HUT77961A - Laundry washing method using a dispensing means for a solid bleaching detergent - 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

Laundry laundry process using a solid bleach detergent dispenser

THE PROCTER & GAMBLE COMPANY, CINCINNATI, Ohio, US

Date of filing: 30.10.1995.

Priority: 9422378.1, 5.11.1994, GB

International Application Number: PCT / US95 / 14077

International Publication Number WO 96/14384

BACKGROUND OF THE INVENTION The present invention relates to a laundry washing process in a household or industrial washing machine, wherein a solid, particularly high density, detergent composition containing a bleaching system capable of providing an organic peroxyacid bleach and a non-three-dimensional phyllosilicate mineral is directly introduced into the wash solution through a dispenser. Typically, the dispenser is filled with an effective amount of detergent product and then placed in the drum of the washing machine prior to commencing the wash cycle. As the rotation of the washing machine drum responds to the mixing of the device and as a result of contact of the detergent product contained therein with the washing water, a gradual detergent dissolution occurs at the beginning of the washing cycle and enters the wash water to produce a temporarily high detergent concentration. An alternative way of administering the detergent is by tabletting.

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DISCLOSURE

EXAMPLE s.B.G. & k

International Patent Office

H-1062 Budapest, Andrássy út 113. Telephone; 34-24-950, Fax: 34-24-323

63 839 / BE

Laundry laundry process using a solid bleach detergent dispenser

THE PROCTER & GAMBLE COMPANY, CINCINNATI, Ohio, US

inventors:

BAILLELY Gerard Marcel, NEWCASTLE UPON TYNE, GB GUEDIRA Nour-Edine, NEWCASTLE UPON TYNE, GB HALL Robin Gibson, NEWCASTLE UPON TYNE, GB

Date of filing: 30.10.1995.

Priority: 9422378.1, 5.11.1994, GB

International Application Number: PCT / US95 / 14077

International Publication Number: WO 96/14384 • · ►

• ··········· · · · · · · · · · · · · · · · · · · · · · ·

BACKGROUND OF THE INVENTION The present invention relates to a process for washing laundry in a household or industrial washing machine, and more particularly to a process for dispensing a bleaching system capable of providing an organic peroxyacid bleach and a non-three-dimensional phyllosilicate mineral into a washing solution through a solid, particularly high density detergent composition. directly into the wash solution.

A particular challenge for the manufacturer of a bleaching composition used in a laundry laundry process is the satisfactory removal of bleachable stains / stains from stained fabrics, such as tea, fruit juice, and colored plant impurities. Conventionally, bleaching components such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids, have been used to remove such bleachable spots. Organic peroxyacids are often obtained by an in situ perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor. Alternatively, the organic peroxyacids may be used as preformed bleach components in the compositions.

The increase in the use of organic peroxyacid bleach precursors allows for lower fabric washing temperatures, which in itself is associated with an increase in the proportion of colored fabrics in a typical household washing machine load.

It has been recognized in the art that there is an advantage in stain removal performance with a laundry laundry process that allows for the creation of high localized instantaneous concentrations of certain detergent types, including builders and surfactants. ·· "· · · · · · · • ·· ······ ····· • · · · · · · · · ···· ► At the beginning of term ^3. J. Bland in Manufacturing Chemist, November 1989, pp. 41-46. page, the article describes such benefits in more detail. High transient concentrations can occur for a variety of reasons. Detergent compositions may in themselves have low solubility per se, delayed solubility in the presence of other substances, such as viscous surfactant phases, or, in the immediate vicinity of the detergent species, the mixing system may not be sufficiently intensive to disperse the dissolved detergent.

A preferred solution for allowing such localized, high transition concentrations to occur is to use a dosing device to deliver the detergent product directly to the wash solution. A suitable solution involves the use of a metering device. Typically, the dispenser is filled with an effective amount of detergent product and then placed in the drum of the washing machine prior to commencing the wash cycle. By rotating the drum of the washing machine in response to the mixing of the device and as a result of contact of the detergent product contained therein with the washing water, a gradual detergent dissolution occurs at the beginning of the washing cycle.

Although the formation of localized, high transient concentrations may be beneficial for certain types of detergent, the problem associated with the formation of localized high concentrations of bleaching agents, particularly organic peroxyacids, may be that the color and material of these localized, high-bleaching fabrics may be damaged. One particular problem we can count on is the localized "blotch discoloration of colored dyes on fabrics. Some toners are particularly sensitive to “blemishes”

discoloration problem.

Where an organic peroxyacid bleach precursor is a component of the composition, the potential problem is particularly high when the detergent composition contains high amounts (e.g.,> 3% by weight) of the peroxyacid bleach precursor and / or sodium percarbonate as a source of hydrogen peroxide rapidly. in soluble form.

It has been found that "blemish damage can be a particularly unpleasant problem for peroxyacid bleach precursor compounds which, by perhydrolysis, give a peroxyacid which is a perbenzoic acid or a non-cationic substituted derivative thereof or a cationic peroxyacid. It has also been found that benzoxazine-type precursor compounds particularly raise this problem.

The development of high density products and their insertion into the drum via a dispensing device only aggravates this problem. Accordingly, there is a need for laundry washing processes wherein the wash solution is provided with organic peroxyacid in such a way that its dissolution and minimizing damage to fabrics and materials during wash hydrolysis while allowing washing of soiled / stained white fabrics is acceptable. provides removal.

The prior art includes many examples of coating or agglomerating organic peroxyacid bleach precursors to enhance their storage stability in detergent compositions and / or to influence their behavior in solution.

t

EP-A-0070474 discloses granular organic peroxyacid bleach precursors, which are an activator / coating of 98: 2 to 90:10 together with an N-acyl or O-acyl compound together with at least one water-soluble cellulose ether, starch or starch derivative. is prepared by spray drying an aqueous pumpable dispersion.

GB-A-1507312 discloses the coating of organic peroxyacid bleach precursors with a mixture of alkali metal (C 822) fatty acids mixed with appropriate fatty acids. GB-A1381121 uses a melt coating of, inter alia, C14-C18 fatty acid blends to protect solid organic peroxyacid bleach precursors. GB-A-1441416 discloses a similar process using a mixture of C12-C14 fatty acids and C10-C20 aliphatic alcohols.

EP-A-0375241 discloses stabilized organic peroxyacid bleach precursor extrudates in which C 5 -C 8 alkyl peroxycarboxylic acid precursors are selected from anionic and nonionic surfactants, film-forming polymers, fatty acids or mixtures thereof with binders. mix.

EP-A-0356700 discloses an organic peroxyacid bleach precursor, a water-soluble film-forming polymer, and formulations containing from 2 to 15% C3-C6 polyvalent carboxylic acid or hydroxycarboxylic acid to increase stability and facilitate dispersion / dissolution. The carboxylic acid, a preferred example of which is citric acid, is dry blended with the organic peroxyacid bleach precursor and then the film image ··· · • · · *

granulation with a polymer. Citric acid is used to provide greater dissolution of the organic peroxyacid bleach precursor particles.

EP-A-0382464 is directed to a process for coating or encapsulating solid particles containing bleaching compounds and organic peroxyacid bleaching precursors, wherein the coating material forms a melt in which the particles form a dispersed phase and the melt destabilizes, is sprayed into a material in which the dispersed phase particles are embedded in a continuous (coating) phase. A number of coating materials are disclosed and taught about certain materials, such as polyacrylic acid and (cellulose acetate) phthalate, that can be used when the dissolution of the coated material is pH dependent.

In the prior art, the entire emphasis is on protecting the organic peroxyacid bleach precursor from adverse environmental conditions during storage, and relatively little attention is paid to the solubility properties of the coated or agglomerated material in use. Where coating and / or agglomeration with poorly soluble materials, such as fatty acids, is suggested, this results in an organic peroxyacid bleaching precursor perhydrolysis rate which is slower than that of the unprotected material. In the context of an agglomerated component, any use of more rapidly soluble materials, such as citric acid, in which the organic peroxyacid bleaching precursor is more rapidly soluble is intended. In both cases, the extremely high localized organic peroxyacid bleaching concentrations remain unresolved »

···· ·· ·· · · · · · · · · · · • ·· • · ·· ······ ·· • · · · · · · · · · · ···· · problem , as perhydrolysis begins as the detergent begins to dissolve and forms an alkaline solution of hydrogen peroxide.

EP-A-0 028 432 discloses a granule comprising a detergent composition comprising 5-80% peroxyacid bleach precursor, 15-60% water-insoluble silicate and 5-40% nonionic binder within the solid detergent composition. This water-insoluble silicate compound, a preferred example of which is a smectite clay, is mixed with the peroxyacid bleach precursor and further bonded with a nonionic surfactant. This combination is used to provide rapid development of perhydroxycarbox anions when added to a hydrogen peroxide source.

EP-A-0 028 432 does not teach the use of a dispenser for a laundry laundry process or any problems associated therewith.

JP5-7296 discloses the general problem of color discoloration of fabrics, but not the "specific problem of spotty discoloration. The patent discloses a composition in which a water-insoluble mineral, a peroxyacid bleach precursor and a bleach compound are mixed in a ratio such that the ratio of said mineral to said precursor and bleach compound is 1:99 and 90:10, preferably 20: 80 to 65:35. The water-insoluble mineral is selected from acid clay, activated clay, kaolin, bentonite, diatomaceous earth and perlite and is said to prevent fading without inhibiting the bleaching effect. JP5-7296 ' ll teaches the use of a dispenser in a laundry detergent process and does not disclose any problems that may arise.

WO92 / 13798 discloses the use of acidic substances with specific properties as coatings of peroxyacid bleach precursors during the initial stages of dissolution / dispersion of a product in soaking water to delay the onset of perhydrolysis.

It has been found that in laundry laundry methods where the detergent is introduced into the wash solution through a dispenser, the observed fabric damage, and in particular the "stain on the stained fabric, can be reduced by directly adding specific amounts of a clay mineral to the bleaching organic peroxyacid bleach. It has also been found that the addition of clay minerals does not significantly compromise the bleachable stain removal ability of the formulation or the storage stability of the bleaching component in the product.

Although it is essential that the clay mineral and the organic peroxyacid or precursor compound are thus in direct contact, it is not necessary to coat the bleaching component with the clay component. Indeed, such a coating is less advantageous due to the complexity of the treatment and, consequently, the higher costs.

Detergent formulations containing clay minerals and clay flocculating agents have been previously disclosed in EP-A-299 575 and EP-A-313 146 to provide fabric softening effects.

Ί in European patent applications. These documents do not teach the use of clay minerals for the prevention of fabric damage, including spotty color damage.

The relevant parts of all documents cited herein are incorporated by reference.

The present invention relates to a method of washing in a household or industrial washing machine comprising providing a device for dispensing an effective amount of a solid detergent composition containing a peroxyacid bleaching composition directly into the drum of a washing machine prior to the commencement of washing, wherein said dispensing device allows dissolving in the wash solution during washing, and said peroxyacid bleaching composition is capable of providing (a) a bleaching system for providing organic peroxyacid bleach in a laundry washing solution, wherein said bleaching system is (i) a source of hydrogen peroxide combined with an organic peroxyacid bleaching precursor compound;

(ii) a preformed organic peroxyacid; and any mixtures thereof; and (b) a non-three-dimensional phyllosilicate mineral, wherein said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three-dimensional phyllosilicate mineral are in close physical proximity.

Preferably, said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and the non-three-dimensional phyllosilicate that are present are in direct contact, most preferably directly mixed within the disclosed composition.

Preferably, said detergent composition comprising said peroxyacid bleach composition is in particulate form, more preferably in granular form, and said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three-dimensional phyllosilicate mineral are present in the same particulate component.

Each granular detergent composition preferably has a high bulk density, more preferably a bulk density of at least 600 g / l.

In a preferred embodiment, the dispenser is provided by filling a dispenser with the solid detergent composition and placing said dispenser in the drum of a washing machine prior to the commencement of the wash.

In another preferred embodiment, said dispenser is provided by tabletting said solid detergent composition and placing said tablet in a washing machine drum prior to commencement of washing.

The non-three-dimensional phyllosilicate mineral is preferably a clay mineral compound or a crystalline layered silicate mineral compound.

The clay mineral compound is preferably a smectite clay compound.

Non-three-dimensional phyllosilicate for mineral or organic peroxyacid bleach precursor compound or precursor thereof.

Weight ratio of organic peroxyacid to form: 1: 6 and

1:99.

Laundry laundry procedure

Typically, the machine washing methods described herein include treating soiled laundry with an aqueous washing solution containing an effective amount of a laundry detergent composition of the invention dissolved or dispersed in the laundry. The detergent is added to the washing solution using a dispenser. An effective amount of a detergent composition is understood to be a product dissolved or dispersed in a volume of 40-300 grams of a solution of solution in a volume of 5 to 65 liters, as typical product dosages and volumes of a dishwashing solution.

In a fundamental aspect, the dispensing device used in the washing process of the invention delivers an effective amount of the detergent product directly into the drum of the washing machine before the start of the wash cycle. The dispenser allows the detergent product to dissolve into the wash solution typically during the early stages of the wash, more typically within the first two minutes of the wash.

In a preferred embodiment, the disclosed device is a metering device. The dispenser is filled with the detergent product and used to place the product directly into the washer drum. Its capacity must be such as to accommodate the required detergent product normally used in the washing process.

Once the washing machine has been filled with the cloth to be washed, the dispenser containing the detergent product is placed inside the drum. At the beginning of the washing cycle of the washing machine, we add water to the drum. · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · «« * · ·· and rotate the drum periodically. The design of the dispenser should be such as to allow the dry detergent product to be retained, but then, during the wash cycle, allow this product to react with agitation and contact with wash water as the drum rotates.

The device for enabling the detergent product to be released during washing may have a plurality of openings through which the product may pass. Alternatively, the device may be made of a material which is liquid permeable but impermeable to the solid product, allowing release of the dissolved product. Preferably, the detergent product dissolves rapidly at the start of the wash cycle, thereby providing a temporarily high local concentration of the product in the washing machine drum at this stage of the wash cycle.

Preferred dispensers are reusable and designed to keep the container intact, both dry and during the wash cycle. Particularly preferred delivery devices for use according to the invention are disclosed in GB-B-2 157 717, GB-B-2 157 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. J. Bland published an article in Manufacturing Chemist, November 1989, pages 41-46, which also discloses particularly advantageous dispensers for use with granular laundry products commonly known as "granules." Another dispensing device for use according to the invention is disclosed in WO94 / 11562.

Particularly advantageous dispensing devices are disclosed in 0343069 and · * J J J T T T T T T T € * *.

European Patent Publication No. 0343070. The latter patent discloses a device comprising a flexible pouch in the form of a bag protruding from a support ring defining an aperture, the aperture being configured to allow a product required for a cycle to be introduced into the bag during the washing process. A portion of the detergent flows through the opening into the bag, dissolves the product, and the solution then flows through the opening into the detergent. The support ring is provided with a casing to prevent the wetted, undissolved product from escaping, typically comprising walls extending radially from a central hub in a spokes wheel configuration or the like structure in which the walls are helical. Alternatively, the dispensing device may be a flexible container such as a bag or pocket. The bag may be provided with a fibrous structure coated with an impermeable protective material to retain its contents, as disclosed in European Patent Publication No. 0018678. Alternatively, it may be formed from a water-insoluble synthetic polymeric material having a water-insoluble edge weld or seal, as disclosed in European Patent Specifications 0011500, 0011501, 0011502 and 0011968. A conventional form of water-break sealing comprises a water-soluble adhesive placed along one edge of a pocket formed from a water-impermeable polymeric film, such as polyethylene or polypropylene.

In another embodiment, the dispensing device is provided by compressing the detergent composition itself into a tablet form. The ··· tablets are then placed in the drum immediately before the start of the wash cycle. Due to their compacted form, local dissolution of the tablets in the washing solution during the early stages of the washing cycle may result in local high concentrations of bleaching species.

Organic Peroxy Acid White!

An essential feature of the invention is an organic peroxyacid bleaching system. In a preferred embodiment, the bleaching system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of organic peroxyacid occurs by in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide are inorganic perhydrate bleaches. In a preferred alternative embodiment, preformed peroxyacid is added directly to the formulation. Compositions comprising a mixture of a hydrogen peroxide source and an organic peroxyacid bleach precursor compound in combination with a preformed peroxyacid may also be contemplated.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are preferred sources of hydrogen peroxide. These salts are usually added in the form of an alkali metal salt, preferably a sodium salt, in an amount 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 are the perborate, percarbonate, perphosphate, persulfate and persilicate salts. Inorganic perhydrate salts are normally alkali metal salts. The inorganic perhydrate salts may be added as a crystalline solid without further protection.

However, for certain perhydrate salts, preferred embodiments of such particulate compositions utilize a coated form of the material that provides improved storage stability of the perhydrate salts in the particulate product.

Sodium perborate can be in the form of the monohydrate or náboje ₂ H ₂ O ₂ -water (3.1) tetrahydrate náboje ₂ H ₂ O ₂ empirical formula.

Preferred perhydrates for incorporation into the compositions of the present invention are alkali metal percarbonates, especially sodium percarbonate. Sodium percarbonate is an addition compound of the formula 2Na ₂ CO ₃ .3H ₂ O ₂ which is commercially available as a crystalline solid. Because sodium percarbonate is a hydrogen peroxide addition compound, it tends to produce very fast hydrogen peroxide upon dissolution, which may increase the tendency to produce local high concentrations of bleach. Most preferably, the percarbonate is included in such formulations in a coated form which provides product stability.

Suitable coating materials for product stability include a mixed salt of a water-soluble alkali metal sulfate and carbonate. Such coatings, together with coating methods, were previously disclosed in GB-1 466 799 (Interox), issued March 9, 1977. The weight ratio of mixed salt coating material to percarbonate is in the range of 1: 200 to 1: 4, more preferably 1:99 to 1: 9 and most preferably 1:49 to 1:19. The mixed salt is preferably composed of sodium sulfate and sodium carbonate which is Na ₂ SO ₄ . n. Na ₂ CO ₃ , wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0, and most preferably n is from 0.2 to 0.5.

• · • ···· ·· ····

Other coatings containing silicate (alone or with borate salts or boric acids or other inorganic compounds), waxes, oils, fatty soaps may also be advantageously used within the present invention.

Potassium peroxy monopersulphate is another inorganic perhydrate salt useful in the detergent compositions of the present invention.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide to produce peroxyacid in a perhydrolysis reaction. In general, peroxyacid bleach precursors are compounds of the formula I in which

L is a leaving group; and

X is essentially any functional group which forms peroxyacid of general formula (II) in perhydrolysis.

The peroxyacid bleach precursor compounds are preferably included in the detergent compositions in an amount of 0.5 to 20% by weight, more preferably 1 to 15% by weight, most preferably 1.5 to 10% by weight.

However, the tendency to form high local concentrations of peroxyacid is greater when the detergent compositions contain more than 3% by weight, more preferably more than 5% by weight of the peroxyacid bleach precursor compound.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors are selected from a wide range of compound groups17 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Suitable groups include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Suitable materials within these groups are, for example, those disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

It has been found that "blemishes are associated in particular with peroxyacid bleach precursor compounds which, in perhydrolysis, provide a peroxyacid which is (i) a perbenzoic acid or a non-cationic substituted derivative thereof; or (ii) a cationic peroxyacid.

We have determined that benzoxazine precursors are particularly sensitive to this problem.

Leaving groups

The leaving group, hereinafter referred to as the L group, must be sufficiently reactive to allow the perhydrolysis reaction to occur at optimal times (e.g., during a wash cycle).

However, this activator is difficult to stabilize for use in a bleaching composition if the L group is too reactive.

Preferred L groups are (a), (b) and (c), (d), (e), (f), (g), (h), (i), (j), (k), Groups (1) and (m) in which

R ¹ is C 1 -C 14 alkyl, aryl or alkylaryl,

R is a C 1-8 alkyl chain,

3 χ

R is hydrogen or R;

Y is hydrogen or a group promoting solubility.

Any of R ¹ , R ³ and R ⁴ may be substituted with substantially any functional group, including, for example, alkyl, hydroxy, alkoxy, halo, amine, nitrosyl, amide, and ammonium or alkylammonium, and mixtures thereof.

Preferred solubility promoting groups are -SO ₃ 'M ⁺ , -CO ₂ ~ M ⁺ ,

-SO ₄ 'M ⁺ , -N ⁺ (R ³ ) 4X and O-N (R ³ ) 3, and most preferred are -SO ₃ ' M ⁺ , -CO ₂ M ⁺ , in which

R ³ is C 1 -C 4 alkyl,

M is a cation that provides solubility to the bleach activator, and

X is an anion that provides solubility to the bleach activator.

M is preferably an alkali metal, ammonium or substituted ammonium cation, most preferably the sodium and potassium ions, and

X is a halide, hydroxide, methyl sulfate or acetate anion.

Perbenzoic acid precursor

The perbenzoic acid precursor compounds give perbenzoic acid during perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted (benzoyloxy) benzenesulfonates, including, for example, the benzoyloxy-benzenesulfonate of formula (III).

Also suitable are benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, including, for example, the compound of formula (IV) wherein Ac = acetyl; Bz = benzoyl.

Imide-type perbenzoic acid precursor compounds include N-benzoyl succinimide, tetrabenzoyl ethylenediamine and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole and other useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine, and benzoylpyroglutamic acid.

Other perbenzoic acid precursors include benzoyl diacyl peroxides, benzoyl tetraacyl peroxides, and V.

Phthalic anhydride of formula (VI) is another suitable perbenzoic acid precursor compound.

Suitable N-acylated lactam perbenzoic acid precursors are compounds of formula VII wherein n is 0 to 8, preferably 0 to 2, and

R ⁶ is benzoyl.

Perbenzoic acid derivative precursors

The perbenzoic acid derivative precursors yield substituted perbenzoic acids by perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include all perbenzoic acid precursors of the present invention in which the benzoyl group is substituted with substantially any non-positively charged (i.e., non-cationic) functional group, including, for example, alkyl, hydroxy, amino, halogen, , nitrosyl and amido groups.

A preferred group of substituted perbenzoic acid precursor compounds is represented by the formula (VIII) or (IX)

R ¹ is C 1 -C 14 aryl or alkyl aryl,

R ² is C 1 -C 14 arylene or alkyl-arylene and R ⁵ is hydrogen or C 1 -C 10 alkyl, aryl or alkylaryl,

L is essentially any leaving group - amide substituted compounds.

Preferably R is 6 to 12 carbon atoms. Preferably R is C 4 -C 8. R may be aryl, substituted aryl or alkylaryl containing branched, substituted, or both, and may be derived from either synthetic sources or natural sources including, for example, tallow fat. For R ² , analogous structural variants are permitted. The substituent may be alkyl, aryl, halogen, nitrogen, sulfur and other representative substituents or organic compounds. ^R5 is preferably hydrogen or methyl. The total of R ¹ and R ^{5 must} not exceed 18 carbon atoms. Amide-substituted bleach activator compounds of this type are disclosed in EP-A-0170386.

Cationic peroxyacid precursors

Upon perhydrolysis of cationic peroxyacid precursor compounds, cationic peroxyacids are formed.

Typically, the cationic peroxyacid precursors are prepared by substitution of a peroxy functional group of a suitable peroxyacid precursor of a peroxyacid with a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. In solid detergent compositions, cationic peroxyacid precursors are typically present as a salt with a suitable anion, such as a halide.

The cationically substituted peroxyacid precursor compound thus obtained may be a perbenzoic acid or a substituted derivative thereof as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor, as described hereinafter.

Cationic peroxyacid precursors are disclosed in USP. 4,904,406;

751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; '5,093,022;

106,528; U.K. 1,382,594; EP 475 512; 458 396;

284,292; and JP 87-318 332.

Preferred cationic peroxyacid precursors are disclosed, for example, in U.K. No. 9407944.9 and U.S. Pat. 08/2989903, 08/298650,

08/298904 and 08/298906.

Suitable cationic peroxyacid precursors are any ammonium or alkylammonium substituted alkyl or benzoyloxy benzenesulfonate, N-acylated caprolactam and monobenzoyl tetraacetyl glucose benzoyl peroxides.

Preferred cationically substituted (benzoyloxy) benzenesulfonate is the 4- (trimethylammonium) methyl derivative of the benzoyloxybenzenesulfonate of formula (n).

In the cationically substituted alkoxy of formula (X), ··· ··· zol sulfonate is preferred.

Preferred cationic peroxyacid precursors of the N-acylated caprolactam group are trialkylammonium methylene benzoyl caprolactams, in particular trimethylammonium methylene benzoyl caprolactams of formula XI.

Other preferred cationic peroxyacid precursors in the N-acylated caprolactam group are the trialkylammoniomethylene benzoyl caprolactams of formula XII wherein n is 0-12.

Another preferred cationic peroxyacid precursor is [2- (Ν, N, N-trimethylammonio) ethyl-sodium-4-sulfophenylcarbonate] chloride.

Alkyl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleaching precursors are converted to percarboxylic acids by perhydrolysis. Preferred precursors of this type provide peracetic acid for perhydrolysis.

Preferred imid-type alkyl percarboxylic acid precursor compounds are Ν, N, N ¹ , N ¹ -tetraacetylated alkylenediamines in which the alkylene group has from 1 to 6 carbon atoms, particularly preferred compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors are sodium 3,5,5-trimethyl (hexanoyloxy) benzenesulfonate (iso-NOBS), sodium (nonanoyloxy) benzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS). ) and pentaacetyl glucose.

Amide substituted alkyl peroxyacid precursors

Also suitable are amide substituted alkyl peroxyacid precursor compounds including the compounds of formulas VIII and IX in which

R ¹ is C 1 -C 14 alkyl;

,,

R is C1-C14 alkyl; and

R ⁵ is hydrogen or C 1-10 alkyl; and L can be substantially any leaving group.

Preferably R ^{1 has from} 6 to 12 carbon atoms. Preferably R ^{2 is C} 4 -C 8. ^R1 may be straight chain or branched alkyl containing branching, substitution, or both, and either synthetic sources or natural sources including for example, tallow fat. Analogous structural variants are allowed for R ² . The substituent may be alkyl, halogen, nitrogen, sulfur and other representative substituents or organic compounds. ^R5 is preferably hydrogen or methyl. The total of R ¹ and R ^{5 must} not exceed 18 carbon atoms. Such amide substituted bleach activator compounds are disclosed in EP-A-0170386.

Benzoxazine-type organic peroxyacid precursors

Benzoxazine-type precursor compounds, such as those disclosed in, for example, EP-A-332 294 and EP-A-482 807, are also particularly suitable.

II

benzoxazinone compounds of the formula:

Ο

II

RíY ^ N ^ C

Rs-substituted benzoxazinones of the formula: wherein:

R _x is hydrogen, alkyl, alkylaryl, aryl, arylalkyl; and

R ₂ , R ₃ , R ₄ and R ₅ are the same or different and are selected from hydrogen, halogen, alkyl, alkenyl, aryl, hydroxy, alkoxy, amino, alkylamino, -COOR ₆ (where R ₆ represents a hydrogen atom or an alkyl group) and carbonyl functional group.

A particularly preferred benzoxazine-type precursor is a

3-phenyl-1H-2,4-benzoxazin-1-one.

Preformed organic peroxyacid

The organic peroxyacid bleaching system may contain, in addition to the organic peroxyacid bleaching precursor compound or optionally, a preformed organic peroxyacid, typically in the range of from 1 to 15% by weight, more preferably from 1 to 10% by weight.

A preferred group of organic peroxyacid compounds are the amide substituents of formula VIII or IX 25 ···· · · · · «

Vegyületek · · vegyületek • <vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek vegyületek

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

R ² is C 1 -C 14 alkylene, arylene and alkylarylene;

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

L is a hydroperoxy group (-OOH).

Preferably R ^{1 has from} 6 to 12 carbon atoms. Preferably R ^{2 is C} 4 -C 8. ^R1 may be straight chain or branched alkyl, substituted aryl or branching, substitution, or alkaryl containing both, and either synthetic sources or natural sources including for example, tallow fat. Structural variants analogous to R are allowed. The substituent may be alkyl, aryl, halogen, nitrogen, sulfur and other representative substituents or organic compounds. ^R5 is preferably hydrogen or methyl. The total of R ¹ and R ^{5 must} not exceed 18 carbon atoms. Amide substituted bleach activator compounds of this type are disclosed in EP-A-0170386.

Other organic peroxy acids are diacyl and tetraacyl peroxides, in particular diperoxy dodecanedioic acid, diperoxy tetradecanedioic acid and diperoxy hexadecanedioic acid. Mono and di-perazelaic acid, mono- and di-perbrasilic acid and N-phthaloylamino-peroxycaproic acid can also be used in the invention.

Non-three-dimensional phyllosilicate mineral compound

A detergent for use in accordance with the present invention provides a non-greasy product. contain three-dimensional phyllosilicate mineral compound. In an essential embodiment, the non-three-dimensional phyllosilicate mineral compound and the organic peroxyacid bleach precursor compound or the preformed organic peroxyacid are in close physical proximity, more preferably in direct contact, most preferably in direct admixture within the disclosed composition.

The non-three-dimensional phyllosilicate mineral compound is preferably in a weight ratio of from 1: 1 to 1:99, preferably from 1: 3 to 1:49, more preferably from 1: 4 to 1:19, relative to the organic peroxyacid bleach precursor compound or preformed organic peroxyacid is present in the bleaching composition.

A non-three-dimensional phyllosilicate mineral compound is used herein to mean a silicate mineral compound in which substantially flat (two-dimensional) sheets are formed by dividing three of the four oxygen atoms of each silicate in the tetrahedrons by adjacent tetrahedrons. This definition excludes the more complex three-dimensional silicate bonding structure, sometimes called "lattice structure minerals." Preferred non-three-dimensional phyllosilicate mineral compounds of the present invention are clay mineral compounds and crystalline layered silicates. For the sake of clarity, it is noted that the term non-three-dimensional phyllosilicate mineral compound as used herein, excludes sodium aluminosilicate zeolite builder compounds which may, however, be included as builder components of the present invention.

The non-three-dimensional phyllosilicate mineral compound is preferably present as an agglomerated particle component containing the organic peroxyacid bleach precursor compound or the preformed organic peroxyacid and optionally other purifying compounds, including polymeric organic binders.

As used herein, clay mineral compound (abbreviated as "clay") is typically an aqueous phyllosilicate having two or three layers of crystalline structure. Further descriptions of clays can be found in: Kirk-Othmer; Encyclopaedis of Chemical Technology, (John Wiley and Sons), 4th edition, Volume 6, page 381.

The clay-mineral compound is preferably a smectite clay compound. Smectite clays are described in U.S.P. 3,862,058; 3,948,790; 3,954,632;

0 62 647; and EP-A-299 575;

European Patent Specifications EP-A-313,146 (each of Procter & Gamble Company).

As used herein, the term smectite clays includes those which contain alumina in a silica grid and those in which magnesium oxide is present in a silica grid. Typical smectite clay compounds include Al ₂ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ O and

Compounds of the formula Mg ₃ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ O. Smectite clays tend to take on an expandable three-layer structure.

Typical examples of suitable smectite clays are materials selected from the group consisting of montmorillo ··· nitrites, hectorites, nontronites, saponites, and sagonites, especially compounds having an alkali or alkaline earth metal ion within the crystal lattice. Sodium or calcium montmorillonite is particularly preferred.

Suitable smectite clays, especially montmorillonites, are sold by a variety of distributors, including English China Clays, Laviose, Fordamin, Georgia Kaolin, and Colin Stewart Minerals.

Preferred smectite clays are Fordamin White Bentonite STP and

Laviosa Chemical Mineria SPA is sold under the brand name Detercal P7.

The clays to be used in the present invention may be subjected to any suitable acid washing treatment with mineral or organic acids. Such clays give an acidic pH when dissolved in distilled water. This type of commercially available 'acidic clay is marketed under the brand name Tonsil P by Sud Chemie AG.

Within the crystal lattice structure of smectite clays, small cations such as protons, sodium ions, potassium ions, magnesium ions and calcium ions and certain organic molecules, including positively charged functional groups, can typically be substituted.

In a preferred embodiment, the crystal lattice structure of the clay mineral compounds may have a cationic fabric softener substituent. Such substituted clays are referred to as "hydrophobically activated clays. Cationic fabric softeners are typically present in a weight ratio of 1: 200 to 1:10, preferably 1: 100 to 1:20, based on clay. Suitable · »<. · ··· ···

V 4 · · • • • • • 4.

cationic fabric softeners include water-insoluble tertiary amines or di- (long-chain) amide materials as disclosed in GB-A-1 514 276 and

EP-B-0 011 340.

A preferred commercially available hydrophobically activated clay is a bentonite clay containing about 40% by weight of dimethylditallow quaternary ammonium salt sold under the tradename Claytone of English China Clays International.

Crystalline layered silicates are preferred for use in the present invention

NaMSi _x O _{2x + 1} * yH ₂ O - in which

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 disclosed in EP-A-0164514 and their preparation processes are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula is 2, 3 or 4, and preferably 2. The most preferred material is 5-Na ₂ Si ₂ O ₅ , which is available as NaSKS-6.

Hoechst AG.

The crystalline layered sodium silicate material is preferably present as a granulate directly mixed with a solid water-soluble, ionizable material in the granular detergent compositions. The solid, water-soluble, ionizable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

• · · ·

Additional cleaning components

The detergent compositions of the present invention may also contain additional detergent components. The exact nature of these auxiliary components and their mixing amounts will depend upon the physical form of the composition and the exact nature of the purification operation for which it is intended.

Preferably, the compositions of the present invention contain one or more additional detergent components selected from the group consisting of surfactants, builders, organic polymer compounds, additional enzymes, antifoams, lime soap dispersants, soil suspending and re-deposition inhibitors, and corrosion inhibitors.

Surfactant

Preferably, the detergent compositions of the present invention comprise a surfactant selected from the group consisting of anionic, cationic, nonionic ampholytes, amphoteric and zwitterionic surfactants, and mixtures thereof.

Typically, the surfactant is present in an amount of 0.1 to 60% by weight. More preferably, the surfactant is present in an amount of 1 to 35% by weight, most preferably 1 to 20% by weight.

A typical list of anionic, nonionic, ampholytic, and zwitterionic groups and types of these surfactants is given in U.S. Pat. No. 3,929,678 to Laughlin and Heuring. Further examples are given in "Surfactants and detergents (Schwartz, Perry and Berch; Surface Active Agents and Detergents, Vol. I and II.). A list of suitable cationic surfactants is provided in U.S.P. No. 4,259,217 ···· ······ · · · · · · · · · · · · · · · · · · · · · ·

3ΐ ..........

(Murphy).

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

Anionic surfactant

Essentially any anionic surfactant useful for cleaning purposes may be included in the compositions. These include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts).

Other anionic surfactants include isethionates, such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-C18 monoesters) (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from tallow oil are also suitable.

Anionic sulphate surfactant

Suitable anionic sultanate surfactants for use in the present invention include linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C 5 -C 17 acyl-N - (C 1 -C 4 alkyl) - and -N- (C 1 -C 2 hydroxyalkyl) 32 · ·························································································· ·· · · · ···

sulphates of glutamine sulphates and alkyl polysaccharides such as alkyl polyglucoside sulphates (nonionic non-sulphated compounds disclosed herein).

The alkyl ethoxysulfate surfactants are preferably selected from the group consisting of C 6 -C 18 alkyl sulfates, which are ethoxylated with about 0.5 to 20 moles per molecule of ethylene oxide. More preferably, the alkyl ethoxysulfate surfactant is an alkyl sulfate having from 6 to 18 carbon atoms, ethoxylated with about 0.5 to 20 moles, preferably about 0.5 to 5 moles, per molecule of ethylene oxide.

Anionic sulfonate surfactant

Suitable anionic sulfonate surfactants for use in the present invention include C 5-20 linear alkyl benzene sulfonates, alkyl ester sulfonates, C 6-22 primary or secondary alkane sulfonates, C 6-24 olefin sulfonates, sulfonated polycarboxylic acids, sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants for use in the present invention include alkyl ethoxycarboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps ("alkyl carboxyls"), particularly certain secondary soaps as described herein.

Preferred alkyl ethoxycarboxylates for use in the present invention are compounds of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COO M ⁺

R is C 6 -C 18 alkyl;

• · x is in the range of 0 to 10 and the ethoxylate weight distribution is such that if x is 0, less than 20%, and if x is greater than 7, the mean x a value of from about 2 to about 4 when the average R is 13 carbon atoms or less, and an average value of x from about 3 to about 10 when the average R is greater than 13; and

M is a cation, preferably a cation selected from alkali metal, alkaline earth metal, ammonium, mono-, di-, triethanolammonium ions, most preferably sodium, potassium, ammonium and mixtures thereof. Preferred alkyl ethoxycarboxylates are those wherein R is C 12 -C 18 alkyl.

Suitable alkyl polyethoxypolycarboxylate surfactants for use in the present invention include

Compounds of the formula RO- (CHR ₁ -CHR ₂ -O) -R ₃ - in which

R is C 6 -C 18 alkyl;

x is from 1 to 25;

R _x and R ₂ are selected from the group consisting of hydrogen, acetyl, succinyl, hydroxysuccinyl and mixtures thereof, wherein at least one of R _x or R _{2 is} a succinyl group or a hydroxysuccinyl group; and

R ₃ is selected from the group consisting of hydrogen, substituted or unsubstituted C 1 -C 8 hydrocarbons and mixtures thereof.

Anionic secondary soap is a surfactant

Preferred soap surfactants are secondary soap surfactants containing a carbonyl unit attached to a secondary carbon atom. The secondary carbon may be in a ring structure, such as in p-octylbenzoic acid or as alkyl-substituted cyclohexylcarboxylates. The secondary soap surfactants preferably do not contain ether linkages, ester linkages or hydroxy groups. The head group (amphiphilic moiety) preferably contains no nitrogen atoms. Secondary soap surfactants usually have from 11 to 15 carbon atoms, although slightly more carbon atoms (e.g. up to 16), such as p-octylbenzoic acid, are tolerated.

Preferred secondary soap surfactants are further illustrated by the following general structures:

A. A very preferred group of secondary soaps is

R ^{3 is a} formula CH (R ⁴ ) COOM in which

R ³ is CH ³ (CH 2) X and R ⁴ is CH 3 (CH ₂ ) _y - wherein y is an integer from 0 to 1 to 4, x is an integer from 4 to 10, and (x + y) preferably contains from 6 to 10, most preferably 8 secondary carboxylic acids.

B. Another preferred class of secondary soaps are carboxy compounds wherein the carboxy substituent is on a cyclic hydrocarbon moiety, i.e.

R ⁵ -R ⁶ -COOM - • · in which

R ⁵ is C 7 -C 10 alkyl, preferably C 8 -C 9 alkyl or alkenyl; and

R ⁶ is a ring structure such as benzene, cyclopentane and cyclohexane. (Note: R ^{5 may be in} ortho, meta or para position with respect to the carbonyl group on the ring.) - Contains secondary soaps.

C. Another preferred class of secondary soaps

CH ₃ (CHR) _k - (CH ₂ ) _m - (CHR) _n -CH (COOM) (CHR) _o - (CH ₂ ) _p - (CHR) _q -CH ₃ - in which each R C 1 -C 4 alkyl groups are k, n, o, q values which are integers from 0 to 8, provided that the total number of carbon atoms (including carboxylates) is in the range of 10 to 18, being secondary carboxy compounds.

In each of the above formulas A, B and C, M is any suitable, highly water-soluble counterion.

Particularly preferred secondary soap surfactants for use in the present invention are a water-soluble member selected from the group consisting of water-soluble salts of 2-methyl undecanoic acid, 2-ethyl decanoic acid, 2-propyl nonanoic acid, 2-butyl octanoic acid, and 2-pentylheptanoic acid.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants include

R-CON (R ¹ ) CH ₂ COOM - wherein

R is a linear or branched alkyl or alkenyl group containing from 5 to 17 carbon atoms;

• · · · · · · ··· ······· · ······

..........

R ¹ is C 1 -C 4 alkyl; and

M is an alkali metal ion - alkali metal sarcosinates. For example, myristyl and oleyl methyl sarcosinates in the form of their sodium salts are preferred.

Nonionic surfactant

Essentially any nonionic surfactant useful for cleaning purposes may be included in the compositions. The following is an example of non-limiting groups of nonionic surfactants that may be used.

Nonionic polyhydroxy fatty acid amide surfactant

Suitable polyhydroxy fatty acid amides for use in the present invention are R ² CONR ^X Z wherein R ¹ is hydrogen, C 1-4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C 1-4 alkyl, more preferably C 1-2 alkyl, most preferably C 1 alkyl (i.e. methyl); and

R is a C 5 -C 31 hydrocarbon, preferably a straight-chained C 5 -C 19 alkyl or alkenyl, more preferably a straight-chained C 9 -C 17 alkyl or alkenyl, most preferably a straight-chained C 11 -C 17 alkyl or alkenyl group, or a mixture thereof. ; and

Z is a polyhydroxy hydrocarbon group having at least 3 hydroxy groups directly attached to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Preferably, Z is a reductant derived from a reducing sugar * · ·········· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·· active amination reaction; more preferably, Z is a glycityl.

Nonionic condensates of alkyl phenols

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use in the present invention. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having from about 6 to about 18 carbon atoms having alkyl groups in either straight or branched configuration with alkylene oxide.

Nonionic ethoxylated alcohol surfactant

Suitable condensation products of aliphatic alcohols with alkyl ethoxylate with about 1 to about 25 moles of ethylene oxide are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary and generally has from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having 8 to 20 carbon atoms with about 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated / propoxylated fatty alcohol surfactants

Ethoxylated are suitable for use in the present invention

C 6-18 fatty alcohols and C 6-18 mixed ethoxylated / propoxylated fatty alcohols. The ethoxylated fatty alcohols are preferably C 10 -C 18 ethoxylated fatty alcohols having 3 to 50 degrees of ethoxylation, most preferably 3 to 40 degrees of ethoxylation.

C 12-18 ethoxylated fatty alcohols. The mixed ethoxylated / propoxylated fatty alcohols is preferably from 10 to 18 carbon atoms • • · · · · · · · ·· • • ······ ····· · · · · _{Λ Λ} ······ ·· they have a chain length of 3 to 30 degrees of ethoxylation and 1 to 10 degrees of propoxylation.

Nonionic EO / PO condensates with propylene glycol

Suitable for use in the present invention are condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic moiety of these compounds preferably has a molecular weight of about 1500 to about 1800 and exhibits water insolubility. Examples of such compounds are the commercially available Pluronic surfactants commercially available from BASF.

Nonionic with propylene oxide / ethylene diamine adducts

EO condensation products

Suitable condensation products for ethylene oxide, propylene oxide and ethylenediamine are the products used in the present invention. The hydrophobic group of these products consists of reaction products of excess ethylene diamine and propylene oxide and generally has a molecular weight of about 2500-3000. Examples of this type of nonionic surfactant are certain Tetronic ™ compounds commercially available from BASF.

Nonionic alkyl polysaccharide surfactant

Suitable alkyl polysaccharides for use in the present invention are disclosed in U.S. Pat. U.S. Patent 4,565,647 (Llenado), which has a hydrophobic group having from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. , They have a polyglucoside containing 3-2.7 saccharide units. Any reducing carbohydrate having 5 to 6 carbon atoms may be used, for example the glucosyl groups may be substituted with the glucose, galactose and galactosyl groups. (Optionally, the hydrophobic group is 2-, 3-,

4- etc. The linkages between the saccharides may be, for example, between one of the following sites on the saccharide moiety and the 2-, 3-, 4- and / or 6-position on the previous saccharide moieties.

Preferred are alkyl polyglucosides

R ² O (C _n H _2n O) t (glycosyl) _x - wherein 2

R is selected from the group consisting of alkyl, alkylfemyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, having from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms;

n is 2 or 3;

t is 0 to 10, preferably 0, and

X is 1.3-8, preferably 1.3-3, most preferably 1.3-2.7.

Glucosyl is preferably derived from glucose.

Nonionic fatty acid amide surfactant

Suitable fatty acid amide surfactants for use in the present invention are of the formula R CON (R) ₂

R ⁶ is a C 7-21, preferably C 9-17, alkyl group; and R ⁷ is hydrogen, (C 1 -C 4) alkyl, (C 1 -C 4) hydroxyalkyl, and - (C ₂ H ₄ O) _X H - wherein x is 1-3 · * · ···· ** · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ··· ·

Amphoteric surfactant

Suitable amphoteric surfactants for use in the present invention are amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable examples for use in the present invention are Miranol (TM) C2M Conc. Manufactured by Miranol, Inc., Dayton, NJ.

Amine oxide surfactant

Amine oxides useful in the present invention include

R (OR) _X NO (R) ₂ - wherein R ³ is selected from C 8 -C ²⁶ alkyl, preferably C 8 -C 18 alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group;

R is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof;

x is 0-5, preferably 0-3; and each R ⁵ is a group with 1-3, preferably 1-2 carbon atoms or a polyethylene oxide group having a hydroxyalkyl group or a C 1-3, preferably 1, ethylene oxide groups. The ^R5 groups can be coupled to each other to form a ring such as through an oxygen or nitrogen atom. These amine oxide surfactants typically contain C 10 -C 18 alkyldimethylamine oxides and C 8 -C 18 alkoxyethyl dihydroxyethylamine oxides. Examples of such materials are dimethyl octylamine oxide, diethyl decyl amine oxide, bis (2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetraadecyl amine oxide , methylethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide, cetyldimethylamine oxide, stearyldimethylamine oxide, tallow dimethylamine oxide and dimethyl 2-hydroxy. octadecyl amine oxide. C 10 -C 18 alkyldimethylamine oxides and C 10 -C 18 acylamidoalkyldimethylamine oxides are preferred.

Zwitterionic surfactant

Zwitterionic surfactants may also be included in the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or as quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants that may be used in the present invention include beta and sultain surfactants.

Betaine type surfactant

Betaines useful in the present invention are compounds having the formula R (R ') ₂ N ⁺ R ² COO - wherein R is a C 6 -C 18 hydrocarbon group, preferably a C 10 -C 16 alkyl group or a C 10 -C 16 acylamidoalkyl group;

each R 'is typically C 1-3 alkyl, preferably methyl; and

R is a C 1 -C 5 hydrocarbon group, preferably a C 1 -C 3 alkylene group, more preferably a C 1 -C 2 alkylene group.

Suitable betaines include, for example, coconut acylamidopropylene dimethyl betaine; hexadecyl dimethyl betaine; C12-C14 acyl42 • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ··· * · · · Amido-propyl-betaine; C 8 -C 14 acylamido hexyl diethyl betaine; 4 - [(C 14 -C 16 acyl) (methylamido) (diethylammonio)] - 1-carboxybutane; C 16 -C 18 acylamido-dimethyl betaine; C 12 -C 16 acylamidopentane diethyl betaine; (C 12 -C 16 acyl) methylamido-dimethyl betaine. Preferred betaines are C 16 -C 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Surfactants in the beta of the complex are also suitable for use in the invention.

Sultain type surfactant

Suitable sultans for use in the present invention are compounds 1 + 2 of the formula R (R) ₂ NR NO ₃ - wherein

R is a hydrocarbon group having from 6 to 18 carbon atoms, preferably

C 10 -C 16 alkyl, more preferably C 12 -C 13 alkyl;

each R ¹ is typically C 1-3 alkyl groups, preferably methyl; and

R is a C 1 -C 6 hydrocarbon group, preferably a C 1 -C 3 alkylene or preferably a hydroxyalkylene group.

Ampholytic surfactant

Ampholytic surfactants may be included in the detergent compositions of the present invention. These surfactants can be described in broad terms as aliphatic derivatives of secondary and tertiary amines, or as aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety may be linear or branched.

Cationic surfactants

Cationic surfactants can also be used in the detergent compositions of the present invention. Suitable cationic surfactants are quaternary ammonium surfactants selected from C 6 -C 16 mono-, preferably C 6 -C 10 N-alkyl or alkenylammonium surfactants in which the remaining N sites are methyl, hydroxyethyl or hydroxy. substituted with propyl groups.

Water soluble builder compound

The detergent compositions of the present invention contain a water-soluble builder compound as a preferred optional component, typically present in an amount of from 1 to 80% by weight of the composition, preferably from 10 to 70% by weight, most preferably from 20 to 60% by weight.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or acid forms thereof, homo- or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid is at least two carboxyl groups, carbonates, dicarbonates, borates, containing mixtures of any of the foregoing.

The carboxylate or polycarboxylate may be of the builder monomeric or oligomeric type, although for reasons of cost and performance, monomeric polycarboxylates are generally preferred.

Suitable carboxylates containing one carboxy group include lactic acid, water-soluble salts of glycolic acid and their ether derivatives. Carboxylates containing two carboxy groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid · · · · · · · · · · · · · · · · · · · Water soluble salts of c ·· acid, and ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitates and citraconates, as well as succinate derivatives such as carboxymethoxysuccinates disclosed in British Patent No. 1,379,241; lactoxysuccinates and a

Amino succinates disclosed in Dutch Patent No. 7205873 and oxy-polycarboxylates disclosed in British Patent No. 1,387,447, such as 2-oxa-1,3,3-propane tricarboxylates.

Polycarboxylates containing four carboxy groups are disclosed in British Patent No. 1,261,829.

1,1,2,2, -ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include

British Patent Nos. 398,421 and 1,398,422 and U.S. Pat. The sulfosuccinate derivatives disclosed in U.S. Patent No. 3,936,448 and the sulfonated, pyrolyzed citrates disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane cis, cis, cis tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran cis,

2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexanehexacarboxylates and carboxymethyl derivatives of polyhydric alcohols, such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates are derivatives of mellitic acid, pyromellitic acid and phthalic acid disclosed in British Patent No. 1,425,343.

Of the above, polycarboxylates and hydroxycarboxylates containing up to three carboxy groups per molecule are preferred, more preferably citrates.

Suitable builder components may include starting weeks of the monomeric or oligomeric chelating agents or mixtures thereof, such as citric acid or citrate / citric acid mixtures.

Borate builders and borate-forming agents which contain borate-producing materials under detergent storage or washing conditions may be used, but are not preferred under washing conditions of less than about 50 ° C, especially less than about 40 ° C.

Carbonate builders include, for example, alkaline earth and alkaline metal carbonates, including sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, as disclosed in U.S. Patent No. 2,321,001, issued November 15, 1973.

Typical examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, about 21 and salts of phytic acid.

Suitable silicates have a water-soluble SiO ₂ : Na ₂ O ratio of 1.0-2.8, preferably 1.6-2.4, most preferably 2.0. sodium silicates. The silicates may be in the form of either anhydrous or hydrated salts. The most preferred silicate is 2.0 SiO ₂ : Na ₂ O sodium silicate.

In the detergent compositions of the present invention, the silicates preferably comprise from 5% to 50% by weight of the composition, more preferably

They are present in an amount of 10-40% by weight. ·

The detergent compositions of the present invention preferably contain from 5 to 50% by weight of the silicates, more preferably

They are present in an amount of 10-40% by weight.

Partially soluble or insoluble builder

The detergent compositions of the present invention may contain a partially soluble or insoluble builder, typically present in an amount of from 1 to 80% by weight, preferably from 10 to 70% by weight, most preferably from 20 to 60% by weight. Examples of bulk water-insoluble builders are sodium aluminum silicates.

Suitable aluminum silicate zeolites have a unit cell of the formula Na ₂ [(AlO ₂ ) _z (SiO ₂ ) _y ] · ΧΗ ₂ Ο - wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5; and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in a hydrated form, preferably in a crystalline, bound form, containing 10-28% water, more preferably 18-22% water.

Aluminum silicate ion-exchange materials may be naturally occurring materials, but are preferably of synthetic origin. Synthetic crystalline aluminum silicate ion exchange agents are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof.

Zeolite A

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · χΗ ₂ Ο - where x is from 20 to 30, typically 27.

Zeolite X Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 276Η ₂ Ο.

Heavy metal ion chelators

The detergent compositions of the present invention may optionally contain a heavy metal ion complexing agent as a preferred component. A heavy metal ion complexing agent is understood to mean those components which act as a heavy metal ion complexing (chelating) agent. These components may also have calcium and magnesium chelating capacities but preferably exhibit selectivity in binding to heavy metal ions such as iron, manganese and copper.

The heavy metal ion complexing agents are generally present in an amount of 0.005 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to 7.5% by weight, and most preferably 0.5 to 5% by weight.

Heavy metal ions of acidic nature, such as phosphonic or carboxylic acid functional groups, may be present as complex / salts in their acid form or with a suitable counter ion such as an alkali or alkaline metal ion, ammonium or substituted ammonium ion or mixtures thereof. Preferably, any complex / salt is water soluble. Preferably, the molar ratio of reported counterion to metal ion complexing agent is at least 1: 1.

Suitable heavy metal ion complexing agents for use in the present invention include organic phosphonates, such as aminoalkylene poly (alkylene phosphonate), alkali metal ethane-1-hydroxyphosphonate and nitrilotrimethylene phosphonate.

Among the foregoing, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate are preferred.

Other heavy metal ion complexing agents suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids, such as ethylenediaminetetraacetic acid, ethylenediamine pentaacetic acid, ethylenediamine dibasic acid, ethylenediamine diglutaric acid, 2-hydroxypropylene diamine. succinic acid or any of their salts.

Particularly preferred is ethylenediamine-N, N'-dibasic succinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. Preferred EDDS compounds are the free acid forms and their sodium or magnesium salts or complexes. Examples of such preferred sodium salts of EDDS are Na ₂ EDDS and Na ₃ EDDS. Preferred magnesium complexes of EDDS include MgEDDS and Mg ₂ EDDS.

Other heavy metal ion complexing agents suitable for use in the present invention include iminodiacetic acid derivatives such as those disclosed in EP-A-317 542 and EP-A-399 133.

2-hydroxyethyl diacetic acid or glyceryl iminodiacetic acid.

• · • · · · ·

Also suitable for use in the present invention are the iminodiacetic acid N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid complexing agents disclosed in EP-A-516 102. Suitable complexing agents for β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodibuccinic acid N, N'-diacetic acid disclosed in EP-A-509 382 are also suitable. .

Suitable amino-based complexing agents are disclosed in EP-A-476 257. EP-A-510 331 discloses suitable complexing agents derived from collagen, keratin or casein. EP-A-528 859 discloses suitable alkyliminodiacetic acid complexing agents. Dipicolinic acid and 2-phosphono-butane-1,2,4-tricarboxylic acid are also suitable. Glycine amide N, Ν'-dibasic acid (GADS), ethylenediamine-N, N'-diglutaric acid (EDDG) and 2-hydroxypropylene diamine-Ν, Ν'-dibasic acid (HPDDS) are also suitable.

Bleaching catalyst

The compositions optionally contain a transition metal bleach catalyst.

A suitable bleach-catalyst type is a catalyst system that contains a heavy metal cation having a specific bleach-catalytic activity, such as copper, iron or manganese, a minor metal cation having little or no bleach-catalytic activity, such as zinc or aluminum. cationic cations and a complexing agent having a stability constant defined for the catalytic and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, ethylene di · · · · amine tetra (methylene phosphonic acid) and their water-soluble salts. Such catalysts are disclosed in U.S.P. 4,430,243.

Other types of bleach catalysts are described in U.S.P. 5,246,621 and

U. Manganese-based complexes disclosed in U.S. Patent No. 5,244,594. Examples of such preferred catalysts include:

Mn ^IV 2 (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (PF ₆ ) ₂ , Mn ¹¹ ^ (uO)! (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2-C 104) 2, Mn ^IV 4 (uO) ₆ (1,4,7-triazacyclononane) ₄ - (C1O _{4) 2,}

Mn-Ert ^ (uO) _x (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (C 1 -C ₄ ) ₃ and mixtures thereof. Others are disclosed in European Patent Publication No. 549,272. Other ligands suitable for use in the present invention include 1,5,9-trimethyl-1,5,9-triaza-cyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7- triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

Suitable bleaching catalysts are described, for example, in

U. No. 4,246,612; 5,227,084.

See also USP 5,194,416 for single-core manganese (IV) complexes such as Μη (1,4,7-triazacyclononane) (OCH ₃ ) ₃ - (PF ₆ ).

Another type of bleach catalyst - as described in U.S.P. No. 5,114,606 discloses a water-soluble manganese (II), (III) and / or (IV) complex with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulcite, mannitol, xylitol, arabic, adonite, erythritol 51, mesoinositol, lactose, and mixtures thereof.

U.S.P. U.S. Patent No. 5,114,611 teaches a complex of transition metals, including a complex of Mn, Co, Fe, or Cu with a non-(macro) -cyclic ligand. The ligands disclosed are of formula (A) wherein

R ¹ , R ² , R ³ and R ⁴ each independently may be hydrogen, substituted alkyl or aryl, such that each of R ¹ -N = CR ² and R ³ -N = CR ^{4 forms} a five or six membered ring. The ring may also be further substituted.

B is a bridging group selected from the group consisting of oxygen, sulfur,> CR ⁵ R ⁶ ,> NR ⁷ and> C = O, wherein R ⁵ , R ⁶ and R ⁷ are each hydrogen, alkyl, or aryl, including substituted and unsubstituted groups.

Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyridazole and triazole rings. Said rings may be optionally substituted with alkyl, aryl, alkoxy, halogen and nitro. Particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleaching catalysts are cobalt, copper, manganese, ferric bispyridylmethane and bispyridylamine complexes. Very preferred catalysts are Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate, Co (2,2-bispyridyl). amine) ₂ O ₂ -C ₁₀ O ₄ , bis (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

Other examples include dinuclear manganese complexed with tetra-N-dentate and bi-N-dentate ligands, including ··· ···

N ₄ Mn ^IXI (u-0) 2Mn ^IV N 4) ⁺ and ^[111 bipyridyl Mn ₂ (u-0) 2Mn ^Iv bipiridil2] - (C10 _{4) 3} respectively.

Other bleach catalysts are disclosed, for example, in European Patent Nos. 408,131 (cobalt complex catalysts), 384,503 and 306,089 (metalloporphyrin catalysts), U.S. Pat. No. 4,728,455 (Manganese / Multidentate Ligand Catalyst), U.S. Pat. European Patent Nos. 4,711,748 and 224,952 (Manganese Absorbed on Aluminum Silicate Catalyst), U.S. Pat. No. 4,601,845 (Aluminum Silicate Carrier with Manganese and Zinc or Magnesium Salt), U.S. Pat. No. 4,626,373 (Manganese / Ligand Catalyst), U.S. Pat. U.S. Patent No. 4,119,557 (Ferri-Complex Catalyst); U.S. Patent No. 2,054,019 (Cobalt Chelating Catalyst); U.S. Patent No. 866,191 (Transition Metal Salts), U.S. Pat. No. 4,430,243 (Chelating agents with manganese and non-catalytic metal cations) and U.S. Pat. No. 4,728,455 (Manganese Gluconate Catalysts).

The bleach catalyst is used in the compositions of the invention in a catalytically effective amount. "Catalytically effective amount" means an amount sufficient to improve bleaching and removal of the affected spot or spots from the target substrate, whatever comparative experimental conditions are used. The test conditions will vary depending on the type of washing application used and the user's habits. Some users choose to use very hot water; others use warm and even cold ··· ··· water during washing operations. Of course, the catalytic performance of the bleaching catalyst will be affected by such considerations and the amounts of bleaching catalyst used in the final detergent and bleaching compositions may be appropriately adjusted. The compositions and methods of the invention may be practically and not limited to providing an amount of active bleach catalyst species in the aqueous wash solution of at least about one part per 10 million, and preferably providing about 1 to about 200 ppm catalyst in the wash water. To further illustrate this point, a 3 micromolar amount of manganese catalyst is effective at 40 ° C, pH 10, under European conditions using perborate and a bleach precursor (e.g. benzoyl caprolactam). U.S. under similar conditions, a 3-5 fold increase in concentration may be required.

Enzyme

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

Preferred added enzymatic agents are commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases commonly used in detergent compositions. Suitable enzymes are disclosed in U.S. Patent Nos. 3,519,570 and 3,533,139.

Commercially available protease enzymes sold by Novo Industries A / S (Denmark) under the trade names Alcalase, Savinase, Primate, Durazym and Esperase, sold by Gist-Brocades under the trade names Maxatase, Maxacal and Maxapem, sold by Genencor International and Solvay Enzymes Enzymes marketed under the trade names Opticlean and Optimase. Protease enzymes may be included in the compositions of the invention in an amount of 0.0001-4% by weight of active enzyme.

Preferred amylases are, for example, α-amylases obtained from a specific strain of B. licheniformis, described in more detail in GB-1 269 839 (Novo). Preferred commercially available amylases are, for example, enzymes sold by Gist-Brocades under the tradename Rapidase and sold by Novo Industries A / S under the tradenames Termamyl and BAN. Amylase enzymes may be present in the compositions of the invention in an amount of 0.0001 to 2% by weight of active enzyme.

The lipolytic enzyme (lipase) may be present in the composition in an amount of 0.0001 to 2% by weight, preferably 0.001 to 1% by weight, most preferably 0.001 to 0.5% by weight.

The lipase may be of fungal or bacterial origin, such as Humicola sp., Thermomyces sp. or Pseudomonas sp. - including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescenes - from a lipase producing strain. Lipases from chemically or genetically modified mutants of these strains can also be used in the present invention.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is disclosed in EP-B-0218272.

Another preferred lipase of the invention is obtained from Humicola lanuginosa by gene cloning and expression of the gene in Aspergillus orysae as host.

EP-A-0258 068, which is commercially available from Novo Industri A / S under the tradename Lipolase in Bagsvaerd, Denmark. This lipase is described in U.S.P. No. 4,810,414 to Huge-Jensen et al.

Organic polymer compounds

Preferred additional components of the detergent compositions of the present invention are present as components of the organic polymer compounds and preferably any particulate components, where they may, for example, act to bind the particulate component. As used herein, the term "organic polymeric compound" refers to any high molecular weight organic polymer compound commonly used in detergent compositions as dispersants and anti-redeposition and suspending agents, as disclosed herein as clay flocculating agents.

The detergent compositions of the present invention will typically contain from about 0.1% to about 30%, preferably from about 0.5% to about 15%, most preferably from about 1% to about 10%, by weight of the organic polymer compound.

Organic polymeric compounds include, for example, water-soluble, organic homo- or copolymeric polycarboxylic acids, or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by up to two carbon atoms. The latter type of polymer is disclosed in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 2000-5000 and their copolymers with maleic anhydride, the salts of maleic anhydride; · · · ···· · · * ···

Such copolymers have a molecular weight of 20,000 to 100,000, especially of 40,000 to 80,000.

Other suitable organic polymer compounds are acrylamide and acrylate polymers having a molecular weight of 3000-100000 and acrylate / fumarate copolymers having a molecular weight of 2000-80000.

Suitable polyamino compounds for use in the present invention include those derived from aspartic acid, e.g., EP-A-305282,

EP-A-305283 and EP-A-351629.

Also suitable for use in the present invention are terpolymers selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, in particular containing monomer units having an average molecular weight of 5,000 to 10,000.

Other organic polymer compounds suitable for use in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.

Further suitable polymeric compounds are polyethylene glycols, in particular 1000 to 10,000, more typically 2000 to 8000 and most preferably about 4000.

Antifoam system

The detergent compositions of the present invention, when formulated for use in machine wash formulations, preferably contain from 0.01% to 15% by weight, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of an antifoam system.

Suitable antifoam systems suitable for use in the present invention are essentially any known antifoam compound57 · * -. · * · * »· J · - · · · ·> * .. ···· ··············································································· 2-alkylalkanol antifoam compounds.

As used herein, an antifoam compound is understood to be any compound or mixture of compounds which, for example, suppresses the foam or foam produced by a solution of a detergent composition, particularly when mixed with this solution.

Particularly preferred antifoam compounds for use in the present invention are any silicone antifoam compound as defined herein as an antifoam compound containing a silicone component. Such silicone antifoam compounds typically also contain a silica gel component. As used herein and generally in the industry as a whole, the term "silicone" encompasses a series of relatively high molecular weight polymers containing siloxane units and various types of hydrocarbon groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl end-blocking units.

Other suitable antifoam compounds are monocarboxylic fatty acids and their soluble salts. These materials are disclosed in U.S.P. No. 2,954,347 to Wayne St. John. For use as an antifoam, monocarboxylic fatty acids and their soluble salts are typically hydrocarbon chains having from 10 to 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium or lithium salts, and ammonium and alkanol ammonium salts.

Other suitable antifoam compounds include high molecular weight fat esters (e.g., fatty acid triglycerides), mice, and the like. Fatty acid esters of alcohols of 58 alcohols, aliphatic C 18 -C 40 ketones (e.g. stearone), N-alkylated aminotriazines, for example, two or three moles of C 1 -C 24 primers or products of secondary amine, propylene oxide, bis-stearic acid amide and monostearyl dialkali metal (e.g., sodium, potassium, lithium) phosphates: trihexalalkylamines or di-tetraalkyl diamine chlorotriazines and phosphate esters.

Ethylene oxide and propylene oxide copolymers, in particular C 10 -C 16, ethoxylated / propoxylated fatty alcohols having 3-30 ethoxylation and 1-10 propoxylation degrees, are also suitable for use in the present invention as an antifoam agent.

Suitable 2-alkylalkanol antifoam compounds for use in the present invention are disclosed in DE 40 21 265. Suitable 2-alkylalkanols for use in the present invention consist of a C 6 -C 16 alkyl chain bearing hydroxy end groups, and the alkyl chain disclosed is substituted in one place with a C 1 -C 10 alkyl chain. Mixtures of 2-alkyl alkanols can be used in the compositions of the invention.

A preferred antifoam system is (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising (i) 50-99% by weight of the silicone antifoam compound, preferably 75-95% by weight of polydimethylsiloxane ; and (ii) the weight of the silicone / silica gel antifoam compound

Containing from 1% to 50%, preferably from 5% to 25%, of silica gel in combination, wherein said silicone / silica gel antifoam compound is present in an amount of 5-50% by weight, preferably 10-40% by weight;

(b) a dispersing compound, most preferably a silicone / glycol rake copolymer having a polyoxyalkylene content of from 72 to 78% and an ethylene oxide / propylene oxide ratio of from 1: 0.9 to 1: 1.1; a particularly preferred silicone / glycol rake copolymer of this type, commercially available from DOW CORNING under the tradename DCO544;

(c) an inert carrier-liquid compound, most preferably an ethoxylated alcohol having from 16 to 50 carbon atoms having from 5 to 50 degrees of ethoxylation, preferably from 8 to 15 degrees by weight of ethoxylation, preferably from 10 to 70% by weight.

A preferred particulate antifoam system for use in the present invention comprises a mixture of alkylated siloxane of the type described above and solid silica gel.

The solid silica gel, silica gel produced by gel forming technique, may be fumed silica or silica gel. Suitable silica gel particles have an average particle size of 0.1 to 50 µm, preferably 1 to 20 µm, and have a surface area of at least 50 m ² / g. These silica gel particles are made more hydrophobic by treatment with dialkylsilyl groups and / or trialkylsilyl groups bonded directly to the silica gel or bonded with a silicone resin. It is preferable to use a silica gel whose particles are made more hydrophobic with dimethyl and / or trimethylsilyl groups. The preferred granular antifoam compound for use in the detergent compositions of the present invention suitably contains, for example, silica gel to silica gel in a weight ratio of from 1: 100 to 3:10, preferably 1:50 to 1: 7 ·····.

Another suitable particulate antifoam system is a hydrophobic silanized (most preferably trimethylsilane) silicone having a particle size in the range of 10-20 nm and a specific surface area above 50 m / g, a molecular weight range of about 500: 200000, about 1: 1 to about 1: 2 / Silanized silica gel directly mixed with dimethyl silicone liquid in weight ratio.

A very preferred granular antifoam system is disclosed in EP-A-0210731, which comprises a silicone antifoam compound and an organic carrier having a melting point in the range of 50-85 ° C, wherein the organic carrier is a glycerol monoester and a C12-20 carbon atom. contains fatty acids. EP-A-0210721 discloses other preferred granular antifoam systems in which the organic carrier is a C12-C20 fatty acid or alcohol or a mixture thereof with a melting point of 45-80 ° C.

Other highly preferred granular antifoam systems are disclosed in pending patent application 91870007.1 (Procter & Gamble Co.), which comprises a silicone antifoam compound, a carrier, an organic coating material and glycerol, glycerol 1: 2 to 3: 1: antifoam compound in a weight ratio. Patent Application 91201342.0, which is also pending, discloses very advantageous granular antifoam systems which are silicone antifoam chemicals.

a carrier, an organic coating material and a crystalline or amorphous aluminosilicate; and a 1: 3 to 3: 1 aluminum silicate: silicone antifoam compound in a weight ratio. In both of the above-mentioned very advantageous granular antifoaming agents, starch is the preferred carrier.

The particulate antifoam system for use in the present invention is, for example, a granular agglomerated component made by an agglomeration process which comprises (i) a silicone antifoam compound comprising 5 to 30% by weight, preferably 8 to 15% by weight, preferably mixed with polydimethylsiloxane and silica gel. component;

(ii) 50-90% by weight, preferably 60-80% by weight of carrier, preferably starch;

(iii) 5-30 wt.%, preferably 10-20 wt.%, of an agglomerated binder, wherein such a compound of the invention may be any compound or mixture thereof typically used as a binder for agglomerates, most preferably the disclosed agglomerated binder is a C 16-18, It contains ethoxylated alcohol having a degree of ethoxylation of from 50 to 100; and (iv) 2 to 15% by weight, preferably 3 to 10% by weight, of C12 to C22 hydrogenated fatty acids combined.

Clay flocculant

The compositions of the present invention may contain a clay flocculating agent which is preferably present in an amount of 0.005 to 10%, more preferably 0.05 to 5%, most preferably 0.1 to 2% by weight of the composition.

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

The clay flocculant works by bringing together any clay compound particles in the washing solution and thereby facilitating their deposition on the surface of the laundry being washed. This functional need thus differs from the clay dispersants which are commonly added to laundry detergent compositions to remove clay contamination from the surface of the fabric and disperse in the washing solution.

Organic polymeric materials having an average molecular weight of from 100,000 to 10,000,000, more preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000 are preferred as clay flocculating agents in the present invention.

Suitable organic polymeric materials are homopolymers or copolymers containing alkylene oxide, in particular ethylene oxide, acrylamide, vinyl alcohol, vinyl pyrrolidone and ethyleneimine monomer units.

EP-A-299 575 and EP-A-313 146 (Procter & Gamble) disclose organic polymeric clay flocculating agents which are preferred for use in the present invention.

Inorganic clay flocculating agents are also preferred in the present invention, such as lime and alum.

Polymeric dye transfer inhibitors

The detergent compositions of the present invention may also contain from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of the polymeric dye transfer inhibitor.

The polymeric dye transfer inhibitors are preferably polyamine

N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers and combinations thereof.

a) Polyamine-N-oxide polymers

Suitable polyamine N-oxide polymers for use in the present invention have the general structural formula (XIII)

P is a polymerizable unit and is OOO

II

A is -NC-, -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, to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is a moiety.

The N-0 group can be represented by the following general formula (o) or (p)

R _x , R ₂ and R ₃ are aliphatic groups, aromatic, heterocyclic or alicyclic groups, or combinations thereof, x or / and y or / and z are 0 or 1 to which the nitrogen of the N-0 group can be attached or in which N- The nitrogen of group 0 is part of these groups. The N-O group may be part of the polymerizable unit (P) or may be attached to the polymer backbone or a combination of the two.

• ·

Suitable polyamine N-oxides wherein the N-O moiety forms part of the polymerizable moiety include polyamine NOxides wherein R is selected from the group consisting of aliphatic, aromatic, alicyclic and heterocyclic groups. A class of polyamine N-oxides disclosed contains a polyamine N-oxide group in which the nitrogen of the N-O group is part of the R group. Preferred polyamine N-oxides wherein R is a heterocyclic group such as pyridine, pyridine, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of polyamine N-oxides disclosed contains a polyamine N-oxide group in which the nitrogen of the N-O group is attached to the R group.

Other suitable polyamine N-oxides are those polyamine oxides wherein the N-O group is attached to the polymerizable moiety.

A preferred group of these polyamine N-oxides is the polyamine N-oxide of formula (I) wherein R is an aromatic, heterocyclic or alicyclic group in which

The nitrogen of the N-O functional group is part of the disclosed R group. Examples of such groups are polyamine oxides in which R is a heterocyclic compound such as pyridine, pyridine, imidazole and derivatives thereof.

Another preferred group of polyamine N-oxides is the polyamine N-oxide of formula (I) wherein R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O functional group is attached to said R groups. These groups include, for example, polyamine N-oxides having

In groups, the R groups may be aromatic, such as phenyl.

Any polymer backbone may be used as long as the resulting amine oxide polymer is water soluble and has dye transfer inhibiting properties. Suitable polymer backbones include, for example, polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates, and mixtures thereof.

Typically, the amine N-oxide polymers of the invention have an amine / amine oxide ratio of from 10: 1 to 1: 1 million. However, the amount of amine oxide groups present in the polyamine oxide polymer may be varied by suitable copolymerization or by appropriate degree of N-oxidation. The amine / amine to N-oxide ratio is preferably from 2: 3 to 1: 1 million. More preferably between 1: 4 and 1: 1000000, most preferably between 1: 7 and 1: 1000000. The polymers of the present invention actually include random or block copolymers wherein one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or another. The amine oxide unit of the polyamine N-oxides has a PKa <10, preferably PKa <7, more preferably PKa <6.

Poly (amine oxides) can be obtained at almost every stage of polymerization. The degree of polymerization is not critical, provided that the material has the desired water solubility and paint suspension strength. The average molecular weight is typically in the range of 500-1000000, preferably 1000-50000, more preferably 2000-30000, most preferably 3000-20000.

b) N-vinylimidazole / N-vinyl pyrrolidone copolymers

Preferred polymers for use in the present invention are N66

polymers selected from the group consisting of -Vinylimidazole / N-vinylpyrrolidone copolymers, wherein said polymer has an average molecular weight range of 5000-50000, more preferably 8000-30000, most preferably 10000-20000. Preferred N-vinylimidazole / N-vinylpyrrolidone copolymers are 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4 N-vinylimidazole / N-vinyl pyrrolidone has a molar ratio.

(c) Poly (vinylpyrrolidone)

The detergent compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of 2500-400000, preferably 5000-200000, more preferably 5000-50000 and most preferably 5000-15000. Suitable polyvinylpyrrolidone is commercially available for PVP K-15 (10,000 viscosity molecular weight), PVP K-30 (40,000 average molecular weight), PVP K-60 (16,000,000 average molecular weight), and PVP K-90 (360000 average molecular weight) product names may be obtained from ISP Corporation, New York, NY and Montreal, Canada. PVP K-15 is also available from ISP Corporation. Other commercially available polyvinylpyrrolidones are commercially available from BASF.

Sokalan HP 165 and Sokalan HP 12.

The polyvinylpyrrolidone may be present in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight, and more preferably 0.1 to 2% by weight. The amount of polyvinylpyrrolidone incorporated into the wash solution is preferably 0.5 to 250 ppm, preferably 2.5 to 150 ppm, more preferably 5 to 100 ppm.

d) Poly (vinyl oxazolidone)

Polyvinyl-oxazolidone-octate may also be used as polymeric sponge inhibitors in the detergent compositions of the present invention. Said polyvinyl oxazolidones have an average molecular weight of 2500-400000, preferably 5000-200000, more preferably 5000-50000 and most preferably 5000-15000.

The amount of polyvinyl oxazolidone used in the detergent compositions may be 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 of polyvinyl oxazolidone incorporated into the wash solution is preferably 0.5 to 250 ppm, preferably 2.5 to 150 ppm, more preferably 5 to 100 ppm.

(e) Poly (vinylimidazole)

The detergent compositions of the present invention may also use polyvinylimidazole as a polymeric dye transfer inhibitor. The polyvinylimidazoles disclosed are preferably in the range of 2500-400000, more preferably 5000-50000 and most preferably 5000-15000.

The amount of polyvinylimidazole incorporated in the detergent compositions may be 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 of polyvinylimidazole transferred to the wash solution is preferably 0.5 to 250 ppm, preferably 2.5 to 150 ppm, more preferably 5 to 100 ppm.

Optical brighteners

The detergent compositions of the present invention may optionally contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibiting effect. When used, the compositions of the invention preferably contain from about 0.01% to about 1% by weight of such optical brighteners.

·· · ···· ·· * ·· · • «·. · · · ·

The hydrophilic optical color enhancers useful in the present invention have the general structural formula (XIV)

R _r is selected from anilino, Ν-2-bis (hydroxyethyl) - and NH-2- (hydroxyethyl) alkyl;

_R2 is Ν-2-bis (hydroxyethyl) - N-2- (hydroxyethyl) -N- (methylamino) -, morpholino, chloro and amino; and

M is a salt-forming cation such as sodium or potassium.

When R _{x in} the above formula is anilino, R ₂ is N-2-bis (hydroxyethyl) and M is, for example, sodium, then the coloring agent is 4,4'-bis {[4-anilino-6- (Ν -2-bis-hydroxyethyl) -s-triazin-2-yl] amino) -2,2'-stilbene disulfonic acid and

disodium salt. This particular coloring agent is marketed under the brand name Tibaopal-ÜNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener for use in detergent compositions of the present invention.

When R _{x in} the above formula is anilino, R ₂ is N-2- (hydroxyethyl) -N-2- (methylamino) and M is a cation such as sodium then the color enhancer is 4,4 '. -bis {[4-anilino-6- (N-2- (hydroxyethyl) -N- (methylamino) -s-triazin-2-yl] amino) -2,2'-stilbene disulfonic acid and disodium salt. This particular coloring agent is marketed under the trademark Ciba-Geigy Corporation Tinopal 5BM-GX.

When R _{1 in} the above formula is anilino, R ₂ is morpholino and M is a cation such as sodium, then the color enhancer is 4,4'-bis {[4-anilino-6- (morpholino-s-triazine) -2- il] amino) -2,2'-stilbene disulfonic acid and its disodium salt.

····

This particular color enhancer is marketed under the brand name Tibaopal AMS-GX by Ciba-Geigy Corporation.

Cationic fabric softeners

The laundry detergent compositions of the present invention may also contain cationic fabric softeners. They may be present as individual components or as components of the hydrophobically activated clay materials described above. Suitable cationic fabric softeners include water-insoluble tertiary amines or di (long chain amide) materials as disclosed in GB-A-1 514 276 and

EP-B-0 011 340.

Cationic fabric softeners are typically added in amounts of from 0.5 to 15% by weight, typically from 1 to 5% by weight.

Other Optional Ingredients Other suitable ingredients that may be included in the compositions of the invention include perfumes, coloring agents and fillers, with sodium sulfate being the preferred filler salt.

preparations Form

The solid compositions of the present invention include various physical forms including. granular and tablet forms may be included. Particulate compositions are particularly so-called concentrated detergent formulations, typically of high bulk density, used for dispensing contaminated film masses into a dispenser drum. The addition of concentrated particulate detergent compositions to the washing solution through a dispenser causes more dissolution problems than when the compositions are introduced through a dispenser portion of the washing machine because of the presence of the fabric mass in the initial stages of the washing cycle. ·· • ►

ΊΟ prevents mixing in the immediate vicinity of the product. While this has the advantage of allowing the formation of high transient builder concentrations, the formation of high transient organic peroxyacid concentrations, as noted above, "results in spotty fabric color damage.

The granular compositions of the present invention preferably have a particle size such that more than 5% of the particles have a diameter greater than 1.7 mm, and the amount of particles less than 0.15 mm in diameter does not exceed 5%.

As used herein, the term average particle size is defined as calculated by sieving a sample of a formulation through a series of Tyler sieves into multiple fractions (typically 5 fractions). The mass fractions thus obtained are plotted against the mesh size of the sieves. The average particle size is the slit size where 50% of the sample mass passes through.

The bulk detergent compositions of the present invention typically have a bulk density of at least 600 g / l, more preferably 650-1200 g / l, most preferably 800-1000 g / l. The bulk density is measured using a simple funnel and cup device consisting of a conical funnel rigidly mounted on a base and fitted with a butterfly valve at the bottom, allowing the contents of the funnel to be emptied into an axially aligned cylindrical cup. The funnel is 130 mm high and has an inner diameter of 130 mm and 40 mm at its upper and lower ends. Mount it so that its lower end is 140 mm above the upper surface of the base. The total height of the cup is 90 mm and its inner height is 87 mm 'and its inside diameter 84 mm. The nominal volume is 500 ml.

To perform the measurement, the funnel is poured by hand, filled with powder, the butterfly valve is opened and the powder is allowed to overflow the cup. The filled cup is removed from the frame and excess dust is removed by pulling a straight-edged device, such as a knife, over the top edge of the cup. The filled cup is then weighed and the weight of the powder is doubled to calculate the bulk density in g / l. If necessary, parallel measurements can be made.

Clay / organic peroxyacid precursor particles

The organic peroxyacid bleach precursor or preformed organic peroxyacid and clay mineral compound are preferably present as particulate components, which preferably contain additional components to promote particle cohesion and optimize their storage stability and flow properties. Particularly preferred further components for providing a good particle structure are binders which may contain, for example, any of the organic polymeric compounds disclosed herein.

The particulate components may be in any suitable form, such as granules, flakes, tablets, small particles or noodles, but preferably granules. The particles themselves may be agglomerates formed by cauldron or drum agglomeration, in-line mixes or by spray-dried particles, which are produced by spraying the aqueous sludge of the ingredients into a stream of hot air, which removes most of the water.

· • '9 W * ·

.. · ♦, J »

V · «· · - ♦ * ·· ······· · ·« «9 · '' ·· *

Packaging of preparations

Commercially available embodiments of bleaching compositions may be packaged in any suitable container, including those made of paper, cardboard, plastics, and any suitable laminates. A preferred packaging embodiment is disclosed in European Patent Application Serial No. 93970141.4.

Abbreviations used in the examples

Component abbreviations used in detergent compositions have the following meanings:

XYAS

25EY

XYEZ

XYEZS

TFAA

silicate

NaSKS-6

Sodium salt of C 1 -C 10 alkyl sulfate

C12-C15 alkylene, condensed with an average of Y moles of ethylene oxide, predominantly linear, primary alcohol having 1x-lye, condensed with an average of Z moles of ethylene oxide, and predominantly linear, with an average of Z moles of ethylene oxide condensed with moles of ethylene oxide. sulphate sodium salt

C 16 -C 18 alkyl-N-methylglucamide amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 2.0)--Na ₂ Si ₂ O ₅ crystalline layered silicate

Carbonate Anhydrous sodium carbonate

MA / AA

1: 4 maleic acid / acrylic acid copolymer having an average molecular weight of 70,000

Zeolite A

Citrate

percarbonate

TAED particle

protease

amylase

cellulase

Lipase: Na ₁₂ (A10 ₂ ) i2-water (1/27), hydrated sodium aluminosilicate, primary particle size in the range 1 to 10 µm: trisodium citrate-water (1/2): coated with a sodium silicate (SiO ₂ : Na ₂ O ratio = 2: 1) anhydrous sodium percarbonate bleach, weight ratio of percarbonate to sodium silicate

39: 1: tetraacetyl ethylene diamine particle; The TAED is formed by agglomerating a 1: 4 citric acid / acrylic acid copolymer having a molecular weight of about 70,000 to a weight ratio of 85:10 TAED: copolymer and then coating said agglomerate at a weight ratio of 95: 5 agglomerate: coating.

: a proteolytic enzyme with 13 KNPU / g activity, sold by Novo Industries A / S under the trade name Savinase.

: an amylolytic enzyme of 300 KNU / g, marketed by Novo Industries A / S under the trademark Termamyl 60T.

is a cellulose-degrading enzyme marketed by Novo Industries A / S with an activity of 1000 CEVU / g.

is a lipolytic enzyme of 165 KLU / g, marketed by Novo Industries A / S under the brand name Lipolase.

· · · · · · · · · · · · · · · · · · · · · ·

CMC: Sodium salt of (carboxymethyl) cellulose.

HEDP: 1,1-hydroxyethane diphosphonic acid

EDDS: ethylenediamine-N, Ν'-dibasic acid, [S, S] isomer, in the form of the sodium salt.

DETPMP: diethylene triamine penta (methylene phosphonic acid),

PVNO: Poly (4-vinylpyridine) -N-oxide copolymer of vinylimidazole and vinylpyrrolidone having an average molecular weight of 10,000.

Clay: calcium montmorillonite

Granular antifoam: 12% silicone / silica gel, 18% stearyl alcohol, 70% starch in granular form

Example 1:

TAED / 1st clay particles

The following agglomerate was prepared in an Eirich Mixer RV02 (trade name).

Crowd%

TAED 85

Clay ** 5

MA / AA * 10

100 * Acquired from BASF as Sokolan 45 (trade name) ** Acquired from Colin Stewart Minchem Ltd as Bentonite (trade name)

TAED and clay are placed in an Eirich mixer and premixed. The powder temperature is 25 ° C. An aqueous solution of MA / AA binder at 60 ° C is added to the powder mixture for 30 seconds by rotating the Eirich paddles and the vessel. The resulting mass is further stirred for 30 seconds. Stirring is then stopped and the agglomerated product is removed from the Eirich mixer and further dried in a fluidized bed dryer to a moisture content of 2%. The product is then sieved and material greater than 1180 µm and less than 250 µm is removed.

TAED / second clay particles

The same procedure as above was repeated except that the clay was replaced by the same amount of acidic clay (Tonsil P (tradename) available from Sud Chemie AG).

TAED / 3rd clay particles

The following agglomerate was prepared in an Eirich Mixer RV02 (trade name).

Crowd%

TAED 80

Clay ** 5

MA / AA * 10

Acquired from BASF as Sokolan 45 (trade name) ★ ★

Acquired from Colin Stewart Minchem Ltd as Bentonite (trade name)

TAED and clay are placed in an Eirich mixer and premixed. The powder temperature is 25 ° C. The molten binder at 60 ° C is added to the powder mixture by rotating the Eirich paddles and the vessel for 30 seconds. The resulting mass was stirred for 30 seconds. Stirring is then stopped and the agglomerated product is removed from the Eirich mixer and further dried in a fluid bed dryer. The product is then sieved and material greater than 1180 µm and less than 250 µm is removed. The resulting agglomerate is then coated with MA / AA in 5:95 coating: agglomerate.

The following granular laundry detergent compositions, A, B, C, D and E, having a bulk density of 750 g / liter, are prepared, wherein said numbers are by weight, comparative compositions A and B, and CE are the compositions used in the laundry laundry process of the invention. with granulate feeder:

THE B C D E 45AS / 25AS (3: 1) 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 2.0 2.0 2.0 2.0 Zeolite A 10.2 10.2 10.2 10.2 10.2 Well SKS-6 / Citric Acid (79:21) 10.6 10, 6 10.6 10.6 10, 6 carbonate 7, 6 7.6 7.6 7.6 7.6 TAED particle 5 6, 67 - - - TAED / Clay Slitting Grass (1) - - 6, 67 - - TAED / Clay Slotted Zinc Ke (2) - - - 6, 67 - TAED / Clay Slitting Grass (3) - - - - 6, 67 percarbonate 22.5 22.5 22.5 22.5 22, 5 DETPMP 0.8 0.8 0.8 0.8 0.8 protease 0.55 0.55 0.55 0.55 0.55 lipase 0, 15 0.15 0, 15 0.15 0.15 cellulase 0.28 0.28 0.28 0.28 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 0.4 PVNO 0.03 0, 03 0.03 0.03 0.03 Granular antifoam 1.5 1.5 1.5 1.5 1.5 Kisefcb / other parts supplemented to 100%

• · • · · ·

Comparative Performance Test

Test procedure 1 - Spot discoloration test

The AE formulations were subjected to a standard size washing machine test using a 12 Miele automatic washer (type WM W698) set at 40 ° C for a short wash cycle for each sample. 12 ° Clark hard water (= 1.8 mmol Ca ²⁺ / liter) was used. The pieces of linen, numbered 1-24 and obtained from High Street stores, are placed in pairs in the washing machine in the following order:

sample code Type of clothes Color Type of fabric 1 & 4 Wool cardigan navy blue 50/50% wool / acrylic 2 & 3 Men's shirt Dark green 100% cotton 5 & 8 T-shirts Black 100% cotton 6 & 7 Men's tracksuit Black 10/90% cotton / polyester 9 & 12 T-shirts Black 100% cotton 10 & 11 Canvas shirt navy blue 100% cotton 13 & 16 Long sleeve warmer Black 50/50% cotton / polyester 14 & 15 Jeans Black 100% cotton 17 & 20 Men's trousers Black 65/35% Polyester / Viscose 18 & 19 Men's cord shirt Green 100% cotton 21 & 24 Men's shirt Dark green 100% cotton 22 & 23 Leggings Black 97/3% pamut / Lycra

Each washing machine is filled with about 1.9 kg of clean sheeting ballast, with a fabric sample on top of 100 g of the type of Ariel Ultra (EP-A-343 070) and commercially available from Procter & Gamble. brand name) granular dispenser for use with granular laundry detergent and a second tissue sample on top. The 30 cm x 30 cm pieces of fabric are folded so as to enclose the detergent composition granule during the first stages of dissolution / dispersion of the detergent composition. The tissue pieces were removed at the end of the cycle and dried in the open air.

The pieces of tissue are then visually graded for fabric discoloration using a grading system that uses three colored pieces of tissue with varying degrees of discoloration as the standard to create a 6-point scale, where 0 means "no discoloration and 5 means" t. The three standards are used to define midpoints between different color fades, ie no discoloration very slight discoloration slight discoloration clearly perceptible discoloration very discolored extremely discolored

Two expert sensory reviewers were employed and their results averaged.

Benchmarking - Spotty discoloration

Compared with the previous test run 1, the discoloration obtained with A-E formulations and the following results are obtained.

A certified piece of fabric ς% preparation 0 1 2 3 4 5 Complete qualification THE 67 17 8 8 0 '0 0, 57 B 58 13 13 12 4 0 0, 91 C 84 0 8 8 0 0 0.40 D 80 4 4 12 0 0 0, 48 E 75 4 8 13 0 0 0.59

It can be seen that the C-E formulations of the present invention are estimated to produce less fabric discoloration than the A and B formulations.

Test Procedure 2 - Stain Removal

Three white cotton pads are prewashed in a non-biological bleach high performance detergent. Then we place tea stains on one sheet, wine stains on the second sheet and coffee stains on the third sheet. Six test pieces of 6 cm x 6 cm test pieces were cut from each sheet.

The batches of tissue are subjected to a washing cycle in an automatic washing machine. The tissue pieces are then evaluated for tea, wine and coffee stain removal using a well-established whiteness measurement procedure.

More specifically, we use a Miele 756 WM automatic washing machine and choose the 40 ° C short cycle program. 12 ° C hard water (= 1.8 mmol Ca / liter) was used. 100 g of detergent added from the granulate dispenser are used. One piece of fabric from each type of fabric is washed with about 1.9 kg of lightly soiled sheets of ballast.

Stain removal is estimated by foot (whiteness) measurements using an X-rite (brand name) color spectrophotometer. a non-stained cotton piece is used as a comparator. The stain removal index, AR, is calculated as follows:

AR = (L Washed ^ Unwashed) / (- ^ Unwashed ^ Comparative) 100

Comparative test - stain removal

Comparison of the efficacy of formulations B and C in the removal of different patch types follows the previous Test Procedure 2. The results obtained are as follows:

PRICE B C Tea 78 76 Skin 82 83 Coffee 75 74

The stain removal obtained for each of formulations B and C is similar.

Example 2:

The granular formulations A-E of Example 1 were compacted to form tablets 2 cm x 2 cm x 2 cm.

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Claims (17)

CLAIMS 1. A method of washing a laundry in a household or industrial washing machine, comprising providing a means for dispensing an effective amount of a solid detergent composition containing a peroxyacid bleach composition directly into a washing machine drum prior to commencement of washing, said dispenser allowing dissolution of said detergent composition. during washing, and said peroxyacid bleaching composition comprises (a) a bleaching system capable of providing an organic peroxyacid bleach in a laundry washing solution, characterized in that said bleaching system is (i) a source of hydrogen peroxide combined with an organic peroxyacid bleach precursor compound; (ii) a preformed organic peroxyacid; and any mixtures thereof; and (b) a non-three-dimensional phyllosilicate mineral compound, wherein said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three-dimensional phyllosilicate mineral compound are in close physical proximity to said composition. The process of claim 1, wherein said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three-dimensional phyllosilicate mineral compound is directly admixed within said composition. A method according to any one of claims 1 and 2, wherein: • 4 · · * · · · · · · · · · · · · · Characterized in that the weight ratio of the non-three-dimensional phyllosilicate mineral compound to said organic peroxyacid bleach precursor compound or to said preformed organic peroxyacid is from 1: 6 to 1:99. A process according to any one of claims 1 to 3, wherein the peroxyacid bleaching composition is in particulate form and said organic peroxyacid bleaching precursor compound or said preformed organic peroxyacid and said non-three-dimensional phyllosilicate mineral compound in the same particulate component. are present. The process of claim 4, wherein said detergent composition is in particulate form and has a bulk density of at least 600 g / l. A method according to any one of claims 1 to 5, characterized in that said dispenser is provided by filling a dispenser with said solid detergent composition and placing said dispenser in a washing machine drum prior to the commencement of washing. Method according to any one of claims 1 to 3, characterized in that said dispensing means is provided by tabletting said solid detergent composition and placing said tablet in the drum of a washing machine prior to the commencement of washing. A process according to any one of claims 1 to 7, wherein said non-three-dimensional phyllosilicate mineral compound is a clay mineral compound. 9. The process of claim 8, wherein the clay mineral compound is a smectite clay compound. Process according to any one of claims 1 to 7, characterized in that said non-three-dimensional phyllosilicate mineral compound is a crystalline layered silicate mineral compound. The process of claim 10, wherein said crystalline layered silicate mineral compound NaMSi _x O _{2x + 1. 1} H ₂ O - in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Process according to any one of claims 1 to 7, characterized in that the hydrogen peroxide source is an inorganic perhydrate salt. The process according to claim 12, wherein said inorganic perhydrate salt is an alkali metal percarbonate salt. A process according to any one of claims 1 to 13, wherein the organic peroxyacid bleach precursor compound is present in an amount greater than 3% by weight of the detergent composition. Process according to any one of claims 1 to 14, characterized in that said organic peroxyacid bleach precursor compound gives peracetic acid upon perhydrolysis. 16. The process of claim 15, wherein said organic peroxyacid bleach precursor compound is tetraacetyl ethylenediamine. 17. A process according to any one of claims 1 to 4, wherein said organic peroxyacid bleaching precursor compound, upon perhydrolysis, provides an organic peroxyacid which is (i) a perbenzoic acid or a non-cationically substituted derivative thereof; or (ii) a cationic peroxyacid. The agent shall: • · · ···· »* ·· * · DISCLOSURE EXAMPLE • · · · ··· ··· • ♦ ··· ·. · · 63,839 7BE 1/5 R ² R ³ 1 I I, R - N = C - B —C = N —R * ··· ·· »···· W397 & Í 2/5 ο II C - CH, - CH, I n ^X 'CH ₂ - [CH ₂ l _n N - R ² - C - L l ₅ 1