 4 4 12 O O O, 48 E 75 4 8 13 O 0 0, 59

As can be seen, compositions C to E of the present invention exhibit appreciably the lowest discoloration of fabrics than compositions A and B.

Test report 2 - stain removal

Three white cotton sheets were prewashed in strong detergents without non-biological bleach. Teaspots were stained on one sheet, wine stains on the other, and coffee stains on the third. Six 6x6 cm test specimens were made from each sheet.

Sets of textile samples were tested in one machine wash cycle. Samples were evaluated for removal of tea, coffee and wine stains using a well-proven light-measuring method.

More specifically, an Miele 756 WTi washer was used, a short cycle at 40 ° C was selected. Water of 12 ° Clark hardness (= 1.8 mmol Ca ²⁺ / liter) was used. 100g of detergents were used, which were dosed from the granulette dispenser. One sample of each type of fabric was washed between the ballast of 1.9 kg (4 lbs) of lightly soiled sheets.

Stain removal was evaluated by LAB measurements using an X-rite (trade name) color spectrophotometer. A spotless sheet was used as a reference. The stain removal index dR was calculated as follows:

dR = (L-washed - L-not washed) / (L-washed - L-referenced) x100

Comparative test - stain removal

The above Test Protocol 2 was used to compare the efficacy of compositions B and C in removing different types of stains. The following results were obtained:

dR% (B) C tea 78 76 wine 82 83 coffee 75 74

The stain removal of compositions B and C was comparable.

Example 2 Granular compositions A to 2x2 tablet form

E from Example 1 x 2 cm.

were pressed into

Industrial applicability

The laundry bleaching compositions of the present invention and the described method of dispensing them directly into the drum of the washing machine allow better bleach removal and reduce color damage to textiles.

Claims (17)

CLAIMS 1. A method of washing laundry in domestic and industrial washing machines, characterized in that there is provided a means for dispensing an effective amount of a solid laundry detergent comprising peroxyacid bleaching agent directly into the drum of the washing machine. washing liquids and wherein the peroxyacid bleaching composition comprises (a) a bleaching system capable of providing an organic peroxyacid bleach to the wash solution, and wherein the bleaching system is selected from (i) a hydrogen peroxide source in combination with an organic peroxyacid precursor (ii) tableted organic peroxyacids and mixtures thereof; (b) a non-three-dimensional phyllosic acid mineral compound wherein the organic peroxyacid precursor or tableted peroxyacid and the non-three-dimensional phyllosic acid mineral compound are in close physical proximity to the composition. osti. 2. The process of claim 1, wherein the organic peroxyacid precursor or tableted organic peroxyacid and the non-three-dimensional phyllosilicate mineral compound are in the composition well mixed. The process according to any one of claims 1 to 2, wherein the weight ratio of the non-three-dimensional phyllosiclate mineral compound to the organic peroxyacid or tablet organic peroxyacid precursor is from 1 ^: 6 to 1-99. The process according to any one of claims 1 to 3, wherein the peroxyacid bleaching agent is in free flowing form and the organic peroxyacid precursor or tableted organic peroxyacid and the non-three-dimensional phyllosiclate mineral compound are present in the same free flowing component. I 'I t> 5. The method of claim 4, wherein the detergent is in granular form and has a bulk density of not less than 600 g / l. A method according to any one of claims 1 to 5, characterized in that the dispensing method is a dispensing device filled with solid detergent and the dispensing device is placed in the drum of the washing machine before the start of the washing. Method according to any one of claims 1 to 3, characterized in that the dosing method is dispensed in the form of a solid detergent such as tablets and placed in the drum of the washing machine before the start of the washing. A detergent composition according to any one of claims 1 to 7, wherein the non-three-dimensional phyllosiclate mineral compound is clay. The method of claim 8, wherein the clay is smectite clay. The process according to any one of claims 1 to 7, wherein the non-three-dimensional phyllosilicate compound is a crystalline layered silicate. 11. The method of claim 10 wherein the crystalline layered silicate has the formula ^: NaMSixO2x + iy H2O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number * from 0 to 20. The process according to any one of claims 1 to 11, wherein the source of hydrogen peroxide is an inorganic perhydrate salt. 13. The process of claim 12 wherein the inorganic perhydrate salt is an alkali metal percarbonate. Process according to any one of claims 1 to 13, characterized in that the peroxyacid precursor is present in a value greater than 3% of the detergent composition. A process according to any one of the preceding claims, wherein perhydrolysis of the claims 1 to 14 provides organic peracetic acid precursor. 16. The process of claim 1 wherein the organic peroxyacid precursor is tetraacetylethylenediamine. 17. The method of any one of the preceding claims wherein the organic peroxyacid precursor is an organic peroxyacid which is (i) a perbensoic acid or a substituted derivative or (i) a cationic peroxyacid. The claims of claims 1 to 14 give perhydrolysis its non-leakage and on and off