CZ2002688A3 - Formulation components resistant to decomposition by aromatization, compositions, and laundry methods employing these components - Google Patents

Abstract

Bleach boosting compounds selected from the group consisting of bleach boosters comprising quaternary imine cations, zwitterions, polyions having a net charge of from about +3 to about -3 and mixtures thereof, bleaching species comprising oxaziridinium cations, zwitterions, polyions having a net charge of from about +3 to about -3 and mixtures thereof, and mixtures thereof are disclosed. The bleach boosting compounds increase bleaching effectiveness even in lower temperature solutions and provide improved stability toward unwanted bleach boosting compound decomposition. The bleach boosting comprounds are ideally suited for inclusion into bleaching compositions including those with detersive surfactants and enzymes. Also provided is a method for laundering a fabric employing the bleach boosting compounds, and a laundry additive product employing the bleach boosting compounds.

Description

Ingredients of the flavor-resistant composition, compositions and methods of washing using these ingredients

Technical field

The present invention relates to formulation components such as bleach-enhancing compounds with enhanced stability and compositions and methods of washing using bleach-enhancing compounds with enhanced stability, more particularly the present invention relates to quaternary bleach-enhancing quinine compounds and / or oxaziridinium bleach particles, detergent compositions and methods, wherein quaternary imine bleach enhancers and / or oxaziridinium bleach particles are used.

BACKGROUND OF THE INVENTION

The use of oxygen bleaching agents in cleaning and personal care products, where they facilitate stain and dirt removal, has been increasingly popular in recent years. Bleaches are particularly desirable for stain removal, dirty fabric cleaning, bleaching and disinfection. Oxygen-based bleaching agents are particularly suitable for use in laundry products such as detergents, washing machine products, and hard surface cleaning products. However, oxygen-based bleaching agents are somewhat limited in their effectiveness. Some of the common drawbacks include deterioration of the color on the fabric and damage to the washing equipment, particularly the rubber hoses that may contain these equipment. In addition, oxygen-based bleaching agents have a high temperature-dependency of effectiveness. So, the colder the solution in which they are used, the less effective bleaching is. A temperature in excess of 60 ° C is typically required for good oxygen bleaching performance.

• · · · · · · · · · · · ««

To solve this temperature dependence, a group of compounds known as "bleach activators" has been developed. Bleach activators are typically perhydrolyzable acyl compounds that carry a leaving group, such as an oxybenzenesulfonate, reacting with an active oxygen group, typically hydrogen peroxide or an anion thereof, to form a more active peroxyacid oxidant. The peroxyacid compound then oxidizes the stained or contaminated substrate. However, the bleach activators are also partly temperature dependent. Bleach activators are more effective in water at 40 ° C to 60 ° C. At a water temperature below 40 ° C, the peroxyacid compounds lose some of their bleaching effect.

The experiments described in U.S. Pat. Nos. 5,360,568, 5,360,569 and 5,370,826 to Madison et al., to develop a bleach system that is effective at a lower water temperature. However, the bleach-enhancing dihydroisoquinolinium compounds described in these patents, when mixed with the peroxide compounds, undergo undesirable decomposition, including the formation of inactive aromatic isoquinolinium, causing a reduction in the potency of the effect.

In light of the above, it is desirable to develop bleach-enhancing active agents which are not subject to decomposition.

Thus, there remains a need for active bleach-enhancing compounds and compositions containing bleach-enhancing compounds that provide efficient bleaching even at low water temperatures and have increased stability for undesirable decomposition of the bleach-enhancing compound.

SUMMARY OF THE INVENTION

Summary of the Invention

This need is met by the present invention which provides longer-lasting bleach-enhancing compounds, in particular bleach-enhancing compounds and / or a bleach-forming group selected from bleach. The bleach-enhancing compounds of the present invention have excellent bleaching performance even at lower water temperatures and also do not undesirably decompose.

A bleaching composition comprising a bleach-enhancing compound, with or without a peroxide source, wherein the bleach-enhancing compound is selected from the group consisting of: (a) a bleach-enhancing compound selected from the group consisting of aryliminium cations, aryliminium zwitterions, aryliminium polyions which have a net charge of +3 to -3 and mixtures thereof; (b) bleaching particles selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyions having a net charge of +3 to -3 and mixtures thereof; and (c) mixtures thereof; is provided in a first embodiment of the present invention.

In another embodiment of the present invention, there is provided a cationic or zwitterionic compound which enhances the effect of the bleaches in the laundry.

In another aspect, the present invention provides a method of washing a fabric in need of washing comprising contacting the fabric with a laundry solution comprising a bleaching composition of the present invention.

In another aspect of the present invention there is provided a detergent additive product comprising a bleach enhancing compound selected from: (a) a potentiating compound selected from the group consisting of aryliminium cations, aryliminium zwitterions, aryliminium polyions having a net charge of +3 to -3 and mixtures thereof; (b) bleaching particles selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyions having a net charge of +3 to -3 and mixtures thereof; and (c) mixtures thereof.

It is therefore an object of the present invention to provide: a bleach enhancing compound which exhibits an improved effect even at lower wash solution temperatures and also avoids undesirable aromatization; a bleaching composition comprising a quaternary imine bleach enhancing effect of bleach and / or oxaziridinium bleach; a method of washing a fabric using a quaternary imine bleach-enhancing effect of bleach and / or oxaziridinium bleach; and a product used as a detergent additive comprising a quaternary imine bleach enhancing agent and / or

These and other objects, features and invention will be read by those skilled in the art from the following description and the appended claims.

All percentages and ratios herein are by weight unless otherwise indicated. All documents cited herein are incorporated herein by reference.

oxaziridinium bleach, advantages of the present invention

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel and highly useful bleach enhancing compounds ("bleach enhancing compounds," bleaching compounds and mixtures thereof), compositions and methods in which these novel bleach enhancing compounds are used. The bleach-enhancing compounds of the present invention provide improved bleaching performance even when used at lower temperatures while avoiding undesirable aromatic decomposition, resulting in increased efficacy. The bleach-enhancing compounds of the present invention act with or without conventional bleaching oxygen sources, thereby achieving said increased bleaching efficiency and avoiding aromatization.

• · · · ·

Definition "A peroxide source, as used in the present invention, refers to materials from which peroxide compounds are formed, and includes peroxide compounds themselves. Examples include, but are not limited to, bleach activators, peroxyacids, percarbonates, peroxyborates, hydrogen peroxide, bleach enhancers, and / or bleach particles (eg, oxaziridinium).

"Peroxide compounds as used in the present invention include peroxyacids and peroxides (eg, hydrogen peroxide, alkyl hydroperoxides, etc.).

"Peroxyacids, as used herein, refers to peroxyacids such as peroxycarboxylic acids and / or peroxymonosulphuric acids (trade name OXONE) and salts thereof.

Bleach enhancing compounds

The bleach enhancing compounds of the present invention are preferably quaternary imine bleach enhancing compounds. More preferably, the bleach enhancing compounds of the present invention are selected from the group consisting of aryliminium cations, aryliminium zwitterions, aryliminium polyions having a net charge of +3 to -3 and mixtures thereof, which are compounds of formula I and formula II:

(I) • • • •

wherein t is 0 or 1; R 1 to R 2 are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; any

R ¹ to R ⁴ are optionally combined to form aryl, fused carbocycle or heterocycles; R ⁵ is substituted or a residue selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; R ⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycles, and the radical:

two adjacent condensed condensed unsubstituted

-T ₀ - (Z _{'), and} where Z' is covalently bonded to T _o, and Z is selected from the group consisting of -C 0 _2, -S0 ₃ -0S0 ₃ ', -S0 ₂ "and -0S0 ₂ ~ aa is 1 or

2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or

- (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C 1 alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3)

H

AND

-ch ₂ -c-ch ^ (4) •

Η

AND

-ChL-C-Cl-L · ² I ²

OH (S) - (CH ₂ ) d (E) (CH ₂ ) f -, wherein d is 2 to 8, f is 1 to 3, and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl;

(7)

H

I —c—

wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ¹⁸ R ¹⁹ -, -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ - and

-CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ CR ²² R ²³ -; R ¹⁴ to R ²³ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 -C 18 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R and R are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 to C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is zero, R ⁷ or R ⁸ is not hydrogen and that, if t is one, either of R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are not hydrogen; wherein any one of R ¹ to R ¹⁰ is optionally linked to any other of R ¹ to R ¹⁰ to form part of a common chain.

Preferred bleach particles of the present invention include, but are not limited to: (1) oxaziridinium cations of formula III wherein R ²⁵ is hydrogen or methyl and R ²⁶ is selected from the group consisting of substituted or unsubstituted radicals consisting of linear or branched C 1 -C 14 alkyl, C 3 -C 4 oxaziridinium ²⁵ is hydrogen or cycloalkyl and C 5 -C ₁₄ aryl; (2) zwitterions of formula IV wherein R 1 is methyl and R ²⁶ is

-T ₀ - (Z) _a

Preferred bleach enhancers include, but are not limited to: (1) Aryliminium cations of formula I wherein R ⁵ is hydrogen or methyl and R ⁶ is selected from the group of substituted or unsubstituted radicals consisting of linear or branched C 1 -C 14 alkyl C ₃ -C 14 cycloalkyl and C ₆ -C 14 aryl; (2) aryliminium zwitterions of the formula II wherein R ⁵ is hydrogen or methyl and R ⁶ is

V (Z ') _and wherein Z' is covalently bonded to To and Z "is selected from the group consisting of -CO 2 ', -SO ₃ ', and -OSO 6 and a is 1 or 2; (3) aryliminium cations of formula I wherein R ⁶ is selected from the group consisting of linear or branched C 1 -C 14 substituted or unsubstituted alkyl, or aryliminium zwitterions of formula II wherein R ⁶ is

-T ₀ - ^(Z ') and wherein Z' is -CO2 ', -S0 ₃ "and -0S0 ₃ \ ajelaT is selected from _the group consisting of

R ⁴⁵

-C) R ⁴⁵ wherein p is an integer from 2 to 4 and R ⁴⁵ is independently selected from the group consisting of hydrogen and linear or branched C 1 -C 18 substituted or unsubstituted alkyl; and (4) aryliminium polyions having a negative net charge in which R ⁵ is hydrogen, Z 1 is -CO 2 ', -SO ₃ and -SO ₃ ', and a is 2.

More preferred bleach enhancers include, but are not limited to: (1) aryliminium cations • this to · to ·· · to * to · to ·· · t · to ·· · Formula (I) in which R ¹ to R ⁵ are hydrogen and R ^{6 is of} formula (I). is a linear or branched C 1 -C ₁₄ substituted or unsubstituted alkyl; (2) aryliminium zwitterions of formula II wherein R ¹ to R ⁵ are hydrogen and R ⁶ is

-T ₀ - (Z _{'), and} where Z' is covalently bonded to T _o, and Z 'is selected from the group consisting of -C 0 _2, -SO 3' and -OSO 3 aa is first

Further, it is preferred that the aryliminium cations, aryliminium zwitterions and aryliminium polyions having a net charge of +3 to -3, all of formula I or formula II, are geminally substituted. The geminally substituted bleach enhancers of the present invention inhibit or prevent the decomposition of cations, zwitterions and polyions by aromatization. The aromatizing (decomposition) reaction of a whitening agent with a six-membered cycle is known in the art, as stated, for example, without being bound by any particular theory, in Hanquet et al., Tetrahedron, 49, 423-438 (1993):

Geminally substituted bleach enhancers increase the efficiency of the active bleach enhancer by preventing the base-induced aromatization mentioned above. Such substitution, without being bound by any particular theory, also prevents the decomposition of cations, zwitterions and polyions in other ways. Other degradation methods include, but are not limited to, nucleophilic treatment of a bleach-enhancing compound and / or a bleaching particle, including, but not limited to, anionic, hydroxide, or anionic species. Peroxyhydroxide, carboxylate, peroxycarboxylate and other nucleophiles present in the wash solution.

The bleach-enhancing quaternary imine compounds of the present invention act in conjunction with a peroxide source to provide a more efficient bleach system. Peroxide sources are well known in the art and the peroxide source used in the present invention includes any of these known sources, including peroxide compounds as well as compounds which, under the conditions in which they are used, will produce an effective amount of peroxide in situ. The peroxide source optionally comprises a hydrogen peroxide source, in situ formation of the peroxyacid anion by reacting the hydrogen peroxide source and the bleach activator, preformed peroxyacid compounds or mixtures of suitable peroxide sources. However, one of skill in the art will appreciate other sources of peroxide that can be used without departing from the scope of the present invention.

The hydrogen peroxide source is any suitable hydrogen peroxide source and is present in such amounts as fully described in U.S. Pat. No. 5,576,282. For example, the peroxide source may be selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof.

The bleach activator is optionally selected from the group consisting of tetraacetylethylenediamine, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium lauroyloxybenzenesulfonate, (6-octanamidocaproyl) oxybenzenesulfonido, (6-decanoyloxybenzenesulfonide), (6-decanoyloxybenzenesulfonido),

Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), (DOBA) benzoyl benzoate benzoate benzoate benzoyl caprolactate, OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (Cs-OBS), peroxyhydrolyzable esters, 4- [2V- (nonanoyl) aminohexanoyloxy] benzenesulfonate sodium (NACA-OBS), examples of which are described in US U.S. Patent No. 5,523,434, lauroyloxybenzene sulfonate or dodecanoyloxybenzene sulfonate (LOBS or C12-OBS),

10-undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturated bond at position a

and and decanoyloxybenzoic mixtures thereof, most preferably benzoylvalerolactam. Especially

10:

preferred bleach activators in the pH range of 8-9.5 are those having an OBS or VL as leaving group.

Other preferred bleach activators are those described in U.S. Pat. U.S. Patent 5,698,504, Christie et al., issued December 16, 1997; U.S. Pat. No. 5,695,679, Christie et al., issued Dec. 9, 1997; U.S. Pat. No. 5,686,401, Willey et al., issued Nov. 11, 1997; U.S. Pat. No. 5,686,014, Hartshorn et al., issued Nov. 11, 1997; U.S. Pat. No. 5,405,412, Willey et al., issued April 11, 1995; U.S. Pat. No. 5,405,413, Willey et al., issued April 11, 1995; U.S. Pat. No. 5,130,045, Mitchel et al., issued July 14, 1992; No. 4,412,934, Chung et al., issued Nov. 1, 1983; the serial numbers patents 08/709 072, 08/064 564, all of which are incorporated herein by reference.

Quaternary substituted bleach activators may also be used. The present detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peroxyacid (QSP), more preferably the former. Preferred QSBA structures are further described in U.S. Pat. No. 5,686,015, Willey et al., issued Nov. 11, 1997; U.S. Pat. No. 5,654,421, Taylor et al., issued Aug. 5, 1997; U.S. Pat. No. 5,460,747 to Gosselink et al., issued Oct. 24, 1995; U.S. Pat. U.S. Patent 5,584,888 to Miracle et al

Ft ft ft ft 4 ft 4 ft

On December 17, 1996; No. 5,578,136, Taylor et al., issued Nov. 26, 1996, all of which are incorporated herein by reference.

Highly preferred bleach activators useful in the present invention are amide substituted as described in U.S. Pat. No. 5,698,504; No. 5,695,679; No. 5,686,014, all of which are cited above. Preferred examples of such bleach activators include (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.

Other useful activators described in US Patent 5,698,504, US Patent 5,698,504, US Patent 5,686,014, cited above, and US Patent 4,966,723, Hodge et al., Issued October 30, 1990, include benzoxazine-type activators. , such as cycle ΟδΗ ₄ , to which positions -C (O) OC (R ¹ ) = N- is attached at positions 1,2.

Depending on the activator and the particular application, good bleaching results can be obtained with bleaching systems having a pH of 6 to 13, preferably 9.0 to 10.5, when used. Typically, for example, activators with electron withdrawing groups are used for a pH in the neutral or near neutral range. Alkaline or buffering agents may be used to provide such pH.

The acyl lactam activators described in U.S. Pat. No. 5,698,504; No. 5,695,679 and U.S. Pat. No. 5,686,014, all of which are cited above, are very useful in the present invention, particularly acyl caprolactams (see, for example, WO 94-28102 A) and acylvalerolactams (see US Patent 5,503,639, Willey et al., issued April 12, 1996, which is incorporated herein by reference).

The preformed peroxyacid compound of the present invention is any conventional compound that is stable and which under the conditions of use by the user produces an effective enhancer of the amount of peroxyacid anion, of course. The bleach effect compounds of the present invention can be used together with a preformed peroxyacid compound selected from the group consisting of peroxycarboxylic acids and salts, percarbonate acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, examples of which are described in U.S. Pat. U.S. Patent No. 5,576,282 to Miracle et al.

One group of suitable organic peroxycarboxylic acids are compounds:

Y-R-C-O-OH wherein R is alkylene or substituted alkylene of 1 to 22 carbon atoms or phenylene or substituted phenylene and Y is hydrogen, halogen, alkyl, aryl, -C (O) OH or -C (O) OOH.

Organic peroxyacids suitable for use in the present invention contain one or two peroxy groups and are aromatic or aliphatic. If the organic peroxycarboxylic acid is aliphatic, then the unsubstituted acid is:

O

AND

Y - (CH ₂ ) - C - O - OH where Y is, for example, H, CH ₃ , CH ₂ Cl, C (O) OH or C (O) OOH, and n is an integer from 0 to 20. If the organic peroxycarboxylic acid is the aromatic, then unsubstituted acid is:

O

Even YC ₆ H-CO-OH, wherein Y is, for example, hydrogen, alkyl, alkylhalogen, halogen, C (O) OH or C (0) OOH.

Typical monoperoxyacids useful in the present invention include alkyl and aryl peroxyacids such as:

(i) a peroxybenzoic acid and a cycle substituted peroxybenzoic acid, eg, peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and o-carboxybenzamidoperoxyhexanoic acid (sodium salt);

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA), and ΔΓ, N-talcaproic acid; ;

(iii) amidoperoxyacids, such as peroxysuccinic acid monononylamide (NAPSA) or peroxyadipic acid (NAPAA).

Typical diperoxy acids useful in the present invention include alkyldiperoxy acids and aryldiperoxy acids such as:

(iv) 1,12-diperoxydodecanoic acid;

(v) 1,9-diperoxyazelaic acid;

(vi) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-1,4-dioic acid;

(viii) 4,4'-sulfonylbisperoxybenzoic acid.

Such bleaching agents are described in U.S. Pat. No. 4,483,781, Hartman, issued November 20, 1984, U.S. Pat.

634,551, Burns et al., European Patent Application

No. 133,354, Banks et al., Issued Feb. 20, 1985; patent

No. 412,934, Chung et al., Issued Nov. 1, 1983. Sources also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al. Peroxy sulphate compounds such as OXONE manufactured commercially by E.I. DuPont de Nemours of Wilmongton, DE can also be used as a suitable source of peroxymonosulphuric acid.

The bleach activator as used in the present invention is any compound which, when used in conjunction with a hydrogen peroxide source, leads in situ to the formation of a peroyl acid corresponding to the bleach activator. Various non-limiting examples of activators are described in U.S. Pat. U.S. Patent No. 5,576,282; No. 4,915,854; See also U.S. Patent 4,412,934. No. 4,634,551, which discloses other typical bleaches and activators useful in the present invention.

The bleach-enhancing quaternary imine compounds of the present invention act together with a peroxide source to enhance the bleaching effect. Without wishing to be bound by theory, it is believed that the bleach booster compound reacts with the hydrogen source to form a more active bleach particle, the quaternary oxaziridinium compound. The oxaziridinium compound has an increased activity at lower temperatures than the peroxide compounds. An oxaziridinium compound is a compound of formula III and a compound of formula IV:

wherein t is 0 or 1; R ³¹ to R ³⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; any two adjacent R ³¹ to R ³⁴ are optionally joined to form a fused aryl, fused carbocycle or fused heterocycle; R ²⁵ is substituted or

unsubstituted radical selected from the group consisting of hydrogen, alkyl, alkaryl, aryl, aralkyls, heterocycle, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy and is substituted or unsubstituted, saturated or unsaturated hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and the radical:

-I ~ (Z '), and where Z' is covalently bonded to T _o, and Z is selected from the group consisting of -C 0 ₂ ', -SO 3', -S0 ₂ -OSO3L -0S0 ₂ 'aa is 1 or

2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or

- (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C 8 alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3)

H

AND

-CH2C-CH2 (4)

H

AND

- ch ₂ -c-chOH (5) - (CH ₂ ) d ( ^E ) (CH ₂ ) f -, wherein d is 2 to 8, f is 1 and 3 is

-C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C ₄ to C ₄ alkyl;

(7)

H

AND

wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ³⁹ R ⁴⁰ -, -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² - and

-CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² CR ⁴³ R ⁴⁴ -; R ³⁵ to R ⁴⁴ are substituted or unsubstituted radicals selected from the linear or branched group consisting of H, C _x to C ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; wherein R ²⁷ to R ³⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 to C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is zero R ²⁷ or R ²⁸ is not hydrogen and that when t is one, either of R ²⁷ and R ²⁸ or R ²⁹ and R ³⁰ are not hydrogen; wherein any of R ²⁵ to R ³⁴ is optionally linked to any other of R ²⁵ to R ³⁴ so as to form part of a common chain. In addition, R ²⁵ to R ³⁰ and R ³¹ to R ³⁴ are optionally the same as R ⁵ to R ¹⁰ and R ¹ to R ⁴ in the bleach enhancing compounds of Formula I and Formula II. Such oxaziridinium compounds can be prepared

(AND)

+ rco ₂

Bleaching particles The bleaching particles of the present invention (oxaziridinium) of the present invention can also be used directly according to the invention. The bleaching particles according to the invention are preferably selected from the group consisting of oxaziridinium cations, oxaziridinium cations.

zwitterions, oxaziridinium polyions having a net charge of +3 to -3, and mixtures thereof, wherein the oxaziridinium compounds are compounds of formula III and compounds of formula IV:

.34 wherein t is 0 or 1; R ³¹ to R ³⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, carboxyl, and carboalkoxy; any optionally linked to a fused carbocycle heterocycles; R ²⁵ is a substituted residue selected from the group consisting of alkaryl, aryl, aralkyls, heterocycles, keto groups, two adjacent R ³¹ to R fused aryl, fused unsubstituted hydrogen, alkyl, forms or nitro groups, halogen, cyano, sulfonato, alkoxy, keto groups carboxyl and carboalkoxy; and R ²⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycles, and the radical:

-T ₀ - (Z ') _and from the group is 1 or

IQ · · · ·

Where Z is covalently bonded to T _o and Z 'is selected from the group consisting of -CO ₂ ', -SO3 ', -OSO3', -SO ₂ 'and -OSO2' aa

2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or

- (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C ₈ alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3)

H

AND

-ch ₂ -c-ch ^ (4:

IN

_R -CH-C-CH-OH (5) - _{(CH2) d} (E) _(CH2) f- wherein d is from 2 to 8, f is from 1 to 3 and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl;

(7)

H

I —c—

wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ³⁹ R ⁴⁰ -, -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² - and

-CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² CR ⁴³ R ⁴⁴ -; R ³⁵ to R ⁴⁴ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 to C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R ²⁷ to R ³⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is 27 28 is zero, neither R nor R is hydrogen and that, if t is one, either R ²⁷ and R ²⁸ or R ²⁹ and R ³⁰ are not hydrogen; wherein any of R ²⁵ to R ³⁴ is optionally linked to any other of R ²⁵ to R ³⁴ so as to form part of a common chain. In addition, R ²⁵ to R ³⁰ and R ³¹ to R ³⁴ are optionally the same as R ⁵ to R ¹⁰ and R ¹ to R ⁴ in the bleach enhancing compounds of Formula I and Formula II.

Preferred bleach particles include, but are not limited to: (1) oxaziridinium cations of formula III wherein R ²⁵ is hydrogen or methyl and R ²⁶ is selected from the group consisting of substituted or unsubstituted radicals consisting of linear or branched C 1 -C 14 alkyl, C 3 -C 4 cycloalkyl and C 6 -C 14 aryl; (2) oxaziridinium zwitterions of formula IV wherein R ²⁵ is hydrogen or methyl and R ²⁶ is -T ₀ - (z ') _and

Preferred bleach enhancers include, but are not limited to: (1) oxaziridinium cations of formula III wherein R ²⁵ is hydrogen or methyl and R ²⁶ is selected from the group of substituted or unsubstituted radicals consisting of linear or branched C 1 -C 14 alkyl C ₃ -C 14 cycloalkyl and C 8 -C 14 aryl; (2) oxaziridinium zwitterions of formula IV wherein R ²⁵ is hydrogen or methyl and R ²⁶ is

-T ₀ - (Z '), and where Z' is covalently bonded to T _o, and Z 'is selected from the group consisting of -CO2', -SO 3 and -OSO 3 'aa is 1 or 2; (3) oxaziridinium cations of formula III wherein R ²⁶ is selected from the group consisting of linear or branched C 1 -C 14 substituted or unsubstituted alkyl, or an aryliminium oxaziridinium of formula IV wherein R ²⁶ is

-T ₀ - (Z-) _a where Z 'is -CO ₂ ^_, -SO 3 "and -OSO 3, ajelaT _o is selected from the group consisting of

Λ

I · · · · · (Op1.45

R p is an integer of 2 to 4 and R ⁴⁵ is independently selected from the group consisting of hydrogen and linear or branched C 1 -C 18 substituted or unsubstituted alkyl; and (4) aryliminium polyions having a negative net charge in which R is hydrogen, Z is -CO ₂ , -SO ₃

-0SO ₃ , and a is 2.

and / or bleaching particles 0.00001% by weight

The bleach enhancing compounds of the present invention can be used with or without, preferably, a peroxide source in the bleaching composition. In the bleaching composition of the present invention, the peroxide source is optionally present in amounts of 0.1 wt% (1 ppm) to 60 wt% (600 ppm) based on the weight of the composition, and preferably 1 wt% (10 ppm) to 40 wt% (400 ppm) ) based on the weight of the composition and the bleach enhancing compound optionally present in an amount (0.0001 ppm) to 10% by weight (100 ppm) based on the weight of the composition, and preferably 0.0001% by weight (0.001 ppm) to 2% by weight (20%). ppm) based on the weight of the composition, more preferably 0.005% by weight (0.05 ppm) to 0.5% by weight (5 ppm) and even more preferably 0.01% by weight (0.1 ppm) to 0.2% by weight (2 ppm ). Most preferably it is 0.02% by weight (0.2 ppm) to 0.1% by weight (1 ppm).

Preferably, the bleaching compositions of the present invention contain an amount of bleach enhancing compound and / or bleaching particles such that the final concentration of the bleach enhancing compound in the wash solution is 0.001 ppm to 5 ppm.

Further preferably, the bleaching compositions of the present invention comprise an amount of a peroxide compound, if present, and a bleach enhancing compound and / or bleaching compound, such that the resulting molar ratio of the peroxide compound to the bleach enhancing compound and / or 9 f · The bleach particles in the wash solution are preferably greater than 1: 1, more preferably greater than 10: 1 and even more preferably greater than 50: 1. The preferred molar ratio of peroxide compound to bleach enhancing compound is 30,000: 1 to 10: 1, more preferably 10,000: 1 to 50: 1, even more preferably 5,000: 1 to 100: 1 and even more preferably 3,500: 1 to 150: 1.

The converted values (in ppm) are given for illustration and are based on the use of the product at a concentration of 1000 ppm. A wash solution of 1000 ppm of the product containing 0.2% by weight of the bleach-enhancing compound will have a final bleach-enhancing compound concentration of 2 ppm. Similarly, a washing solution having a concentration of 3500 ppm of a product containing 0.2% by weight of a bleach-enhancing compound will have a final bleach-enhancing compound concentration of 6.5 ppm.

The method of delivering the bleach enhancing compounds of the present invention and the method of delivering bleaching compositions (products) containing such bleach enhancing compounds that are particularly useful in the methods of the present invention are the cases where the bleach enhancing compounds and compositions in which they are contained, fulfilling a preferred method of bleaching a contaminated substrate in an aqueous medium with a peroxide source and a bleach-enhancing compound, the structure of which is defined in the present invention, wherein the medium contains active peroxide compound in an amount of 0.05 ppm to 250 ppm per liter medium and a bleaching enhancing effect in an amount of 0.001 ppm to 5 ppm, preferably 0.01 ppm to 3 ppm, more preferably 0.1 ppm to 2 ppm, and most preferably 0.2 ppm to 1 ppm.

Such a preferred method of bleaching a contaminated substrate in a substrate

aqueous medium se source peroxide and compound amplifying whitening effect Yippee particularly suitable for where it is need to pay attention on retention colors polluted substrate, that is needed clean. In such uses them preferred

.:. .. .........

performance (i.e. 0.01 ppm to 3 ppm) of particular importance for achieving acceptable fabric color retention. For other applications where less attention is needed to maintain the color of the contaminated substrate to be cleaned, higher concentrations are preferred.

The bleaching compositions of the present invention can be advantageously used for washing, including, but not limited to, bleaching, stain bleaching, dye transfer inhibition, bleaching, hard surface cleaning, dishwasher use, as well as cosmetic applications such as dentures, teeth , hair and skin. However, due to the unique advantage of increased bleaching efficiency at lower solution temperatures, the bleach-enhancing compounds of the present invention are ideal for use in laundering applications, such as bleaching fabrics with bleach-containing detergents or bleaching additives for laundering. In addition, the bleach enhancing compounds of the present invention can be used both in the form of granules and in the form of liquid compositions.

The bleaching compositions of the present invention optionally comprise various additional ingredients which are suitable for washing. Such ingredients include detergent surfactants, bleach catalysts, fillers, chelating agents, enzymes, polymeric soil release agents, brighteners, and various other ingredients. Compositions comprising any of these various additional components preferably have a pH of 6 to 12 and a 1% bleach solution, expressed as a percentage by weight, preferably a pH of 8 to 10.5.

The bleaching compositions preferably comprise at least one detergent surfactant, at least one chelating agent, at least one detergent enzyme, and preferably have a pH of 6 to 12, preferably 8 to 10.5, in a 1% bleach solution, expressed as a percentage by weight.

In a further aspect, the present invention provides cationic or zwitterionic compounds which enhance the bleaching effect of the wash. Such bleach enhancing compounds are preferably selected from the group consisting of compounds of formula I, compounds of formula II, compounds of formula III, and compounds of formula IV:

and mixtures thereof; wherein in the compound of formula I and the compound of formula II t is 0 or 1; R ¹ to R ⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyls, cycloalkyls, aryl, heterocycles, nitro, halogens, cyano, sulfonato, alkoxy, ·-keto, carboxyl, and carboalkoxy groups; any of which are optionally combined to form a fused carbocycle or heterocycle; R ⁵ is substituted or a residue selected from the group consisting of cycloalkyls, alkaryl, aryl, aralkyls, two adjacent R ^x to R fused aryl, fused unsubstituted hydrogen, alkyl, heterocycle, nitro, halogen, cyano, sulfonato, alkoxy, keto groups , carboxyl groups and carboalkoxy groups; R ⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and radical:

-T ₀ - (Z ') and wherein Z "is covalently bonded to T _o and Z' is selected from the group consisting of -CCk", -SO 3 ', -OSO 3 ", -SO ₂ and -SO ₂ and a is 1 or

2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or

- (C (R ¹² ) 2) - / wherein R ¹² is independently selected from hydrogen or C 1 to C 8 alkyl; (2) -CH ₂ (C ₆ H 4) -; (3)

H

AND

- CH ₂ -C-CH _r (4)

H

AND

-CH ₂ -C-CH _r OH (5) - _(CH2) d (E) _(CH2) f- wherein d is from 2 to 8, f is from 1 to 3 and E is

-C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C 4 alkyl;

(7)

H

I —c— and (8) i <

• ·

• · · · ·

wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ¹⁸ R ¹⁹ -, -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ - and -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ CR ²² R ²³ -; R ¹⁴ to R ²³ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 -C 18 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R ⁷ to R ¹⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyls, cycloalkyls and heterocycles, with the proviso that when t is zero R ⁷ or R ⁸ is not hydrogen and that when t is one, either of R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are not hydrogen; wherein any one of R ¹ to R ¹⁰ is optionally linked to any other of R ¹ to R ¹⁰ to form part of a common chain; and wherein in the compound of formula III and the compound of formula IV, t is 0 or 1; R ³¹ to R ³⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; any two adjacent R ³¹ to R ³⁴ are optionally joined to form fused aryl, fused carbocycle or fused heterocycles; R ²⁵ is a substituted or unsubstituted radical selected from the group consisting of hydrogen, alkyl, alkaryl, aryl, aralkyls, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy, and R ²⁶ is substituted or unsubstituted an unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycles and a radical:

-T ₀ - _{(Z), and} wherein Z is covalently bonded to T _o, and Z is selected from the group consisting of -C 0 _2, -SO 3 ', -OSO 3, -S0 _2, and -OSO _2' aa is 1 or

2; T _o is selected from the group consisting of: (1) - (CH (R ¹² ) 2) - or - (C (R ¹² ) 2) - / wherein R ¹² is independently selected from hydrogen or C 1 -C 8 alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3)

H

AND

- CH ₂ -C Chfy

H

AND

-CH ₂ -C-Cl-phy

OH (S) - (CH ₂ ) d (E) (CH ₂ ) f -, wherein d is 2 to 8, f is 1 to 3, and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl;

(7)

H

I —c—

wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ³⁹ R ⁴⁰ -, -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² - and

-CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² CR ⁴³ R ⁴⁴ -;

R ³⁵ to R ⁴⁴ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 -C 18 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R ²⁷ to R ³⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyls, cycloalkyls and heterocycles, provided that when t is

zero, R ²⁷ or R ²⁸ is not hydrogen and that when t is one, either of R ²⁷ and R ²⁸ or R ²⁹ and R ³⁰ are not hydrogen; wherein any of R ²⁵ to R ³⁴ is optionally linked to any other of R ²⁵ to R ³⁴ so as to form part of a common chain. In another embodiment, the present invention provides a method of washing a fabric that needs washing. A preferred method comprises contacting the fabric with a wash solution. The fabric includes virtually any fabric that can be washed under normal conditions. The wash solution comprises a bleaching agent which is fully described in the present invention. The temperature of the water used for this washing process is preferably 0 ° C to 50 ° C. The water to fabric ratio is preferably 1: 1 to 15: 1.

The wash solution further optionally comprises at least one additional ingredient selected from the group consisting of detergent surfactants, chelating agents, detergent enzymes, and mixtures thereof. Preferably, the wash solution has a pH of 6 to 12 and more preferably 8 to 10.5 in a 1% bleach solution, expressed as a percentage by weight.

In another aspect, the present invention provides a product that is added to a laundry. This product, which is added to the wash, comprises the bleach-enhancing compound described above. Such a product which is added to the laundry is ideally designed for use in a laundry process where increased bleaching efficiency is desired. Such cases include, but are not limited to, use in a low temperature wash solution.

Suitably, the product to be added to the wash further comprises a peroxide source which has been fully described above. The product to be added to the laundry also comprises a powder or liquid composition comprising a peroxide source as described above.

Further, if the product to be added to the wash comprises a source of hydrogen peroxide, it is desirable that the product to be added to the wash further comprises a bleach activator as described above.

• · · · ·

Preferably, the product to be added to the wash is packaged in a dosage form to be added to the wash, wherein a peroxide source is used and increased bleaching efficiency is desired. Such unit dosage form is a pill, tablet, gel container or other unit dosage form such as pre-metered powders or liquids. If necessary, a filler or carrier may be used to increase the volume of the composition. Suitable fillers or carriers can be selected from, but not limited to, salts of sulphates, carbonates and silicates as well as talc, clays and the like. Fillers or carriers for liquid formulations are water or low molecular weight primary and secondary alcohols including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Other mohohydroxy alcohols may also be used. The compositions comprise from 5% to 90% by weight of such materials. Acidic fillers may be used to lower the pH.

If the bleach-enhancing compounds of the present invention are other than aryliminium zwitterions or oxaziridinium zwitterions, then suitable charge-balancing counterions that are compatible with bleaching are also present.

Bleaching compositions containing bleach enhancing compounds

In addition to using the bleach enhancing compounds mentioned above, the bleach enhancing compounds of the present invention can be used with or without, preferably, a peroxide source in other bleaching compositions regardless of their form. For example, bleach enhancers can be used in the product to be added to the laundry. In the bleaching composition of the present invention, the peroxide source is optionally present in amounts of from 0.1% to 60% by weight of the composition, and preferably from 1% to 40% by weight of the composition. In the composition, the bleach-enhancing compound is optionally present in an amount of 0.001% to 10% by weight of the composition, and preferably 0.005% to 5% by weight of the composition. In the bleaching compositions of the present invention, the peroxide source is optionally present in amounts of 0.1 wt% (1 ppm) to 60 wt% (600 ppm) based on the weight of the composition, and preferably 1 wt% (10 ppm) to 40 wt% (400 ppm) ) based on the weight of the composition, and the bleach enhancing compound is optionally present in an amount of 0.00001% by weight (0.0001 ppm) to 10% by weight (100 ppm) of the composition and preferably 0.0001% by weight (0.001 ppm) 2% by weight (20 ppm) based on the weight of the composition, more preferably 0.005% by weight (0.05 ppm) to 0.5% by weight (5 ppm) and even more preferably 0.01% by weight (0.1 ppm) to 0.2 % by weight (2 ppm). Most preferably, 0.02 wt% (0.2 ppm) to 0.1 wt% (1 ppm).

The converted values (in ppm) are given for illustration and are based on the use of the product at a concentration of 1000 ppm. A wash solution of 1000 ppm of the product containing 0.2% by weight of the bleach-enhancing compound will have a final bleach-enhancing compound concentration of 2 ppm. Similarly, a washing solution having a concentration of 3500 ppm of a product containing 0.2% by weight of a bleach-enhancing compound will have a final bleach-enhancing compound concentration of 6.5 ppm.

The preferred concentration of the bleach enhancing compound is based on the molecular weight of the bleach enhancing compound 300 grams per mole, although the bleach enhancing compounds optionally have a molecular weight of 150 grams per mole to 1000 grams per mole or higher for bleach enhancing oligomeric or polymeric compounds. . For example, in the bleaching compositions of the present invention, if the bleach enhancing compound is more preferably present in an amount of 0.005% by weight (0.05 ppm) to 0.5% by weight (5 ppm), then the molar concentration of the bleach enhancing compound is 1. 7 x 10 ^{8 8} M to 1.7 x 10 ⁵ Μ. When a higher molecular weight bleach enhancing compound is used in the bleaching compositions of the present invention, the preferred molar concentration will remain unchanged, while the preferred weight concentration (in ppm) will correspondingly increase. For example, the bleach-enhancing compound with a molecular weight of 600 grams per mole is preferably present in an amount of 0.01 wt% (0.1 ppm) to 1.0 wt% (10 ppm). For bleach enhancing oligomeric or polymeric compounds, the preferred molar concentration is based on the monomeric unit associated with the iminium or oxaziridinium active center.

The bleaching compositions of the present invention can be advantageously used for washing, cleaning hard surfaces, dishwasher use, as well as cosmetic applications such as dentures, teeth, hair and skin. However, due to the unique advantage of increased color protection and increased efficacy in both cold and warm aqueous solutions, due to increased stability, the bleach enhancing compounds of the present invention are ideal for use in laundering applications such as bleaching fabrics with bleach-containing detergents or bleaching additives for washing. In addition, the bleach enhancing compounds of the present invention can be used both in the form of granules and in the form of liquid compositions.

Bleach-enhancing compounds and bleaching compositions containing these bleach-enhancing compounds can be used as antimicrobial agents and disinfectants.

The bleaching compositions of the present invention optionally comprise various additional ingredients which are suitable for washing. Such ingredients include detergent surfactants, bleach catalysts, fillers, chelating agents, enzymes, polymeric soil release agents, brighteners, and various other ingredients. Compositions comprising any of these various additional components preferably have a pH of 6 to 12 and a 1% bleach solution, expressed as a percentage by weight, preferably a pH of 8 to 10.5.

The bleaching compositions preferably comprise at least one detergent surfactant, at least one chelating agent, at least one detergent enzyme, and preferably have a pH of 6 to 12, preferably 8 to 10.5, in a 1% bleach solution, expressed as a percentage by weight.

In another embodiment, the present invention provides a method of washing a fabric in need of washing comprising contacting the fabric with a laundry solution comprising a bleaching composition of the present invention. The fabric includes virtually any fabric that can be washed under normal conditions. The wash solution comprises a bleaching agent which is fully described in the present invention. The temperature of the water used for this washing process is preferably 0 ° C to 50 ° C. The water to fabric ratio is preferably 1: 1 to 15: 1.

The wash solution further optionally comprises at least one additional ingredient selected from the group consisting of detergent surfactants, chelating agents, detergent enzymes, and mixtures thereof. Preferably, the wash solution has a pH of 6 to 12 and more preferably 8 to 10.5 in a 1% bleach solution, expressed as a percentage by weight.

In another aspect, the present invention provides a product that is added to a laundry. This product, which is added to the wash, comprises the bleach-enhancing compound described above. Such a product which is added to the laundry is ideally designed for use in a laundry process where increased bleaching efficiency is desired. Such cases include, but are not limited to, use in a low temperature wash solution.

• ·.:. .. · .........

Suitably, the product to be added to the wash further comprises a peroxide source which has been fully described above. The product to be added to the laundry also comprises a powder or liquid composition comprising a peroxide source as described above.

Further, if the product to be added to the wash comprises a source of hydrogen peroxide, it is desirable that the product to be added to the wash further comprises a bleach activator as described above.

Preferably, the product to be added to the wash is packaged in a dosage form to be added to the wash, wherein a peroxide source is used and increased bleaching efficiency is desired. Such unit dosage form is a pill, tablet, gel container or other unit dosage form such as pre-metered powders or liquids. If necessary, a filler or carrier may be used to increase the volume of the composition. Suitable fillers or carriers can be selected from, but not limited to, salts of sulphates, carbonates and silicates as well as talc, clays and the like. Fillers or carriers for liquid formulations are water or low molecular weight primary and secondary alcohols including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Other mohohydroxy alcohols may also be used. The compositions comprise from 5% to 90% by weight of such materials. Acidic fillers may be used to lower the pH.

A preferred bleaching composition is a bleaching composition comprising:

(a) a peroxide source; and (b) bleach enhancing compounds;

wherein the bleach enhancing compounds become active in the bleach-containing wash solution for some time after the peroxide source becomes active. The peroxide source is preferably selected from the group consisting of:

(i) reshaped peroxyacid compounds selected from the group consisting of peroxycarboxylic acids and salts;

peroxycarbonate acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts and mixtures thereof, and (ii) hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate compounds, peroxyphosphate compounds and mixtures thereof, and a bleach activator.

Bleaching system

In addition to the bleach enhancing compounds of the present invention, the bleaching compositions of the present invention preferably comprise a bleach system. Bleaching systems typically contain a peroxide source. Peroxide sources are well known in the art and the peroxide source used in the present invention includes any of these known sources, including peroxide compounds as well as compounds which, under the conditions in which they are used, will produce an effective amount of peroxide in situ. The peroxide source optionally comprises a hydrogen peroxide source, in situ formation of the peroxyacid anion by reacting the hydrogen peroxide source and the bleach activator, preformed peroxyacid compounds or mixtures of suitable peroxide sources. However, one of skill in the art will appreciate other sources of peroxide that can be used without departing from the scope of the present invention. Preferably, the peroxide source is selected from the group consisting of:

(i) reshaped peroxyacid compounds selected from the group consisting of peroxycarboxylic acids and salts, percarbonate acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof; and (ii) hydrogen peroxide sources selected from the group consisting of peroxyborate compounds, percarbonate compounds , peroxyphosphate compounds and mixtures thereof, and a bleach activator.

If present, sources of peroxide (peroxyacids and / or sources of hydrogen peroxide) typically make up 1% by weight. preferably 5% to 30% by weight, preferably up to 20% by weight of the composition. If present, the amount of bleach activator will typically be 0.1% by weight, preferably 0.5% to 60% by weight, preferably up to 40% by weight, based on the bleaching composition containing the bleaching agent plus the bleach activator.

Pre-formed peroxyacids

The preformed peroxyacid compound as used in the present invention is any conventional compound that is stable and which, under the conditions of use by the consumer, provides an effective amount of the peroxyacid anion. The bleach enhancing compounds of the present invention may, of course, be used in conjunction with a preformed peroxyacid compound selected from the group consisting of peroxycarboxylic acids and percarbonate acids and their acids and salts thereof, peroxymonosulfuric acids and salts and mixtures thereof, examples of which are described in U.S. Pat. U.S. Patent No. 5,576,282 to Miracle et al.

One group of suitable organic peroxycarboxylic acids are compounds:

O

AND

YRCO-OH salts, salts, perimide salts thereof wherein R is alkylene or substituted alkylene of 1 to 22 carbon atoms or phenylene or substituted phenylene and Y is hydrogen, halogen, alkyl, aryl, -C (O) OH or -C (O ) OOH.

Organic peroxyacids suitable for use in the present invention contain one or two peroxy groups and are aromatic or aliphatic. If the organic peroxycarboxylic acid is aliphatic, then the unsubstituted acid is:

O

AND

Y - (CH ₂ ) - C - O - OH - where Y is, for example, H, CH ₃ , CH ₂ Cl, C (O) OH or C (O) OOH, and n is an integer from 0 to 20. If the organic peroxycarboxylic acid is aromatic, then the unsubstituted acid is:

O

AND

YC ₆ H — CO-OH wherein Y is, for example, hydrogen, alkyl, alkyl halogen, halogen, C (O) OH or C (O) OOH.

Typical monoperoxyacids useful in the present invention include alkyl and aryl peroxyacids such as:

(i) a peroxybenzoic acid and a cycle substituted peroxybenzoic acid, e.g., peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and o-carboxybenzamidoperoxyhexanoic acid (sodium salt);

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA), and N, N-phthaloyl amino acid );

(iii) amidoperoxyacids, such as peroxysuccinic acid monononylamide (NAPSA) or peroxyadipic acid (NAPAA).

Typical diperoxy acids useful in the present invention include alkyldiperoxy acids and aryldiperoxy acids such as:

(iv) 1,12-diperoxydodecanoic acid;

(v) 1,9-diperoxyazelaic acid;

(vi) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-1,4-dioic acid;

(viii) 4,4'-sulfonylbisperoxybenzoic acid.

Such bleaching agents are described in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent 4,634,551, Burns et al., European Patent Application. ·· * ·

No. 133,354, Banks et al., Issued Feb. 20, 1985; No. 4,412,934, Chung et al., issued November 1, 1983. Sources also include 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al. Peroxy sulphate compounds such as OXONE manufactured commercially by E.I. DuPont de Nemours of Wilmongton, DE can also be used as a suitable source of peroxymonosulphuric acid.

b. Sources of hydrogen peroxide

The hydrogen peroxide source is any suitable hydrogen peroxide source and is present in such amounts as fully described in U.S. Pat. No. 5,576,282. For example, the peroxide source may be selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof.

Sources of hydrogen peroxide are described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, 4th edition (1992, John Wiley &amp; Sons), Vol. 4, pp. 271-300, &quot; Bleaching Agents (Survey) &quot; and include various forms of sodium perborate and sodium percarbonate including coated and formulated forms.

The preferred hydrogen peroxide source used in the present invention is any conventional source including hydrogen peroxide itself. For example, a perborate, such as sodium perborate (any hydrate but preferably mono or tetrahydrate), sodium carbonate peroxyhydrate or equivalent of percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide may be used according to the present invention. Also available are sources of available oxygen such as persulfate bleach (e.g., OXONE manufactured by DuPont). Sodium percarbonate monohydrate and sodium percarbonate are particularly preferred with "######" ###################################### · »♦ ··» preferred. Mixtures of any conventional sources of hydrogen peroxide can also be used.

A preferred percarbonate bleach comprises dry particles having a mean particle size of 500 microns to 1000 microns, with no more than 10% by weight of the particles being less than 200 microns and no more than 10% by weight being greater than 1250 microns. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

The compositions of the present invention optionally also contain a chlorine-based bleaching material as a bleaching agent. Such agents are well known in the art and include, for example, dichloroisocyanurate ("NaDCC"). However, chlorine-based bleaches are less preferred for enzyme-containing compositions.

preferably up to the composition.

b. Bleach activators

Preferably, the peroxide source in the composition is mixed with an activator (a peroxyacid precursor). The activator is present in amounts of 0.01% to 0.5% by weight, more preferably 1% to 15% by weight, 10% by weight, more preferably 8% by weight. The bleach activator as used in the present invention is any compound which use with a source of hydrogen peroxide leads to a peroxyacid corresponding to the bleach activator. Various non-limiting examples of activators are described in U.S. Pat. U.S. Patent No. 5,576,282; No. 4,915,854; See also U.S. Patent 4,412,934. No. 4,634,551, which discloses other typical bleaches and activators useful in the present invention.

Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoyl caprolactam (BzCL), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, lactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOB), decanoyloxybenzenesulfonate (C10-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate ( _C8 -OBS), peroxyhydrolyzable esters and mixtures thereof, and most preferably are benzoyl caprolactam and benzoylvalerolactam. Particularly preferred bleach activators for the pH range of 8-9.5 are those containing OBS or VL as a leaving group.

Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS), 4- [N - (nonanoyl) aminohexanoyloxy] benzenesulfonate sodium (NACA-OBS), examples of which are described in U.S. Pat. No. 5,523,434, lauroyloxybenzenesulfonate or dodecanoyloxybenzenesulfonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or Cu-OBS with unsaturated bond at position 10), and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in U.S. Pat. U.S. Patent 5,698,504, Christie et al., issued December 16, 1997; U.S. Pat. No. 5,695,679, Christie et al., issued Dec. 9, 1997; U.S. Pat. No. 5,686,401, Willey et al., issued Nov. 11, 1997; U.S. Pat. No. 5,686,014,

Hartshorn et al., issued November 11 1997; U.S. Pat. patent 5 405 412 Willey a et al., issued April 11 1995; U.S. Pat. patent 5,405,413, Willey a et al., issued April 11 1995; U.S. Pat. patent 5,130,045, Mitchel et al., issued July 14 1992 and U.S. Pat.

No. 4,412,934, Chung et al., issued Nov. 1, 1983; the serial numbers patents 08/709 072, 08/064 564, all of which are incorporated herein by reference.

The molar ratio of the peroxygen bleach compound (such as AvO) to the bleach activator in the present invention is generally at least 1: 1, preferably 20: 1, more preferably 10: 1 to 1: 1, preferably 3: 1.

• · ································

Quaternary substituted bleach activators may also be used. The present detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peroxyacid (QSP), more preferably the former. Preferred QSBA structures are further described in U.S. Pat. patent

No. 5,686,015, Willey et al., issued on 11. November 1997; U.S. Pat. No. 5,654,421, Taylor a issued on 5. August 1997; U.S. Pat. No. 5,460,747 Gosselink et al 24. October 1995; U.S. Pat. patent 5,584,888, Miracle and col. , issued December 17, 1996 and U.S. Pat. No. 5,578 136, Taylor et al. , issued November 26, 1996, which are here all listed as a reference. Very preferred activators bleaching useful

in the present invention are amide substituted as described in U.S. Pat. No. 5,698,504; No. 5,695,679; No. 5,686,014, all of which are cited above. Preferred examples of such bleach activators include (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.

Other useful activators described in US Patent 5,698,504, US Patent 5,695,679, US Patent 5,686,014, cited above, and US Patent 4,966,723, Hodge et al., Issued October 30, 1990, include benzoxazine-type activators. , such as the C ₆ H ₄ cycle to which the -C (O) OC (R ¹ ) = N- group is attached at positions 1,2.

Depending on the activator and the particular application, good bleaching results can be obtained with bleaching systems having a pH of 6 to 13, preferably 9.0 to 10.5, when used. Typically, for example, activators with electron withdrawing groups are used for a pH in the neutral or near neutral range. Alkaline or buffering agents may be used to provide such pH.

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

The acyl lactam activators described in U.S. Pat. No. 5,698,504; No. 5,695,679 and U.S. Pat. No. 5,686,014, all of which are cited above, are very useful in the present invention, particularly acyl caprolactams (see, for example, WO 94-28102 A) and acylvalerolactams (see US Patent 5,503,639, Willey et al., issued April 12, 1996, which is incorporated herein by reference).

d. Organic peroxides, especially diacyl peroxides

In addition to the bleaching agents described above, the bleaching compositions of the present invention optionally also contain organic peroxides. Organic peroxides are extensively described in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley & Sons, 1982 on pages 27 to 90, and in particular on pages 63 to 72, all of which are incorporated herein by reference. If diacyl peroxide is used, it is preferably used that minimizes the adverse effect on staining or film formation.

e. Metal-containing bleach catalysts

The bleaching compositions also optionally comprise metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts.

One type of metal-containing catalyst is a catalyst system comprising a transition metal cation with defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese, a metal cation having little or no bleach catalytic activity, such as zinc or aluminum; and a complexing agent having a defined stability constant for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts. Such catalysts are described in U.S. Patent 4,430,243, Bragg, issued Feb. 2, 1982.

• ···················································.

i. Manganese complexes

If appropriate, the compositions of the present invention can be catalyzed by manganese compounds. Such compounds and the amounts in which they are used are well known in the art and include, for example, the manganese-based catalysts described in U.S. Patent 5,576,282, Miracle et al., Issued November 19, 1996; U.S. Patent 5,426,621, Favre et al., Issued September 21, 1993; U.S. Patent 5,244,594, Favre et al., Issued September 14, 1993; U.S. Patent 5,194,416, Jureller et al., Issued March 16, 1993; U.S. Patent 5,114,606, van Vliet et al., Issued May 19, 1992 and European Patent Applications Nos. 549,271 A1, 549,272 A1, 544,440 A2 and 544,490 A1. Preferred examples of these catalysts include Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PFg) 2,

Mn ^TII 2 (µ-O) 3 (µ-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (CIO 4) 2, Mn ^IV 2 (µO) 6 (1,4 7-triazacyclononane) 4 (C1O ₄ ) 4,

^{Μη Ιι; [Μη} ιν 4 (UO) 1 (u-OAc) 2 (1,4,7-trimethyl-l, 4,7-triazacyclononane) 2 (ClO4) 3, Mn ^IV 2 (1,4,7 trimethyl-1,4,7-triazacyclononane) 2 (OCH ₃ ) 3 (PF ₆ ) and mixtures thereof. Other bleach catalysts for

base of metals include those that are described in U.S. Pat. patent 4 430 243, which has already been cited above, and U.S. Pat. patent 5 114 611, van Kralingen, published May 19 1992. Use

manganese with various complex ligands to improve bleaching is also disclosed in the following patents: U.S. Pat. U.S. Patent 4,728,455, Rerek, issued March 1, 1988; U.S. Pat. U.S. Patent 5,284,944, Madison, issued Feb. 8, 1994; U.S. Pat. U.S. Patent 5,246,612, van Dijk et al., issued September 21, 1993; U.S. Pat. No. 5,256,779, Kerschner et al., issued October 26, 1993; U.S. Pat. U.S. Patent 5,280,117 to Kerschner et al., issued Jan. 18, 1994; U.S. Pat. U.S. Patent 5,274,147, Kerschner et al., issued Dec. 28, 1993; U.S. Pat. No. 5,153,161, Kerschner et al., issued Oct. 6, 1992; No. 5,227,084, Martens et al., issued July 13, 1993.

Ii. Cobalt complexes

The cobalt-based bleach catalysts useful in the present invention are known and are described, for example, in U.S. Pat

U.S. Pat. U.S. Patent 28 January 1997; January 21, 1997;

No. 597,936, U.S. Pat. U.S. Pat. patent

Perkins and 5,595,967,

703 030, col. Miracle Perkins, et al., Et al., Issued December 30, 1997; and ML to You "Base Hydrolysis of Transition-Metal Complexes, Adv. Inorg. Bioinorg. Mech., 2: 1-94 (1983). The most preferred cobalt useful in the present invention is the cobalt pentaamine acetate salt [Co (NH ₃ ) sOAc] T _y , represents the cobalt pentaamine acetate chloride acetate group,

T _y is an anion, the catalysts are wherein "OAc and especially [Co (NH ₃ ) 5 OAC] Cl 2; as well as [Co (NH _{3) 5} 0Ac] (OAc) 2; [Co (NH ₃ ) ₅ OAc] (PF ₆ ) ₂ ; [Co (NH ₃ ) ₅ OAc] (SO ₄ ); [Co (NH ₃ ) ₅ OAc] (BF ₄ ) 2 and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) 2 (abbreviated hereinafter as "PAC").

These cobalt catalysts can be readily prepared by known methods such as those described in U.S. Pat. No. 5,597,936; No. 5,595,967; No. 5,703,030, cited above, the article by You and the references cited therein; No. 4,810,410, Diakun et al., issued Mar. 7, 1989, J. Chem. Ed., 66 (12), 1043-1045 (1989); Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (PrenticeHall; 1970), pp. 461-463; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

The macropolycyclic transition metal transition metal of the present invention also optionally provides a transition metal complex catalyst with a rigid ligand. Term iii. Rigid ligand complexes

The compositions according to the invention comprise as a bleaching agent with a macropolycyclic cycle and the superstructure type "macropolycyclic rigid ligand" is abbreviated hereinafter as "MRL." The amount used is a catalytically effective amount, preferably 1 ppb or more, for example up to 99.9% by weight, more typically 0.001 ppm or more, preferably 0.05 ppm to 500 ppm (wherein "ppb refers to parts per billion by weight and" ppm refers to parts per million by weight).

Suitable transition metals, e.g., Mn, are illustrated below. “Macropolycyclic means that MRL is both macrocycle and polycyclic. "Polycyclic" means at least bicyclic. The term "rigid," as used herein, means that it "has a superstructure and is" cross-bridged. “Rigid was defined as a forced change of flexibility: see D.H. Busch, Chemical Reviews, 93, 847-860 (1993). More specifically, "rigid as used in the present invention means that the MRL must be appreciably more rigid than the macrocycle (the" original macrocycle "), which is otherwise the same (having the same size and number of atoms in the main cycle) but not (especially linking groups or preferably a cross-bridging group) that is in the MRL. In determining comparable rigidity of macrocycles with and without superstructures, the skilled artisan will use the free form (without bound metal) of macrocycles. Rigidity is well applicable when comparing a tool to determine, measure, or include computational methods (see, for example, Zimmer, Chemical Reviews, 95 (38), 2629-2648 (1995) or Hancock et al., Inorganica Chimica Acta, 164, 73-84) (1989).

Preferred MRLs of the present invention are particularly particular types of ultrarigid ligands that are cross-bridged. “Cross bridging is illustrated in a non-limiting way in 1.11. In 1.11, the -CH ₂ CH ₂ group is a cross bridging. Bridges N ¹ and N ⁸ in an illustrative structure. By comparing the bridging "on the same side, for example if introduced between N ¹ and N 12 in 1.11," cross bridging is not achieved and therefore this variant is not preferred.

macrocycles; suitable rigidity comparison • ···· · · ··· «··· · ············· · · ···· · «·

Suitable metals in rigid ligand complexes include Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II) ), Co (III), Ni (II), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV) ), Cr (V), V (III), V (V), V (V), Mo (V), Mo (V), Mo (V), W (V), W (V), W (V) ), Pd (II), Ru (II), Ru (III) and Ru (IV). Preferred transition metals in said transition metal bleach catalysts include manganese, iron and chromium.

More generally, the MRLs (and corresponding transition metal catalysts) of the present invention preferably comprise:

(a) at least one macrocyclic backbone containing four or more heteroatoms; and (b) a covalently attached non-metallic superstructure capable of increasing the rigidity of the macrocycle, preferably selected from (i) a bridged superstructure as linking groups;

(ii) cross-bridged superstructure as cross-linking groups; and (iii) combinations thereof.

The term "superstructure" as used herein has been defined in the literature by Busch et al., See, for example, the articles in "Chemical Reviews" by Busch.

Preferred superstructures according to the present invention not only increase the rigidity of the original macrocycle, but also facilitate the composition of the macrocycle by coordinating the metal into the tongs. Suitable superstructures can be very simple, for example, any of the following structures shown in Figure 1 and Figure 2 can be used as the bridging group.

(CHA Figure 1 wherein n is an integer, for example 2 to 6, typically 2 to 4 or preferably lower

A Z figure 2 wherein n and m are integers 1 to 8, more preferably 1 to 3; Z is N or CH; and T is a compatible substituent such as hydrogen, alkyl, trialkylammonium, halogen, nitro, sulfonate, and the like. The aromatic ring in 1.10 can be replaced by a saturated ring in which the Z atom joining the ring is optionally N, O, S or C.

Suitable MRLs are further illustrated in a non-limiting manner by the following compound:

Figure 3

This is the MRL of the present invention, which is a highly preferred, cross-bridged, methyl substituted (all nitrogen atoms are tertiary) cyclamide derivative. Formally, this ligand can be named as 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane using the von Baeyer system extension. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993" by R. Panico, W.H. Powell and J.-C. Richer (eds), Blackwell Scientific Publications, Boston, 1993; see in particular section R-2.4.2.1.

Transition metal bleach catalysts with macrocyclic rigid ligands suitable for use in the compositions of the present invention generally include known compounds which are in accordance with the definition given in the present invention. · · ········ ··· »· · ·

AfJ · · · · ···

Or, more preferably, any amount of new compounds that are continually proposed for use in washing or cleaning and non-limiting examples thereof are as follows:

dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) hexafluorophosphate aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate diaquo-5,12-dimethyl-1,5,8,12 -tetraazabicyclo [6.6.2] manganese hexadecane (II) dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (III) hexafluorophosphate dichloro-5,12-dibutyl-1 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5-butyl -12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II).

(f) Other bleach catalysts

Optionally, the composition of the present invention comprises one or more additional bleach catalysts. Preferred bleach catalysts are the zwitterionic bleach catalysts described in U.S. Pat. No. 5,576,282 (especially 3- (3,4-dihydroisoquinolinium) propanesulfonate). Other bleach catalysts include cationic bleach catalysts that patent

482 515,

No. 5,360,569, 5,442,066,

550,256 and WO 95/13351 are described in U.S. Pat. 5,470,357, 5,370,826,

WO 95/13352 and WO 95/13353.

«· • β • ·

For practical reasons, which does not imply any limitation of the present invention, the compositions and cleaning processes of the present invention may be modified to provide on the order of at least one part per hundred million active bleach catalyst particles in an aqueous wash medium and preferably provide 0.01 ppm to 25 ppm, more preferably 0.05 ppm to 10 ppm, and most preferably 0.1 ppm to 5 ppm of the bleach catalyst particles in the wash solution. In order to achieve such an amount in the wash solution of an automatic wash, typical compositions of the present invention comprise 0.0005% by weight to 0.2% by weight, more preferably 0.004% by weight to 0.08% by weight of bleach catalyst, especially manganese or cobalt catalysts based on on the weight of the cleaning agents.

Preferably, the peroxide source is selected from hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate peroxyphosphate compounds, and bleach mixtures thereof.

Preferably, the bleach activator is selected from the group consisting of the hydrophobic bleach activators described in the present invention.

The purpose of such a bleaching composition is to alleviate the unwanted decomposition of the bleach-enhancing compound and to allow peroxyacids to achieve a bleaching effect on a fabric that needs to be washed, such as a soiled fabric, in a wash solution prior to the bleach-enhancing compound.

The time between which the active compounds become active in the wash solution is from 1 second to 24 hours.

Alternatively, since the bleach enhancing compounds are relatively stable in the wash solution, the peroxyacid becomes active in the wash solution only after the bleach enhancing compound becomes active or available.

compounds, and an activator of the group which is a peroxyacid, and thereby the bleaching enhancing effect of &quot; Controlled &quot;

Compositions

The aim of the later addition of a bleaching composition (which can be used, but need not be used, in the present invention) is to allow the peroxyacid to achieve maximum bleaching effect on a fabric to be cleaned, such as a soiled fabric, in the wash solution before loading. In other words, a bleaching composition comprising a bleach-enhancing compound that becomes active in the wash solution upon insertion of the fabric in need of cleaning into the wash solution. Methods for delayed (sequential) addition of bleach enhancing compounds are described in more detail in commonly-assigned U.S. Pat. U.S. Patent Application, Laundry Methods Employing Same

27 August 1999 (P&G attorney, file number 7749P).

Alternatively, since the bleach enhancing compounds have a higher stability, bleaching compositions comprising a bleach enhancing compound that becomes active in the wash solution before adding the fabric to be cleaned to the wash solution can be used.

The bleaching compositions of the present invention also preferably contain, in addition to one or more of the bleach enhancing compounds described above, one or more additional cleaning components, preferably compatible with bleach enhancing compounds and / or any enzyme present in the bleaching composition. The term "compatible" as used herein means that the bleaching materials do not reduce the bleaching activity of the bleach-enhancing compound and / or any enzymatic activity of any enzyme present in the bleaching composition to the extent that the bleach-enhancing compound and / or enzyme it is not effective as required in normal use. The term "additional cleansing component," as used herein, refers to any liquid, solid or gaseous material selected for a particular type of desired bleaching composition. and according to the form of the product (eg, liquid; granules; powder; stick; paste; spray; tablet; gel; foaming agent), which materials are also preferably compatible with the protease enzymes and bleaching agents used in the formulation. Granular compositions may also be in "compact form" and liquid compositions may also be in "concentrated form."

The particular choice of additional cleaning components can be readily made according to the surface, component or fabric to be cleaned and the desired form of the composition for the cleaning conditions in use (eg, as a laundry detergent). Examples of suitable additional cleaning ingredients include, but are not limited to, surfactants, fillers, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelators, optical brighteners, soil release polymers, dye transfer inhibiting agents, dispersants, agents suds suppressors, dyes, fragrances, filler salts, hydrotropes, fluorescent agents, conditioners photoactivators, for fabric, hydrolysable surfactants, preservatives, antioxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti-gloss agents and / or agents anticorrosion, alkaline sources, solubilizing agents, carriers, processing aids, pigments and pH adjusting agents as described in US Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014, and a bleaching component

646 101. More specifically described below If the adjuvants are not compatible cleaning ingredients with protease variants in the bleaching compositions, then suitable methods may be used to keep the additional cleaning ingredients and protease variants separate (so that they are not in contact with each other) until mixing both components. Suitable methods are any procedures known in the art, such as gel containers, encapsulation, tablets, physical separation, etc.

Such bleaches include detergent compositions for cleaning hard surfaces in any form (eg, liquid, granular, paste, foam, spray, etc.); detergents for cleaning fabrics in any form (eg, granular, liquid, sticks, etc.); dishwashing compositions (in any form and including granular and liquid dishwashing compositions); oral whitening agents in any form (eg, cleaning powder, toothpaste and mouthwash); and dentifrice whitening compositions in any form (eg, liquid or as tablets).

The fabric bleaching compositions of the present invention are mainly intended for use in an automatic washing machine wash cycle; however, other uses, such as prewashing agents for heavily soiled fabrics or soaking agents, are also contemplated; the use is not necessarily limited to an automatic washing machine, and the compositions of the present invention can be used alone or in combination with compatible hand wash compositions.

Optionally, the bleaching compositions comprise from 1% to 99.9% by weight of the composition of the additional cleaning components.

As used in the present invention, "non-fabric bleaching compositions include hard surface bleaching agents, dishwashing compositions, oral bleaching compositions, dentifrice bleaching compositions, and personal care compositions.

When the bleaching compositions of the present invention are used in a composition suitable for use in automatic laundry washing, the compositions of the present invention preferably comprise a surfactant component and a filler component and in addition one or more additional cleaning components preferably selected from organic polymeric compounds, bleaching agents, enzymes, suds suppressors, lime soap, antifoaming agents

The detergent compositions also optionally contain dispersants, dispersion suspending and settling dispersants, and corrosion inhibitors containing plasticizers and other additional cleaning components.

The compositions of the present invention may also optionally be used as additional detergent products in solid or liquid form. Such additive products are intended to supplement or enhance the performance of conventional detergent compositions and may be added at any stage of the cleaning process.

When used as hand dishwashing compositions, the compositions of the present invention preferably comprise a surfactant and preferably other additional cleaning ingredients selected from organic polymeric compounds, suds boosters, Group II metal ions, solvents, hydrotropes and additional enzymes .

If desired, the density of the laundry detergent compositions of the present invention is 400 g / l to 1200 g / l, preferably 500 g / l to 950 g / l of the composition, measured at 20 ° C.

The compact form of the bleaching compositions of the present invention is best characterized by its density and, in terms of composition, the amount of inorganic filler salt; inorganic builder salts are conventional liquid detergent builders; in conventional compositions, filler salts are present in amounts, typically 17% to 35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% by weight of the total composition, preferably not exceeding 10% by weight and most preferably not exceeding 5% by weight of the composition. The inorganic filler salts used in the compositions of the present invention are selected from alkali metal salts and alkaline earth metal salts of sulphates and chlorides. A preferred builder salt is sodium sulfate.

detergent in essential ····················································· · ·· ·· · ···

The liquid compositions of the present invention are also optionally in "concentrated form" and in such a case the liquid bleaches of the present invention contain a lower amount of water as compared to conventional detergent compositions. Typically, the water content of the concentrated liquid bleaching composition is preferably less than 40% by weight, more preferably less than 30% by weight, and most preferably less than 20% by weight of the bleaching composition.

Additional cleaning components

Although not essential for carrying out the present invention, the additional cleaning ingredients illustrated below are suitable for use in ready-to-use bleaching compositions and can be advantageously used in preferred embodiments of the present invention, for example, to promote or improve cleaning efficiency, to treat a cleaned substrate or to treat the aesthetic properties of the bleaching agent need to be fragrance ingredients, colorants and the like. The exact nature of these additional cleaning ingredients and the amount in which they are used will depend on the physical form of the composition and the nature of the cleaning operation to which the composition will be used. Unless otherwise indicated, the bleaching compositions of the present invention are in the form of granules or powders for general use or cleaning agents for "severe soiling, in particular laundry detergents; liquids, gels or pastes for general use as cleaning agents, in particular heavy-duty type fluids; liquid detergents for delicate fabrics; hand dishwashing agents or heavily soiled dishwashing agents, especially those that are very foaming; agents for use in dishwashers, including various tablets, granules, fluids and rinse agents for domestic and industrial use; liquid cleaning and disinfecting agents including antibacterial types for hand washing, washing soaps, mouthwashes, dentifrice cleaners, car shampoos or carpet shampoos, bathroom cleansers; hair shampoos;

Shower gels and foams for baths and metal cleaners; as well as cleaning aids such as bleaching additives and pretreatment agents.

in the present

Tenžidy

The compositions of the present invention preferably comprise a detergent surfactant. The detergent surfactant is typically selected from the group consisting of anionic, nonionic, cationic, ampholytic, zwitterionic surfactants and mixtures thereof. By selecting the type and amount of the detergent surfactant, together with the additional ingredients described herein, the detergent compositions of the invention can be formulated washing or other cleaning operations, in particular for washing dishes. Therefore, the particular surfactants used vary depending on the particular end use. Suitable surfactants are described below. Examples of suitable nonionic, anionic, cationic, amphoteric and zwitterionic surfactants are described in "Surface Active Agents and Detergents," (Vol. I and II, Schwartz, Perry and Berch). Many of these surfactants are also generally described in U.S. Pat. No. 3,929,678, Laughlin et al., issued December 30, 1975, at section 23, line 58 to section 29, line 23.

The surfactant is typically used in an amount of 0.1% by weight, preferably 1% by weight, more preferably 5% by weight of bleaching agents up to 99.9% by weight, preferably up to 80% by weight, more preferably up to 35% by weight and most preferably up to 30% by weight bleaching agents. resources.

Anionic surfactants

Anionic surfactants useful in the present invention are preferably selected alkylbenzene sulfonate, alkyl ester, from the group consisting of linear and ~ olefin sulfonate, paraffin sulfonates, alkyl sulfates, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxy, ·· · alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount, typically 0.5% to 90% by weight, preferably 5% to 60% by weight, more preferably 10% to 30% by weight of the anionic detergent surfactant may be used according to the present invention.

Alkyl sulfate surfactants are another type of anionic surfactant suitable for use in the present invention. In addition to having an excellent overall cleaning performance when used with polyhydroxy fatty acid amides (see below), including a good grease / oil cleaning effect over a wide range of temperatures, concentrations and times, dissolution of alkyl sulfates and thus good incorporation into liquid detergent compositions can be achieved. where water soluble salts or acids ROSO 3 M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 to C ₂ o alkyl component, preferably a C12 to C₁₅ alkyl or hydroxyalkyl, and M is H or a cation, e.g. alkali metal (group la of the periodic table) (e.g. sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl, dimethyl and trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium and alkanolamine-derived cations such as is ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like obně. Typically, C12 to C16 alkyl chains for lower wash temperatures (e.g., below 50 ° C) and C 3-6 to C 18 alkyl chains for higher wash temperatures (e.g., above 50 ° C) are preferred.

Alkylalkoxylated sulfate surfactants are another class of useful anionic surfactants. These surfactants are water-soluble salts or acids of RO (A) _m SO 3 M, wherein R is unsubstituted C 10 -C ₂₄ alkyl or hydroxyalkyl containing a C 10 -C ₂₄ alkyl component, preferably C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy group, m is greater than zero, typically 0.5 to 6, more preferably 0.5 to 3, and M is hydrogen or a VS cation, which is optionally a metal cation (eg, sodium, potassium, lithium, etc.), an ammonium cation or a substituted ammonium cation. This group includes alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates. Specific examples of substituted ammonium cations trimethylammonium and include methyl, quaternary ammonium dimethyl, and cations, e.g.

for use according to natural or chain types, tetramethylammonium and dimethylpiperidinium and cations derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants are C _i2 to C ₈ alkyl polyethoxylate (1.0) sulfate, C12-Cis alkyl polyethoxylate (2.25) sulfate, C12-Cis alkyl polyethoxylate (3.0) sulfate, and C12-Cis alkyl polyethoxylate (4.0) sulfate wherein M is selected from sodium and potassium. The surfactants of the present invention can be made from synthetic alcohol sources. Lengths average hydrocarbon distribution including branching.

In addition, and preferably, the surfactant is a mid-chain branched alkyl sulfate, a mid-chain branched alkyl alkoxylate, or a mid-chain branched alkyl alkoxylate sulfate. These surfactants are further described in No. 60/061 971, Attorney File 6881P, October 14, 1997, No. 60/061 975, Attorney File 6882P, October 14, 1997, No. 60/062 086, No. 6883P, 14 October 1997, No 60/061 916, 6884P, 14 October 1997, No 60/061 970, 6885P, 14 October 1997, No 60 / 062 407, attorney file 6886P, October 14, 1997. Other suitable mid-chain branched surfactants can be found in US Patent Application Serial Numbers 60/032 035 (file no. 6401P), 60/031 845 (file no.

No. 6402P), 60/031 916 (File No. 6403P), 60/031 917

No. 6404P), 60/031 761 (file no.

No. 6406P) and 60/031 844 (branched surfactants with conventional linear surfactants are also suitable for use in the present compositions.

6405P), 60/031 762

No. 6409P). Mixtures (the file (the file of these) are modified

Some suitable

Other preferred anionic surfactants are alkylbenzene sulfonate surfactants or MLASs.

MLAS surfactants, methods for their preparation, and examples of compositions are further described in commonly-assigned U.S. Pat. Patent Applications Serial Nos. 60/053 319 (File No. 6766P), 60/053 318 (File No. 6767P), 60/053 321 (File No. 6768P), 60/053 209 (File No. 6769P), 60 / 053 328 (file no. 6770P), 60/053 186 (file no. 6771P), 60/055 437 (file no. 6796P), 60/105 017 (file no. 7303P) and 60/104 962 (file no. 7304P).

Examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents," (Vol. I and II, Schwartz, Perry and Berch).

Non-ionic detergent surfactants

Suitable nonionic detergent surfactants are generally described in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6, which is incorporated herein by reference. Examples of non-limiting groups of useful nonionic surfactants include: amine oxides, alkyl ethoxylate, alkanoyl glucosamide, alkyl betaines, sulfobetaine, and mixtures thereof.

Amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides containing one alkyl group of 10 to 18 carbon atoms and two groups selected from the group consisting of alkyls and hydroxyalkyls of 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl group of 10 to 18 carbon atoms and two groups selected from the group consisting of alkyls and hydroxyalkyls of 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl group of 10 to 18 carbon atoms and a group selected from the group consisting of alkyls and hydroxyalkyls of 1 to 3 carbon atoms.

• · · · · · · · · · · · ·

Semi-polar nonionic detergent surfactants include amine oxide surfactants:

O

R ³ (OR ⁴ ) -N- (R ⁵ ) ₂ wherein R ³ is alkyl, hydroxyalkyl or alkylphenyl or mixtures thereof of 8 to 22 carbon atoms; R ⁴ is an alkylene or hydroxyalkylene of 2 to 3 carbon atoms or a mixture thereof; x is 0 to 3; and each of R ⁵ is alkyl or hydroxyalkyl of 1 to 3 carbon atoms or polyethylene oxide of 1 to 3 ethylene oxide groups. The R ⁵ groups are optionally linked to one another, eg via an oxygen atom or a nitrogen atom, to form a cyclic structure.

These amine oxide surfactants in particular include _Clo-Ci8 alkyl dimethyl amine oxides and Cs to C12 alkoxyethyldihydroxyethylaminoxidy. Preferably, the amine oxide is present in the composition in an effective amount, more preferably in an amount of 0.1% to 20% by weight, even more preferably 0.1% to 15% by weight, and most preferably 0.5% to 10% by weight.

Of the polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols, polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkylphenols bearing alkyl of 6 to 12 carbon atoms in a straight or branched configuration with alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount of 5 moles to 25 moles of ethylene oxide per mole of alkyl phenols. Commercially available nonionic surfactants of this type include Igepal® CO-630, marketed by GAF Corporation; and Triton® X-45, X-114, X-100 and X-102, all of which are sold by the Rohm & Haas Company. These compounds are generally referred to as alkylphenolalkoxylates (e.g.

alkylphenol ethoxylates).

In the case of the condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide, the alkyl chain of the aliphatic alcohol is straight or branched, primary or secondary, and generally consists of 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols bearing alkyl having 10 to 20 carbon atoms with 2 to 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ~ 15-S-9 (the condensation product of C _at C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol ~ 24-L-6 NMW (the condensation product of C12-C24 primary alcohol with 6 moles of narrow molecular weight ethylene oxide), both sold by Union Carbide Corporation; Neodol® 45-9 (condensation product of C14 to C15 linear alcohol with 6 moles of ethylene oxide), Neodol® 23-6,5 (condensation product of C12 to C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (condensation product) C _i4 to C15 linear alcohol with 7 moles of ethylene oxide), Neodol 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide) marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide ) sold by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8® sold by Shell Chemical Company and Genapol UD-080® sold by Hoechst. This category of nonionic surfactants is commonly referred to as "alkyl ethoxylates.

Preferred alkyl polyglycosides are:

R ² O (C _n H 2 _n O ( _t (glycosyl)) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyls consist of 10 to 18, preferably 12 to 14 n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; and x is 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7. In the preparation of these compounds, an alcohol or an alkylpolyethoxy alcohol is first formed and then reacted with a glucose or a source of glucose to form a glucoside (attachment at 1-). glycosyl units can then be attached by combining their 1- and 2-, 3-, 4- and / or positions

6- the preceding glycosyl units, preferably mainly the 2- position.

Fatty acid amide surfactants are:

O

JI 7 R ^? CN (R ⁷ ) ₂ wherein R ⁶ is alkyl consisting of 7 to 21 (preferably 9 to 17) carbon atoms and each R ⁷ is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and - ( C ² H ⁴ O) _X H, wherein x is 1 to 3.

Preferred amides are C ₂ to C of ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.

Preferably, nonionic surfactants, when present in the composition, are used in an effective amount, preferably 0.1% to 20% by weight, more preferably 0.1% to 15% by weight, and most preferably 0.5% to 10% by weight .

Surfactants based on polyhydroxy fatty acid amides

Optionally, the detergent compositions of the present invention also comprise an effective amount of a polyhydroxy fatty acid amide surfactant. An effective amount means that in preparing the composition, the amount of polyhydroxy fatty acid amide added to the composition can be selected to improve the cleaning performance of the detergent composition. In general, the use of 1% by weight of polyhydroxy fatty acid amide will improve cleaning efficiency in common use.

The detergent compositions of the present invention typically comprise 1% by weight of a polyhydroxy fatty acid amide surfactant, preferably 3% to 30% by weight of a polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant comprises the compound:

• »pour o

₂ II

R-CNZ wherein R ¹ is hydrogen, C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C ₂ alkyl, most preferably C 1 alkyl (ie methyl); and ^R2 is a C5-C31 hydrocarbyl, preferably C7 -C19 alkyl or alkenyl, straight chain, more preferably a Cg-C17 alkyl or alkenyl, most preferably straight chain Cll-C15 alkyl or alkenyl chain or mixtures thereof; and Z is a polyhydroxy hydrocarbon having a linear hydrocarbon chain bearing at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar by a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. In addition to these individual sugars, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup may be used as starting materials. These corn syrups eventually result in a mixture of sugar components such as Z. It should be understood, however, that this does not exclude other suitable raw materials. Z is preferably selected from the group

-CH ₂ - (CHOH) _n -CH ₂ OH consisting of

-CH (CH ₂ OH) - (CHOH) _n -CH ₂ OH, -CH ₂ - (CHOH) ₂ (CHO ₂ ) (CHOH) -CH ₂ OH, and their alkoxylated derivatives, wherein n is an integer from 3 to 5, inclusive, and R 'is hydrogen or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially -CH ₂ - (CHOH) ₄ -CH ₂ OH.

R 'is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ² -CO-N? Is, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallow acid amide, etc.

An amination reaction

N-alkylpolyhydroxyamine N-alkylpolyhydroxyamine

Z is 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,

1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive manner to form the corresponding and then reacting with an fatty aliphatic acid ester or triglyceride in a condensation / amidation step to form a N-alkyl, 17-polyhydroxy fatty acid amide. acid. Methods for making polyhydroxy fatty acid amide compositions are described, for example, in G.B. No. 809,060, Thomas Hedley & Co., Ltd., issued Feb. 18, 1959; No. 2,965,576, E.R. Wilson, issued December 20, 1960; U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955; No. 1,985,424, Piggot, issued May

On December 25, 1934, all of which are incorporated herein by reference.

Diaminy

Preferred liquid detergent compositions, such as mild soil contamination (LDL) compositions useful in the methods of the present invention optionally further comprise one or more diamines, preferably such an amount of diamine that the ratio of anionic surfactant to diamine present is 40: 1 to 2 : 1. These diamines allow improved grease and greasy food residue removal while maintaining an appropriate level of lather.

Diamines suitable for use in the compositions of the present invention are:

R ^{2 ',} R ^20' / NXN wherein each R ²⁰ is independently selected from the group consisting of hydrogen, C 1 to C ₄ linear or branched alkyl, alkyleneoxy:

- (R ²¹ O) _y R ²² wherein R ²¹ is C 2 to C 4 linear or branched alkylene and mixtures thereof; R ²² is hydrogen, C ₄ -C ₄ alkyl, and mixtures thereof; y is 1 to 10; X is a unit selected from:

i) C3-C10 linear alkylene, C 3 to C ₀ branched alkylene, C3 C3.0 cyclic alkylene, C3-C10 branched cyclic alkylene, alkyleneoxyalkylene:

- (R ²¹ O) _y R - wherein R ^{21 and} y are as defined above;

ii) C 3 to C 10 linear alkylene, C 3 to C 10 branched alkylene, C 3 to C 10 cyclic alkylene, C ₃ to C 10 branched cyclic alkylene, C 6 to C 10 arylene, the unit comprising one or more electron delivery groups or electron withdrawing groups to cause that said diamine has a pK _and greater than 8; and iii) mixtures i) and ii) provided that said diamine has a pK _and at least 8.

Preferred diamines of the present invention have pK ₂ and pK ₂ , both in the range of 8 to 11.5, preferably in the range of 8.4 to 11, and even more preferably 8.6 to 10.75. For purposes of the present invention the term _"pK equivalent to" pK i "PK _second The term pK _a is used in the present invention and throughout the application in the same manner as those skilled in the art. _PKa values can be readily obtained from standard literature sources, for example, "Critical Stability Constants: Volume 2, Amines by Smith and Martel, Plenum Press, NY and London (1975).

As defined in the present invention, pK _and diamines are reported as being measured in aqueous solution.

· ··· ···· · · · · · ·············· · · · · · · · · · · · · · · · · · · při · at 25 As used in the present invention, the pK _a is an equilibrium constant dependent on temperature and ionic strength, and therefore, the values reported in the literature not measured under these conditions may not be consistent with the values disclosing the present invention. To avoid confusion, the corresponding conditions and / or references used for pK _and in the present invention are the same as defined in Critical Stability Constants: Volume 2, Amines. One typical measurement method is potentiometric titration of acid with sodium hydroxide and pK determination, _{and by} suitable methods as described in The Chemist's Ready Reference Handbook, Shugar and Dean, McGraw Hill, NY, 1990.

Preferred diamines in terms of potency and availability are 1,3-bis (methylamino) cyclohexane,

1,3-diaminopropane (ρΚχ = 10.5; pK ₂ - 8.8), 1,6-diaminohexane (ρΚχ = 11; pK ₂ = 10), 1,3-diaminopentane (Dytek EP) (ρΚχ = 10, 5, pK ₂ = 8.9), 2-methyl-1,5-diaminopentane (Dytek A) (ρΚχ = 11.2; pK ₂ = 10.0). Other preferred materials are primary / primary diamines having C ₄ to C ₈ alkylene linkages. In general, primary diamines are more preferred than secondary and tertiary diamines.

The following are non-limiting examples of diamines suitable for use in the present invention.

1-N, N-dimethylamino-3-aminopropane:

1,6-diaminohexane:

1,3-diaminopropane:

2-methyl-1,5-diaminopentane:

· * · * * <<<<<<<<<<<<<<<<<<

.

1,3-diaminopentane available under the trade name Dytek EP:

1,3-diaminobutane:

Jeffamin EDR 148, a diamine having an alkyleneoxy backbone:

, NH "

3-Methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine):

and 1,3-bis (methylamino) cyclohexane:

Additional detergent ingredients

The following are non-limiting examples of additional detergent ingredients useful in bleaching compositions, in particular the laundry detergent compositions of the present invention, which include builders, optical brighteners, soil release polymers, color transfer inhibiting agents, dispersants, enzymes, suds suppressors, dyes , fragrances, filler salts, hydrotropes, photoactivators, fluorescent agents, fabric conditioners, hydrolysable surfactants, preservatives, antioxidants, chelating agents, stabilizers, anti-shrinkage agents, anti-crease agents, germicides, fungicides, anti-corrosion agents and mixtures thereof.

Fillers

The bleaching compositions of the present invention preferably comprise one or more detergent builders or builder systems. If present, the compositions typically comprise at least 1% by weight of a builder, preferably 5% by weight, more preferably 10% to 80% by weight, preferably up to 50% by weight, and even more preferably up to 30% by weight of the detergent builder.

The amount of filler will depend on the end use of the composition and the desired physical form. If present, the compositions typically comprise at least 1% by weight of the filler. The compositions typically comprise from about 5% to about 50%, more typically from about 5% to about 30%, by weight of the detergent builder. Granular compositions typically comprise from about 10% to about 80%, more typically from about 15% to about 50%, by weight of the detergent builder. However, lower amounts of filler are not excluded.

Inorganic or phosphorous-containing detergent builders include, but are not limited to, alkali metal, ammonium, and alkanolammonium salts of polyphosphates (such as tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including hydrogene) ), sulfates and aluminosilicates. However, phosphorus-free fillers are required in some areas. Importantly, the compositions of the present invention work surprisingly well even in the presence of "weak fillers (as compared to phosphates), such as" ··········· · o · · · o / ·········································· it occurs with zeolite or layered silicate builders.

Examples of silicate builders are alkali metal silicates, especially those having a SiO 2: Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates such as sodium layered silicates described in US Patent 4,664,839 to Rieck , issued May 12, 1987. NaSKS-6 is a trademark for crystalline layered silicate sold by Hoechst (generally abbreviated to "SKS-6" in the present invention). Unlike zeolite builders, NaSKS-6 silicate builder does not contain aluminum, NaSKS-6 has 5-Na ₂ SiO ₅ morphological form of layered silicate. It can be made by the processes described in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use in the present invention, but other embodiments of the present invention may be used layered silicates such as NaMSi _x O2x + iH ₂ O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Various other layered silicates from Hoechst companies include NaSKS-6, NaSKS-7 and NaSKS-11 in α, β, and y forms. As mentioned above, for use in the present invention, 6-Na ₂ SiC> 5 (form NaSKS-6) is most preferred. Other silicates can also be used, such as magnesium silicate, which can be used as a brittle-enhancing agent of granular compositions, as a stabilizer for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkali metal and alkaline earth metal carbonates described in German Patent Application No. 2,321,001, issued November 15, 1973.

Aluminosilicate builders are also useful in the present invention. Aluminosilicate builders are very important in the best-selling granular detergent compositions intended for heavy soiling and may also be an important builder component in liquid detergent compositions. Aluminosilicate builders include:

[M _z (zA10 ₂ ) _y ] · Η ₂ 0 where z and y are integers of at least 6, the molar ratio of z to y is 1.0 to 0.5 and x is an integer of 15 to 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates are crystalline or amorphous structures and are natural aluminosilicates or synthetically obtained aluminosilicates. Methods for making aluminosilicate ion exchange materials are described in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the designations Zeolite A, Zeolite P (Β), Zeolite MAP and Zeolite X. In a particularly preferred embodiment is an aluminosilicate ion exchange material:

Nai 2 [(AlO ₂ ) i ₂ (SiO ₂ ) 12] · χΗ ₂ 0 where x is 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 to 10) can also be used in the present invention . Preferably, the aluminosilicates have a particle size of between 0.1 microns and 10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having many carboxylate groups, preferably at least three carboxylates. The polycarboxylate builder can generally be added to the composition in the form of an acid, but can also be added in the form of a neutralized salt. When used in salt form, alkali metal salts such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Polycarboxylate builders include a wide variety of categories of useful materials. One important category of polycarboxylate builders includes ether polycarboxylates

Including oxydisuccinate as described in U.S. Pat. No. 3,128,287, Berg, issued Apr. 7, 1964; No. 3,635,830, Lamberti et al., issued Jan. 18, 1972; No. 3,936,448, Lamberti, issued Feb. 3, 1976. See also &quot; TMS / TDS fillers of U.S. Pat. No. 4,663,071, Bush et al., issued May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Pat. U.S. Patent 3,923,667, Rapko, issued Dec. 2, 1975; U.S. Pat.

Crutchfield et al., Issued 19th Patent 4,120,874, Crutchfield et al. Patent 4,158,635, June 1979; U.S. Pat.

1,3,5-trihydroxycyclohexyloxy-issued 17 October 1978; and U.S. Pat. No. 4,102,903 issued to Crutchfield et al

July 25, 1978.

Other useful detergent builders include ether hydropolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, benzene-2,4,6-trisulfonic acid and succinic acid, various alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

Particularly important for heavy-duty liquid detergent compositions are citrate builders, such as citric acid and its soluble salts, as they are available from renewable sources and are biodegradable. Citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicate builders. Oxydisuccinates are also very suitable for use in such compositions and combinations thereof.

Also suitable for the bleaching compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related

4 4 «4 4 4 ·· • 4 4 4 4 4 4 4 4 4 4444 44 ·

44444 »444444

The compounds described in U.S. Patent 4,566,984, Bush, issued Jan. 28, 1986. Applicable fillers based on succinic acid include C ₅ to C ₂ alkyl and alkenyl succinic acids and their salts. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinates are preferred fillers from this group and are described in European ed

No. 86200690.5 / 0 200 263, patent application, Nov. 5, 1986.

Other suitable polycarboxylates are described in U.S. Pat. No. 4,144,226, Crutchfield et al., issued March 13, 1979; No. 3,308,067, Diehl, issued Mar. 7, 1967. See also U.S. Pat. U.S. Patent 3,723,322 to Diehl.

Fatty acids, e.g., C ₁₂ to C ₁₈ monocarboxylic acids, can also be used in the compositions alone or in combination with the aforementioned fillers, especially citrate and / or succinate builders, thereby providing increased filler activity. Such use of fatty acids will generally result in a decrease in foaming, which must be taken into account when formulating the compositions.

In the situation where phosphorus-based fillers can be used, and in particular in the manufacture of pieces of laundry detergent compositions, various alkali metal phosphates such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

Chelating agents

The bleaching compositions of the present invention optionally also comprise one or more iron and / or manganese chelating agents. Tissue chelating agents may be selected from the group consisting of

• ♦ · * ♦ ♦ 4 11 r 11 · r ♦

U 4

ΊΙ consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which are defined below. Without wishing to be bound by theory, it is believed that the utility of these materials lies in part in their exceptional ability to remove iron ions and manganese ions from washing solutions by forming soluble chelates.

Examples of suitable chelating agents and the amounts in which they are used are described in U.S. Pat. Nos. 5,576,282 and 5,728,671.

A preferred biodegradable chelator for use in the present invention is ethylenediamine disuccinate ("EDDS"), in particular the [S, 5] isomer described in U.S. Pat. No. 4,704,233, Hartman and Perkins, Nov. 3, 1987.

The compositions of the present invention also optionally comprise water-soluble salts of methylglycine di-acetic acid (MGDA) (or its acid form) as a chelating agent or as a glue useful, for example, together with insoluble builders such as zeolites, layered silicates and the like.

When used, these chelating agents generally comprise from 0.1% by weight of the bleaching compositions of the present invention to up to 15% by weight, more preferably up to 3.0% by weight of the bleaching compositions of the present invention.

Color transfer inhibiting agents

Optionally, the bleaching compositions of the present invention also comprise one or more compounds that act as color transfer inhibiting agents to prevent color transfer from one fabric to another when solubilizing and suspending dyes that occur during fabric washing and treatment involving color fabrics.

Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone

4 · 9 9 9 c c kop c N- c c c c c c c c c c c c polymer polymers, polyamine-N-oxide polymers, copolymers N- vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are described in U.S. Pat. U.S. Patent Nos. 5,707,950 and 5,707,951.

Other suitable dye transfer inhibiting agents include, but are not limited to, crosslinked polymers. Crosslinked polymers are polymers whose backbone is interconnected to some degree; these linkers are of a chemical or physical nature, optionally with active groups on the backbone or in the branches. Crosslinked polymers have been described in Journal of Polymer Science, Vol. 22, pages 1035 to 1039.

In one embodiment, the crosslinked polymers are made to form a three-dimensional solid structure that captures colors into the pores formed by the three-dimensional structure.

In another embodiment, the crosslinked polymers capture the colors by swelling.

Suitable cross-linked polymers are described in co-pending European patent application 94870213.9.

The addition of such polymers will also improve the efficiency of the enzymes in the bleaching compositions of the present invention.

The dye transfer inhibiting agents have the ability to complex or volatile dyes washed out of the colored fabrics before the dyes are able to act on other washed fabrics.

When present in the bleaching compositions of the present invention, the dye transfer inhibiting agents are used in amounts of 0.0001% by weight, more preferably 0.01% by weight, most preferably 0.05% by weight of the bleaching compositions up to 10% by weight, more preferably 2% by weight and most preferably 1% by weight of bleaching compositions.

• · · · · · · · · · · · ·

13.

Dispersants

The bleaching compositions of the present invention optionally also contain dispersants. Suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, in which the polycarboxylic acid contains at least two carboxyl residues separated from each other by not more than two carbon atoms.

Polymers of this type are described in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 200 to 5000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of 1000 to 100 000.

In particular, acrylate / methacrylate copolymers such as 48ON having a molecular weight of 4000 in an amount of 0.5% to 20% by weight of the composition can be added to the detergent compositions of the present invention.

The compositions of the present invention optionally comprise a lime soap peptizing compound having a lime soap dispersing force (LSDP) as defined below, not more than 8, preferably not more than 7, most preferably not more than 6. The lime peptizing compound the soap is preferably used in an amount of 0% by weight to 20% by weight.

The numerical performance of the lime soap peptizer is given by the lime soap dispersing force (LSDP), which is determined using the lime soap dispersion test as described in H.C. Bogherty and C.A. Bergman, J. Am. Oil. Chem. Soc., Vol. 27, pages 88-90 (1950). This method of lime soap dispersion test is widely used in the art, as can be seen, for example, from the following review articles: W.N. Linfield, Surfactant Science Series, Vol. 7, page 3; W.N. Linfield, Tenside Surf. det., Vol. 27, pp. 159-163 (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Volume 104, pages 71-73 (1989). LSDPs are the percent by weight of dispersant to oleate by weight of the dispersant to oleate needed to disperse the lime soap formed from 0.025 g of sodium oleate in 30 ml of water containing 333 ppm of CaCl2 (Ca: Mg = 3: 2) equivalent hardness.

Surfactants that have a good ability to peptize lime soap include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Examples of surfactants having an LSDP of not more than 8 for use in the present invention include C ₁₆ to C ₁₈ dimethylamine oxide, C ₁₂ to C ₁₈ degree of ethoxylation of 1 to alkyl ethoxy sulfate surfactants (LSDP = 4) and C ₄ to alkyl ethoxy sulfates with an average of 5, in particular C12 ₁₅ with a degree of ethoxylation of 3

C15 ethoxylated alcohols with an average degree of ethoxylation of 12 (LSDP = 6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 by BASF GmbH.

Polymeric lime soap peptizers suitable for use in the present invention are described in M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Vol. 104, pages 71-73 (1989).

Hydrophobic bleaches such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [IV-decanoyl-6-aminohexanoyl] benzenesulfonate and mixtures thereof, and nonanoyloxybenzenesulfonate together with hydrophilic / hydrophobic bleaching agents.

Enzymes

In addition to the amylase of the present invention, the bleaching compositions additionally optionally contain one or more detergent enzymes which have a cleaning effect and / or have a positive fabric care effect. Such enzymes include proteases, amylases, cellulases, and lipases. They can be used in the non-aqueous liquid bleaching compositions of the present invention in the form of suspensions. Other suitable types of enzymes include those which are in the form of an enzyme suspension in nonionic surfactants, such as enzymes sold by Novo Nordisk under the trade name "SL" or microencapsulated enzymes sold by Novo Nordisk under the trade name "LDP." Suitable enzymes and amounts thereof are described in U.S. Pat. No. 5,576,282.

Enzymes added to the compositions of the present invention in the form of conventional enzyme powders are particularly preferred for use herein. Such powders generally have a size of 100 micrometers to 1000 micrometers, more preferably 200 micrometers to 800 micrometers, and can be suspended in the non-aqueous liquid phase of the composition. It has been found that these powders in the compositions of the present invention, in comparison with other forms of enzymes, exhibit particularly good enzyme stability in terms of maintaining enzyme activity over a period of time. Therefore, such compositions need not include conventional enzyme stabilizers, which otherwise need to be frequently used when the enzymes are used in aqueous liquid detergent compositions.

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, tanliosases, pullilanases, pullilanases, pullilanases, pullilanases, pullilanases malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, lactases, known amylases, mannanases, xyloglucanases and mixtures thereof. A preferred combination is a bleaching composition comprising a mixture of commonly used enzymes such as protease, lipase, cutinase and / or cellulase together with the amylase of the present invention.

Examples of such suitable enzymes are described in U.S. Pat. U.S. Patent Nos. 5,576,282, 5,728,671, and 5,707,950.

Suitable proteases are subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (substilisin BPN and BPN '). One suitable protease is obtained from a Bacillus strain, has a maximum activity at a pH in the range of 8-12, and was developed and marketed as ESPERASE® by Nono Industries A / S of Denmark, hereinafter referred to as &quot; Novo. The preparation of this enzyme and analogous enzymes is described in GB 1 243 784, Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal-modified protein) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed

On April 28, 1987 (in particular pages 17, 24 and 98), which are referred to in the present invention as "Protease B," and in European patent application 199 404, Venegas, issued

October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, which in the present invention is referred to as "Protease A. Preferably, the enzyme is referred to in the present invention" Protease C, which is a variant of an alkaline serine protease from Bacillus in which the lysine at position 27 is replaced by arginine, the tyrosine at position 104 is replaced by valine, the serine at position 123 is replaced by asparagine, and the alanine at position 274 is replaced by threonine. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Genetically engineered variants, particularly protease C, also fall within the scope of the present invention. See also high pH protease from Bacillus strain NCIMB 40338 described in WO 93/18140 A, Novo. Enzyme detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A, Novo. If desired, a protease having reduced adsorption and increased hydrolysability is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-type protease for detergents suitable in accordance with the present invention is described in WO 94/25583, Novo.

More specifically, the protease referred to as "Protease D is a carbonyl hydrolase variant having a non-natural amino acid sequence that is derived from a carbonyl hydrolase precursor by replacing different amino acids with other amino acid residues at a position corresponding to +76 in the original carbonylhydrolase, preferably in combination with one or more amino acid residues at positions corresponding to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, + 135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 corresponding Bacillus subtilisin numbering amyloliquefaciens as described in WO 95/10615, issued April 20, 1995, to Genencor International. Also suitable for the present invention are the proteases described in patent application EP 251 446 and WO 91/06637 and the BLAP® protease described in WO 91/02792. Proteolytic enzymes are used in the bleaching compositions of the present invention in an amount of 0.0001% by weight to 2% by weight, preferably 0.001% by weight to 0.2% by weight, more preferably 0.005% by weight to 0.1% by weight of pure enzyme per weight of composition.

Useful proteases are also described in PCT publications: WO 95/30010, published November 9, 1995, The Procter & Gamble Company; WO 95/30011, issued November 9, 1995 to The Procter & Gamble Company; WO 95/29979, issued November 9, 1995 to The Procter & Gamble Company.

Other particularly useful proteases are multiple substituted protease variants comprising substituting an amino acid residue for another natural amino acid at a position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with an amino acid substitution by another natural amino acid at one or more positions

corresponding positions 1, 3, 4, 8, 9 10, 12, 13, 16, 17, 18, 19, 20, 21, 22 , 24, 27 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72 , 75, 76 77, 78, 79, 86, 87, 89, 97, 98, 99,

101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121

123, 126, 128, 130, 131, 133, 147, 158, 159, 160, 166, 167, 183, 184, 185, 188, 192, 194, 210, 211, 212, 213, 214, 215, 228, 230, 232, 236, 237, 238, 247, 248, 249, 251, 252, 253, 260, 261, 262, 263, 265, 268,

Bacillus amyloli subtilisin

8 ··· · · · · · · ·  · · · • · · · · • · · · • · · • · · · · · 134, 137, 140, 141, 142, 146, 170, 173, 174, 177, 181, 182, 198, 203, 204, 205, 206, 209, 216, 217, 218, 222, 224, 227, 240, 242, 243, 244, 245, 246, 254, 255, 256, 257, 258, 259, 269, 270, 271, 272, 274 a 275 uefac iens; where when, that

the protease variant comprises an amino acid residue substitution at positions corresponding to positions 103 and 76, then also comprises an amino acid residue substitution at one or more positions other than positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisin and / or multiple substituted protease variants comprising amino acid substitution for another natural amino acid at one or more positions corresponding to positions 62, 212, 230, 232 , 252 and 257 of Bacillus amyloliquefaciens subtilisin, as described in PCT Publication Nos. WO 99/20727, WO 99/20726 and WO 99/20723, all The Procter & Gamble Company.

More preferably, the protease variant comprises a series of substitutions selected from the group consisting of:

12/76/103/104/130/222/245/261;

62/103/104/159/232/23 6/245/248/2 52;

62/103/104/159/213/232/236/245/248/252;

62/101/103/104/159/212/213/232/236/245/248/252;

68/103/104/159/232/236/245;

68/103/104/159/230/232/236/245;

68/103/104/159/209/232/236/245;

68/103/104/159/232/236/245/257;

68/76/103/104/159/213/232/236/245/260;

68/103/104/159/213/232/236/245/248/252; 68/103/104/159/183/232/236/245/248/252;

·························

TQ · · · ··· '-? ··· ·· · · * ·· ··· »

68/103/104/159/185/232/236/245/248/252;

68/103/104/159/185/210/232/236/245/248/252;

68/103/104/159/210/232/236/245/248/252;

68/103/104/159/213/232/236/245;

98/103/104/159/232/236/245/248/252;

98/102/103/104/159/212/232/236/245/248/252;

101/103/104/159/232/236/245/248/252;

102/103/104/159/232/236/245/248/252;

103/104/159/230/236/245;

103/104/159/232/236/245/248/252;

103/104/159/217/232/236/245/248/252;

103/104/130/159/232/236/245/248/252;

103/104/131/159/232/236/245/248/252;

103/104/159/213/232/236/245/248/252; and

103/104/159/232/236/245.

Even more preferred is a protease variant comprising a series of substitutions selected from the group consisting of:

12R / 76D / 103A / 104T / 130T / 222S / 245R / 261D;

62D / 103A / 104I / 159D / 232V / 236H / 245R / 248D;

62D / 103A / 104I / 159D / 213R / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 209W / 232V / 236H / 245R;

68A / 76D / 103A / 104I / 159D / 213R / 232V / 236H / 245R / 260A;

68A / 103A / 104I / 159D / 213E / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 183D / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 232V / 236H / 245R;

68A / 103A / 104I / 159V / 230V / 232V / 236H / 245R;

68A / 103A / 104I / 159D / 232V / 236H / 245R / 257V;

68A / 103A / 104I / 159D / 213G / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 185D / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 185D / 210L / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 210L / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 213G / 232V / 236H / 245R;

98L / 103A / 104I / 159D / 232V / 236H / 245R / 248D;

·· # ·· ······· · · ··· ·· ·· · «· ····

98L / 102A / 103A / 104I / 159D / 212G / 232V / 236H / 245R / 248D;

101G / 103A / 104I / 159D / 232V / 236H / 245R / 248D / 252K;

102A / 103A / 104I / 159D / 232V / 236H / 245R / 248D;

103A / 104I / 159D / 230V / 236H / 245R;

103A / 104I / 159D / 232V / 236H / 245R / 248D;

103A / 104I / 159D / 217E / 232V / 236H / 245R / 248D;

103A / 104I / 130G / 159D / 232V / 236H / 245R / 248D;

103A / 104I / 131V / 159D / 232V / 236H / 245R / 248D;

103A / 104I / 159D / 213R / 232V / 236H / 245R / 248D; and

103A / 104I / 159D / 232V / 236H / 245R.

The most preferred protease variant comprises a series of 101/103/104/159/232/236/245/248/252 substitutions, preferably 101G / 103A / 104I / 159D / 232V / 236H / 245R / 248D / 252K.

Cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, they have a pH optimum of 5 to 9.5. Suitable cellulases are described in U.S. Pat. No. 4,435,307 to Barbesgoard et al., which discloses fungal cellulase obtained from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2,095,275 and DE-OS-2,247,832.

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola grisea var. Thermoidea), in particular Humicola DSM 1800.

Other suitable cellulases are cellulases derived from Humicola insolens having a molecular weight of 50 kDa, an isoelectric point of 5.5 and consisting of 415 amino acids; and a 43 kDa endoglucanase obtained from Humicola insolens, DSM 1800, showing cellulase activity; a preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243. Also suitable are cellulases of EGIII from Trichoderma longibrachiatum described in WO 94/21801, Genencor, issued September 29, 1994. Particularly suitable cellulases are cellulases which have a positive effect on colors. Examples of such cellulases are cellulases described in European Patent Application No. 91202879.2, filed Nov. 6, 1991. Particularly useful are Carezym and Celluzy (novo Nordisk A / S). See also WO 91/17243.

Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing bleaching agents are described, for example, in U.S. Pat. U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950, PCT International Applications WO 89/099813, WO 89/09813, and European Patent Application No. 91202882.6, filed November 6, 1991, and EP No. 96870013.8, filed February 20, 1996. A laccase enzyme is also suitable.

Preferred transcription enhancers are substituted phenthiazine and phenoxazine 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinpropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3 to C5 substituted alkylsyringates) and phenols. Preferred hydrogen peroxide sources are sodium percarbonate and sodium perborate.

Said peroxidases are normally incorporated into the bleaching agent in amounts of 0.0001% by weight to 2% by weight of the active enzyme per weight of the bleaching agent.

Other preferred enzymes that can be used in the bleaching compositions of the present invention include lipases. Suitable lipase enzymes for use in detergents include those producing Pseudomonas family microorganisms, such as Pseudomonas stutzeri ATCC 19.154, which is described in British Patent 1,372,034. Suitable lipases include those that exhibit a positive immunological cross-reaction with an antibody to the lipase produced by Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P &quot; Amano, hereinafter referred to as &quot; Amano-P. Other suitable commercial lipases include

Amano-CES, Chromobacter viscosum lipases, e.g., Chromobacter viscosum lipases from U.S. Pat. Biochemical Corp., USA and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 LIPASE® and LIPOMAX® (Gist-Brocades) and LIPOLASE® and LIPOLASE ULTRA® (Novo), which are very effective when used in combination with the compositions of the present invention.

Cutinases [EC 3.1.1.50] are also suitable and can be considered a special kind of lipase, namely a lipase that does not require interphase activation. The addition of cutin to the bleaching compositions has been described, for example, in WO 88/09367 (Genencor).

Lipases and / or cutinases are normally used in bleaching compositions in an amount of 0.0001% by weight to 2% by weight of the active enzyme per weight of bleaching composition.

Known amylases and and / or β) can be used to remove sugar-based stains. WO 94/02597, Novo Nordisk A / S, issued February 3, 1994, discloses cleaning compositions in which mutant amylases are used. See also WO 94/18314, Genencor, issued August 18, 1994 and WO 95/10603, Novo Nordisk A / S, issued April 20, 1995. Other amylases known for use in bleaching compositions include α- and β-amylases. α-amylases are known in the art and include those described in US Patent 5,003,257, EP 252,666; WO 91/00353; FR 2,676,456; EP 285 123; EP 525,610; EP 368 341 and British Patent Application No. 1,296,839 (Novo). Other suitable amylases are the enhanced stability amylases including the PURAFACT OX AM® disclosed in WO 94/18314, published August 18, 1994 and WO 96/05295, Genencor, issued June 22, 1996, and the amylase variants from Novo Nordisk A / S described in WO 95/10603, issued April 1995.

Examples of commercial amylase products are TERMAMYL®, BAN®, FUNGAMYL® and DURAMYL®, all of which are available from Novo Nordisk A / S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases, characterized in that they have a specific activity at least 25% higher than that specific.

activity of TERMAMYL® in the temperature range of 25 ° C to 55 ° C and at pH values of 8 to 10, as measured by the Phadebas® α-amylase activity assay. Other amylolytic enzymes with improved activity properties and a combination of thermostability and higher activity are described in WO 95/35382.

The compositions of the present invention optionally also comprise a mannanase enzyme. Preferably, the mannanase is selected from the group consisting of: three mannanase degrading enzymes:

EC 3.2.1.78: endo-1,4-pmannosiase, referred to as' mannanase and β-mannosidase, is further

EC 3.2.1.25: dasa which polysacharas are

EC 3.2.1.100: 1,4-p-mannobiosidase and mixtures thereof. ("IUPAC Classification-Enzyme Nomenclature, 1992 ISBN 0-12-227165-3 Academic Press").

More preferably, the mannanase present in the compositions of the present invention is β-1,4-mannosidase (E.C. 3.2.1.78) referred to as mannanase. The term &quot; mannanase or &quot; galactomannanase refers to a mannanase enzyme defined according to the art, where it is officially named endo-1,4-β-mannosidase mannanate and has alternative names β-mannanase and enco-1,4-mannanase and catalyzes reactions: random hydrolysis 1 4? -D-mannoside linkages in mannan, galactomannan, glucomannan, and galactoglucomannan.

In particular, mannanases (EC 3.2.1.78) that break down mannans capable of cleaving polyose mannose units, i.e. capable of cleaving glycosidic bonds in mannan, glucomannan, galactomannan and galactoglucomannan. Mannanes are polysaccharides having a backbone composed of β-1,4 linked mannose; glucomannans are polysaccharides having a backbone of more or less regularly alternating β-1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with α-1,6 attached galactose form a group and refer to enzymes, chains containing side branches. These compounds are optionally acetylated.

The degradation of galactomannan and galactoglucomannan is facilitated by the total or partial removal of the galactose side branches. Further, the degradation of acetylated mannan, glucomannan, galactomannan, and galactoglucomannan is facilitated by total or partial deacetylation. Acetyl groups can be removed by alkaline or mannan acetylesterase. Oligomers released by mannanase or a combination of mannanase and α-galactosidase and / or mannanacetylesterase can be further degraded by liberating free maltose by β-mannosidase and / or β-glucosidase.

Mannanases have been detected in some Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol. 56, No. 11, pp. 3505-3510 (1990), describes β-mannanase obtained from Bacillus stearothermophilus in dimeric form having a molecular weight of 162 kDa and a pH optimum of 5.5 to 7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) discloses β-mannanase obtained from Bacillus subtilis with a molecular weight of 38 kDa and optimal activity at pH 5.0 and 55 ° C and a pH of 4.8. JP-03047076 discloses β-mannanase obtained from a 373 kDa Bacillus strain measured by gel filtration, a pH optimum of 8-10 and a pH of 5.3-5.4. JP-63056289 discloses the production of an alkaline thermostable β-mannanase which hydrolyzes β-1,4-D-mannopyranoside linkages in eg mannan and produces mannooligosaccharides. JP-63036774 describes a Bacillus FERM P-8856 microorganism that produces β-mannanase and β-mannosidase at alkaline pH. JP-08051975 discloses alkaline β-mannanases from the alkalophilic Bacillus AM-001 strain. Purified Bacillus amyloliguefaciens mannanase useful for bleaching pulp and paper, and a process for its preparation, is described in WO 97/11164. WO 91/18974 discloses a hemicellulase such as glucanase, xylanase or mannanase active at extreme pH and temperature. WO 94/25576 discloses an enzyme of Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity that can be used to degrade or treat cell wall material of plants or algae. WO 93/24622 discloses mannanase isolated from Trichoderma reseei useful for bleaching lignocellulose pulp. Hemicellulose capable of degrading mannan containing hemicellulose is described in WO 91/18974 and purified mannanase from Bacillus amyloliguefaciens is disclosed in WO 97/11164.

Preferably, the mannanase enzyme is an alkaline mannanase as defined below, more preferably it is a bacterial source mannanase. In particular, the laundry detergent composition of the present invention comprises an alkaline mannanase selected from mannanase from Bacillus agaradhaerens strain NICMB 40482; mannanases from Bacillus subtilis strain AAI12. The most preferred mannanase for use in the detergent compositions of the present invention is a mannanase enzyme obtained from a Bacillus sp. 1663, which is described in co-pending Danish patent application No. PA 1998 01340.

The term "alkali mannanase enzyme" includes an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of the maximum activity at a given pH in the range of 7 to 12, preferably 7.5 to 10.5.

Alkaline mannanase from Bacillus agaradhaerens NICM 40482 is disclosed in commonly-assigned U.S. Pat. Serial No. 09 / 111,256. More specifically, the mannanase is:

i) a polypeptide produced by Bacillus agaradhaerens NICM 40482; or ii) a polypeptide comprising the amino acid sequence set forth in positions 32 to 343 of SEQ ID NO. No. 2 disclosed in U.S. Pat. Serial No. 09 / 111,256; or (iii) an analogue of the polypeptide of (vi) or (ii) which is at least 70% homologous to or derived from the polypeptide by replacement, omission or addition of one or more amino acids or immunologically · Ft!!!!!!!!!! <<<<<«« «« ««!! «« * *! * * * * * * * Reactive with a polyclonal antibody raised against the polypeptide in purified form.

Also included is a corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising the sequence set forth in SEQ ID NO. No. 1, from nucleotide 97 to nucleotide 1029, as set forth in U.S. Pat. Serial No. 09 / 111,256;

(b) substances homologous to (a);

(c) polynucleotide molecules encoding a polypeptide having mannanase activity are at least 70% identical to amino acid sequence id. No. 2, from amino acid 32 to amino acid 343, as set forth in U.S. Pat. Serial No. 09 / 111,256;

(d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

Plasmid pSJ1667 containing a polynucleotide molecule (DNA sequence) encoding this mannanase was transformed into an Escherichia coli strain which was invented by the inventors under the Budapest Agreement on the International Recognition of Stored Microorganisms for Patent Procedure at Deutsche Sammlung von Microorganismen und Zellkulturen GmbH, Mascheroder Weg 1b. 38124 Braunschweig, Germany, May 18, 1998 under DSM 12180.

A second more preferred enzyme is Bacillus subtilis mannanase strain 168, which is described in co-pending U.S. Pat. More specifically, the mannanase is:

i) encoded by the coding portion of the DNA sequence set forth in SEQ ID NO. No. 5 disclosed in U.S. Pat. Serial No. 09 / 095,163 or an analogue thereof; and / or in v - * * 0 * t »r ·· 0 · 0000000 0 0 0000000 0 0 0 0

(Ii) a polypeptide comprising the amino acid sequence shown as SEQ ID NO: 040; No. 6 in U.S. Pat. Serial No. 09 / 095,163; or iii) an analogue of the polypeptide defined in ii) that is at least 70% homologous to or derived from the polypeptide by replacement, omission or addition of one or more amino acids or immunologically reactive with the polyclonal antibody raised against the polypeptide in purified form .

Also included is a corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising the sequence set forth in SEQ ID NO. No. 5, as disclosed in U.S. Pat. Serial No. 09 / 095,163;

(b) substances homologous to (a);

(c) polynucleotide molecules encoding a polypeptide having mannanase activity are at least 70% identical to amino acid sequence id. No. 2, as disclosed in U.S. Pat. Serial No. 09 / 095,163;

(d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

A third more preferred mannanase is described in Danish co-pending patent application PA 1998 01340. More specifically, the mannanase is:

i) a polypeptide produced by a Bacillus 1633 strain;

ii) a polypeptide comprising the amino acid sequence shown in SEQ ID NO. or (iii) an analogue of a polypeptide as defined in (vi) or (ii) which is at least 65% homologous to the polypeptide or derived from the polypeptide by substitution, omission or addition one or more amino acids or is immunologically.

reactive with a polyclonal antibody raised against the polypeptide in purified form.

Also included is a corresponding isolated polynucleotide molecule having mannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising the sequence set forth in SEQ ID NO. No. 1 from nucleotide 317 to nucleotide 1243 as disclosed in Danish application No. PA 1998 01340;

(b) substances homologous to (a);

(c) polynucleotide molecules encoding a polypeptide having mannanase activity are at least 65% identical to amino acid sequence id. No. 2 from amino acid 33 to amino acid 340 as disclosed in Danish Application No. PA 1998 01340;

(d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pBXM3 containing a polynucleotide molecule (DNA sequence) encoding mannanase according to the present invention was transformed into an Escherichia coli strain which was invented by the inventors under the Budapest Agreement on the International Recognition of Stored Microorganisms for Patent Procedure at Deutsche Sammlung von Microorganismen und Zellkulturen GmbH, Mascheroder Wegb. D-38124 Braunschweig, Germany, May 29, 1998 under the storage number DSM 12197.

A fourth more preferred mannanase is described in co-pending Danish patent application PA 1998 01341. More specifically, the mannanase is:

i) a polypeptide produced by a Bacillus AAI 12 strain;

ii) a polypeptide comprising the amino acid sequence shown in SEQ ID NO. No. 2 at positions 25-362 of Danish Application No. PA 1998 01341; or • iii) an analogue of the polypeptides defined in vi) or ii) which is at least 65% homologous to or derived from the polypeptide by replacement, omission or addition of one or more amino acids or immunologically reactive with a polyclonal antibody raised against the polypeptide in purified form.

Also included is a corresponding isolated polynucleotide molecule having mannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising the sequence set forth in SEQ ID NO. No. 1 from nucleotide 225 to nucleotide 1236 as disclosed in Danish application No. PA 1998 01341;

(b) substances homologous to (a);

(c) polynucleotide molecules encoding a polypeptide having mannanase activity are at least 65% identical to amino acid sequence id. No. 2 from amino acid 25 to amino acid 362 as disclosed in Danish Application No. PA 1998 01341;

(d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pBXM1 containing the polynucleotide molecule (DNA sequence) encoding mannanase according to the present invention was transformed into the Escherichia coli strain which was invented by the inventors under the Budapest Agreement on the International Recognition of Stored Microorganisms for Patent Procedure at Deutsche Sammlung von Microorganismen und Zellkulturen GmbH, Mascheroder Wegb. D-38124 Braunschweig, Germany, 7 October 1998 under the storage number DSM 12433.

Mannanase, if present, is used in the compositions of the present invention preferably in amounts of from 0.0001% to 2% by weight, more preferably from 0.0005% to 0.1% by weight, and most preferably from 0.001%, of the term "endoglucanase enzyme to hydrolyze % to 0.02% pure enzyme by weight of the composition.

The compositions of the present invention also optionally comprise a xyloglucanase enzyme. Xyloglucanases suitable for the purposes of the present invention are enzymes exhibiting xyloglucan-specific endoglucanase activity, preferably in an amount of 0.00% to 1% by weight, more preferably 0.01% to 0.5% by weight of the composition. As used in the present invention, activity refers to ability

1,4-β-D-glycosidic bonds present in any cellulosic material, such as cellulose, cellulose derivatives, lichenin, β-D-glucan or xyloglucan. Endoglucanase activity can be determined by methods known in the art, examples of which are described in WO 94/14953 and hereinafter. One unit of endoglucanase activity (eg, CMCU, AVIU, XGU, or BGU) is defined as the production of 1 pmole of reducing sugar per minute from a glucan substrate, with the glucan substrate being eg CMCU (CMCU), acid swollen Avicell (AVIU), xyloglucan (XGU) ) or cereal β-glucan (BGU). Reducing sugars are determined by the method described in WO 94/14953 and hereinafter. The specific endoglucanase activity to the substrate is defined as units per milligram of protein.

Suitable enzymes exhibiting endoglucanase activity (hereinafter referred to as "xyloglucan-specific") as the highest XGU activity, which is an enzyme which:

(i) is encoded by a DNA sequence containing or included at least one of the following partial sequences:

(and) ATTCATTTGT GGACAGTGGA C (SEQ ID NO . : 1 (b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2) (C) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3) (d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4) (E) TTAACATCTT TTCACCATGA (SEQ ID NO: 5) (F) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6)

• · · • · · · • · · · · 91 * A · * “· · · · · • · · • · · • · · · • · · · • · · • · · · · · • · • · • · · · • (G) GCCACCCTGG CTTCCGCTGC (sequence id. No: 7) (h) GACAGTAGCA ATCCAGCATT (sequence id. No: 8) (and) AGCATCAGCC GCTTTGTACA (sequence id. No: 9) (j) CCATGAAGTT CACCGTATTG (sequence id. No: 10) (to) GCACTGCTTC TCTCCCAGGT (sequence id. No: 11) (1) GTGGGCGGCC CCTCAGGCAA (sequence id. No: 12) (m) ACGCTCCTCC AATTTTCTCT (sequence id. No: 13) (n) GGCTGGTAG TAATGAGTCT (sequence id. No: 14) (O) GGCGCAGAGT TTGGCCAGGC (sequence id. No: 15) (P) CAACATCCCC GGTGTTCTGG G (SEQ ID NO . : 16) (q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCC

AGCCGACCGA

TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT

TCCCTTCTCT

CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG

CGGTCAGTGG

GATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA

GACGGCCGGC

ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACAATCGC

TTGTCACACC

AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID NO: 17) or (r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG

GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG

TGTTTCAGTC

CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA

GGAGACGCTG

TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT

CCTGTACATA

CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAAAAAAAAAAAA

AAAA (SEQ ID NO: 18) or a sequence homologous to said coding polypeptide specific for xyloglucan with endoglucanase activity, (ii) is immunologically reactive with an antibody to a highly pure endoglucanase encoded by the DNA sequence defined in (i) and derived from Aspergillus aculeatus, CBS 101.43, which is specific for xyloglucan.

More specifically, as used herein, the term "xyloglucan-specific" means that the endoglucanase enzyme exhibits the highest endoglucanase activity on the xyloglucan substrate and preferably less than 75% activity, more preferably less than 50% activity, most preferably less than 25% activity , to other substrates containing cellulose or other glucans.

Preferably, the specificity of endoglucanase to xyloglucan is further defined as the relative activity determined as the release of reducing sugars in optimal incubation of the enzyme with xyloglucan substrates. For example, the xyloglucan activity of conditions achieved and others tested can be defined as specificity for β-glucan activity (XBU / BGU), xyloglucan activity for carboxymethylcellulose activity (XGU / CMCU) or xyloglucan activity for acidic swollen activity of Avicell (XGU / AVIU) preferably greater than 50, such as 75, 90 or 100.

The term "derived from" as used herein not only refers to the endoglucanase produced by the CBS 101.43 strain, but also to the endoglucanase encoded by the DNA sequence isolated from the CBS 101.43 strain and produced in the host organism transformed with the DNA sequence. The term "homolog" as used herein refers to a polypeptide encoded by a DNA that hybridizes to the same probe as the DNA encoding the xyloglucan-specific endoglucanase enzyme under certain specific conditions (such as pre-soaking in 5xSSC and prehybridizing for 1 h at -40 ° C at solution of 5xSSC, 5xDenhardt solution and 50 µg of denatured bovine thymus DNA, followed by hybridization in the same solution supplemented with 50 µCi 32-P-dCTP labeled probe for 18 h at -40 ° C and washed three times in 2xSSc 0.2% SDS at 40 ° C for 30 minutes). More specifically, the term is intended to designate a DNA sequence that is at least 70% homologous to any xyloglucan-specific endoglucanase sequence cited above containing at least 75%, at least 80%, at least 85%, at least 90% or even 95% of any of the sequences listed above. The term is intended to include modifications to any of the DNA sequences listed above, such as a nucleotide replacement that does not result in another amino acid sequence of the polypeptide encoded by the sequence, but which corresponds to the use of a host organism codon into which a DNA construct containing any of the DNA sequences is inserted. , or nucleotide substitutions that result in a different amino acid sequence of the polypeptide encoded by the sequence, and therefore, optionally, result in a different protein structure that eventually results in an engoglucanase mutant with properties other than the natural enzyme. Other examples of possible modifications are inserting one or more nucleotides into the sequence, adding one or more nucleotides to one of the ends of the sequence, or omitting one or more nucleotides at one of the ends of the sequence or inside the sequence.

The xycloglucan-specific endoglucanase useful in the present invention is preferably one having an XGU / BGU, XGU / CMU and / or XGU / AVIU ratio (as defined above) of greater than 50, such as 75, 90 or 100.

In addition, the xyloglucan-specific endoglucanase is preferably substantially free of β-glucan activity and / or exhibits at most 25%, such as 10% or 5%, activity against carboxymethylcellulose and / or Avicell, wherein the activity against xyloglucan is 100%.

%. In addition, the endoglucase specific for the present invention is preferably devoid of transferase activity that has been observed with most endoglucanases specific for plant xyloglucan.

xyloglucan substantially preferred by specific endoglucanases desirable extensive

Xyloglucan-specific endoglucanase can be obtained from the fungal strain A. aculeatus described in WO 94/14953. Xyloglucan-specific microbial endoglucanases are also described in WO 94/14953. Xyloglucan-specific endoglucanases from rotlin have been described, but these enzymes have transferase activity and are therefore less compared to microbial to xyloglucan wherever xyloglucan is degraded. A further advantage of the microbial enzyme is that it can generally be produced in large quantities in microbial host cells, unlike enzymes of other origin.

The xyloglucanase, if present, is used in the compositions of the present invention preferably in an amount of 0.0001% by weight to 2% by weight, more preferably 0.0005% by weight to 0.1% by weight, and most preferably 0.001% by weight to 0.02% by weight % of pure enzyme by weight of the composition.

The above enzymes are optionally of any origin, such as vegetable, animal, bacterial, fungal and yeast. Purified or unpurified forms of these enzymes may be used. Also included in the definition are natural enzyme mutants. Mutants can be obtained, for example, by protein and / or genetic engineering techniques, by chemical and / or physical treatment of natural enzymes. Equally common practice is the expression of enzymes by host organisms in which the material responsible for enzyme production has been cloned.

Said enzymes are normally used in bleaching compositions in amounts of 0.0001% by weight to 2% by weight of active enzyme per weight of bleaching composition. Enzymes can be added as separate individual components (powders, granulates, stabilized fluids, etc. containing one enzyme) or as a mixture of two or more enzymes (eg cogranulates).

• ·

Other suitable enzyme components that can be added are substances that inhibit the oxidation of enzymes. Examples of such enzyme oxidation inhibiting agents are ethoxylated tetraethylene polyamines.

A variety of enzyme materials and a method for including them in synthetic bleaching compositions are also described in WO 93/07263 and WO 93/07260, Genencor International, WO 89/08694, Novo and U.S. Pat. No. 3,553,139, issued Jan. 5, 1971 to McCarthy et al. Enzymes are further described in U.S. Pat. No. 4,101,457, Place et al., issued July 18, 1978; No. 4,507,219, Hughes, issued Mar. 26, 1985. Enzyme materials useful in, and incorporation into, liquid detergent compositions are disclosed in U.S. Pat. No. 4,261,868, Hora et al., Apr. 14, 1981.

Enzyme stabilizers

Enzymes intended for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al., EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Pat. No. 3,519,570. A useful strain of Bacillus, sp. AC 13 providing proteases, xylanases and cellulases is described in WO 9 401 532, Novo. The enzymes useful in the present invention can be stabilized by the presence of water-soluble sources of calcium and / or magnesium ions in the final compositions which then provide such ions to the enzymes. Suitable enzyme stabilizers and the amounts in which they are used are described in U.S. Pat. No. 5,576,282.

Other Detergent Ingredients The bleaching compositions of the present invention optionally comprise one or a polymer dispersing agent of the present invention also more than one of the following ingredients: soil retardant and soil release agents; Brighteners, suds suppressors, dyes, fragrances, elasticizers, fabric softeners, carriers, hydrotropes, processing aids and / or pigments. Suitable examples of such other ingredients and their amounts can be found in U.S. Pat. No. 5,576,282.

Methods of cleaning

In addition to the methods of cleaning fabrics, dishes and other hard surfaces and body parts described in the present invention, the invention also includes treating fabrics that have been soiled or stained prior to washing involving direct contact of stains and / or dirt with the highly concentrated form of bleaching agent described above washing such fabrics using conventional aqueous laundry solutions. Preferably, the bleaching agent remains in contact with the dirt / stain for 30 seconds to 24 hours prior to washing the prewashed soiled / stained substrate in a conventional manner. More preferably, the prewash time is 1 minute to 180 minutes.

The following examples are given only as examples of the compositions of the present invention, but do not limit or otherwise define the scope of the present invention.

In the following examples, some abbreviations known to those skilled in the art are used.

DETAILED DESCRIPTION OF THE INVENTION

Synthetic examples

Example 1

Preparation of 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate (compound of structural formula 7)

Step 1

Preparation of dimethylbenzyl cyanide (compound of structural formula 2) 9

Dimethyl sulfoxide (200 mL) was poured into a 1 L three-necked, round-bottomed flask equipped with two dropping funnels, a Y cap, with an ammonium hydroxide, reflux condenser, stirrer, thermometer, and frit scattering feed gas, and cooled with an ice bath. Methyl chloride was introduced into the dimethylsulfoxide with stirring. After 15 minutes, sodium hydroxide (50% by weight in water, 32.9 g) and benzyl cyanide (compound was washed with a mechanical structural formula) were added dropwise from both dropping funnels simultaneously.

1,

11.7 g (1 equivalent) at a rate such that the temperature of the reaction mixture did not exceed 35 ° C. After the addition of sodium hydroxide and benzyl cyanide was complete, the reaction mixture was stirred at room temperature. Methyl chloride was further introduced into the reaction mixture for 1 h. After 1 h, the introduction of methyl chloride was complete (38.8 g total, 3.8 equivalents) and the reaction mixture was extracted with toluene (3 x 100 mL) and diethyl ether (100 mL). The combined organic layers were washed with saturated sodium bicarbonate solution (2 x 100 mL), saturated sodium chloride solution (100 mL), dried over sodium sulfate and evaporated to give compound of structural formula 2. This preparation corresponds to the following reaction:

(1)

Step 2

Preparation of 1-amino-2,2-dimethyl-2-phenylethane (compound of structural formula 3)

Diethyl ether (100 ml) was poured into a 250 ml three-necked round-bottomed flask equipped with a dropping funnel with side pressure equalization by-pass, argon inlet and reflux condenser and cooled in an ice bath. Powdered lithium aluminum hydride (3.68 g, equivalents) was then slowly added.

After the addition was complete, it was slowly running (compound

The reaction mixture was added dropwise with structural formula 2 (dimethylbenzyl cyanide 7.00 g, 1 equivalent) and allowed to warm to room temperature with stirring overnight. Water (7.0 mL) was added and after 15 minutes sodium hydroxide (15% solution in water, 7.0 g). The resulting mixture was stirred for 1h and then additional water (21.0 mL) was added. The reaction mixture was diluted with diethyl ether (100 mL) and filtered under reduced pressure. The filter cake was washed with diethyl ether (8 x 50 mL), and the combined organic layers were dried over magnesium sulfate and evaporated under reduced pressure to give compound of structural formula 3, reaction:

This preparation corresponds to the following

Step 3

Preparation of 4,4-dimethyl-3,4-dihydroisoquinoline (compound of structural formula 4)

In a 30 ml round bottom flask equipped with a magnetic stirrer and distillation apparatus was charged 1-amino-2,2-dimethyl-2-phenylethane (4.15 g, 1 equivalent) and formic acid (6.65 g, 3, 5 equivalents), the resulting mixture was stirred for 1 h at 100 ° C and then a further portion of formic acid (2 mL, 0.9 equivalents) was added. After stirring for an additional hour, the reaction mixture was heated to 200 ° C and the pressure was reduced. When excess unreacted formic acid and water were removed, the residual oil, N-formyl-β, β-β-γίιηθύΐιγί-β-β-phenethylamine, was cooled to room temperature.

In a 100 ml round bottom flask equipped with a Y-tip, dropping funnel and mechanical stirrer was added • 4 ·· · * · · · ·

4 4 · *

4 4 4

Polysulfic acid (29.7 g) and phosphorus pentoxide (4.74 g). The mixture was stirred and heated to 180 ° C for 1h and then cooled to 150 ° C. N-formyl-β, β-dimethyl-O-phenethylamine was melted and poured into a mixture of acids. The reaction mixture was warmed to 180 ° C and stirred overnight. The reaction mixture was then cooled to 60 ° C and slowly mixed with ice water (250 mL). The diluted reaction mixture was washed with diethyl ether (2 x 100 mL). The aqueous solution was cooled with an acetone / dry ice bath and a solution of potassium hydroxide in water was added. When the pH of the reaction mixture reached 9, the mixture was extracted with diethyl ether (4 x 100 mL). The organic layers were washed with pH 10 buffer (200 mL), dried over magnesium sulfate and evaporated under reduced pressure to give compound of structural formula 4. This preparation corresponds to

Step 4

Preparation of 1,2-decanediol cyclic sulfate (compound of structural formula 6).

A 500 ml three-necked round-bottomed flask fitted with a dropping funnel with side-bypass for pressure equalization, mechanical stirrer and reflux condenser was placed

1,2-decanediol (compound of structural formula 5, 8.72 g, 50.0 mmol) and 50 ml of carbon tetrachloride. After dissolution

1.2-decanediol was added dropwise at room temperature thionyl chloride (5.5 mL, 75 mmol) and the reaction mixture was heated to 60 ° C. After 2 h, the reaction mixture was cooled with an ice bath. Then water (50 mL) and acetonitrile (75 mL) were added. Then ruthenium chloride hydrate (0.131 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) were added and the reaction mixture was stirred for 1 hour at room temperature. Then * «

* © © • 4 4 • γ γ γ γ γ γ

100, the reaction mixture was extracted with diethyl ether (4 x 175 mL), the organic layers were washed with water (5 x 100 mL), saturated sodium bicarbonate solution (3 x 100 mL), saturated sodium chloride solution (2 x 100 mL), filtered through a mixture kieselguhr and silica gel and dried over magnesium sulfate. The clear liquid was evaporated to give the compound of Formula 6 as a clear oil. This preparation corresponds to the following reaction:

OH

HIM

Preparation of 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate (compound of structural formula 7)

In a 100 mL round bottom flask equipped with a magnetic stirrer was added 4,4-dimethyl-3,4-dihydroisoquinoline (2.45 g, 15.4 mmol) and acetonitrile (15.2 mL). To this solution was added 1,2-decanediol cyclic sulfate (compound of structural formula 6, 3.78 g, 16.0 mmol) all at once. The resulting reaction mixture was strongly thickened over 5 minutes, so additional acetonitrile (60 mL) was added. The reaction mixture was then stirred overnight. The precipitate was filtered off, washed with acetone and allowed to air dry to give the compound of formula 7. This preparation corresponds to the following reaction:

(7)

101 ** in V * 5 * <5 * 9 * «9» «concentrated»

Example 2

Preparation of 1- (3,3-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate (compound of structural formula 11)

Preparation of N-formyl-α, α-dimethyl-β-phenethylamine (compound of Structural Formula 9)

A 1 L 3-neck round bottom flask equipped with a thermometer, an ammonium hydroxide washer, a reflux condenser, a mechanical stirrer, and a side-by-side pressure equalizing funnel was poured into glacial acetic acid (83.0 mL) and then cooled with an ice bath. Sodium cyanide (16.3 g, 1 equivalent) and a solution of sulfuric acid in acetic acid (160 g / 83.0 mL) were added at a rate such that the temperature of the reaction mixture was less than 20 ° C. precautions to avoid contact with toxic gas). 2-Methyl-1-phenyl-2-propanol (compound of structural formula 8, 50.0 g, 1 equivalent) was then slowly added to the reaction mixture and the resulting mixture was stirred overnight at room temperature. The solution was then bubbled with argon for 3 h and poured into ice water (300 mL). The resulting oil layer was separated and stored. The aqueous layer was neutralized to pH 7 with sodium carbonate and extracted with diethyl ether (3 x 200 mL). The organic layers were combined with a previously separated oil, dried over magnesium sulfate and evaporated to give the compound of structural formula 9. This preparation corresponds to the following reaction:

(9)

· · ·

102

Step 2

Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline (compound of structural formula 10)

Polysulfuric acid (378 g) and phosphorous pentoxide (60.4 g) were charged to a 1-L three-necked round bottom flask equipped with a Y extension, dropping funnel, and mechanical stirrer. The mixture was stirred and heated to 180 ° C for 1 h and then cooled to 150 ° C. N-formyl-β, β-dimethyl-β-phenethylamine was melted and poured into a mixture of acids. The reaction mixture was warmed to 180 ° C and stirred overnight. Then the reaction mixture was cooled to 100 ° C and slowly mixed with ice water (2 L). The diluted reaction mixture was filtered through diatomaceous earth. The filtrate was washed with diethyl ether (2 x 100 mL). The aqueous solution was cooled with an acetone / dry ice bath and a solution of potassium hydroxide in water was added. When the pH of the reaction mixture reached 9, the mixture was extracted with diethyl ether (4 x 100 mL). The organic layers were washed with pH 10 buffer (200 mL), dried over magnesium sulfate and concentrated under reduced pressure to give the compound of structural formula 10. This preparation corresponds to the following reaction:

Italy (9)

Step 3

Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline tetrafluoroborate (compound of structural formula 11)

In a round-bottom flask equipped with a magnetic stirrer was added trimethyloxonium tetrafluoroborate (Meerwein's salt, 1.13 g, 7.7 mmol) and dichloromethane (15 mL) at 0 ° C. To this stirred solution was added a solution over 5 minutes

3,3-dimethyl-3,4-dihydroisoquinoline (1.11 g, 7.0 mmol) in dichloromethane (40 mL). The heterogeneous solution was allowed to warm to room temperature and allowed to stir overnight. The resulting solution was evaporated and ethanol was added to the resulting oil to cause crystallization of the compound of structural formula 11. This preparation corresponds to the following reaction:

Example 3

Preparation of 1,1-diphenyl-3-durylpseudoisoindolinium tetrafluoroborate (compound of structural formula 15)

Step 1

The preparation of 1,1-diphenyl-3-durylpseudoisoindole (compound of structural formula 12) was carried out as described in the art, for example in R.C. Fuson, J. Org. Chem., 16, 648 (1951).

Step 2

Preparation of 1,2-hexanediol cyclic sulfate (compound of structural formula 14).

A 500 ml three-necked round-bottomed flask fitted with a dropping funnel with side-bypass for pressure equalization, mechanical stirrer and reflux condenser was placed

1,2-hexanediol (compound of structural formula 13, 5.91 g, 50.0 mmol) and 50 ml of carbon tetrachloride. After dissolution

1.2-hexanediol was added dropwise at room temperature thionyl chloride (5.5 mL, 75 mmol) and the reaction mixture was heated to 60 ° C. After 2 h, the reaction mixture was cooled with an ice bath. Then water (50 mL) and acetonitrile (75 mL) were added. Then ruthenium chloride hydrate (0.131 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) were added and the reaction

The 104 mixture was stirred for 1 hour at room temperature. Then the reaction mixture was extracted with diethyl ether (4 x 175 mL), the organic layers were washed with water (5 x 100 mL), saturated sodium bicarbonate solution (3 x 100 mL), saturated sodium chloride solution (2 x 100 mL), filtered through a mixture kieselguhr and silica gel and dried over magnesium sulfate. The clear liquid was evaporated to give the compound of Formula 14 as a clear oil. This preparation corresponds to the following reaction:

Step 3

Preparation of 1,1-diphenyl-3-durylpseudoisoindolinium tetrafluoroborate (compound of structural formula 15)

In a 200 mL round bottom flask equipped with a magnetic stirrer was charged 1,1-diphenyl-3-durylpseudoindole (compound of formula 12, 5.55 g, 20.0 mmol) and acetonitrile (30 mL). To this solution was added all at once

1,2-hexanediol cyclic sulfate (compound of Formula 14, 2.60 g, 22.0 mmol). The resulting reaction mixture became strongly thick over minutes, so additional acetonitrile (60 mL) was added. The reaction mixture was then stirred overnight. The precipitate was filtered off, washed with acetone and allowed to air dry to give the compound of Formula 15. This preparation corresponds to the following reaction:

(15)

Formulation Examples Example 4

Examples of bleaching detergent compositions in the form of granular laundry detergents are as follows.

AND (B) C D E Effective compound 0.05 0.01 0.13 0.04 0.07 bleaching * Common Activator (NOBS) 0.00 2.00 1.20 0.70 0.00 Common Activator (TAED) 3.00 0.00 2.00 0.00 0.00 Common Activator (NACA-OBS) 3.00 0.00 0.00 0.00 2.20 Sodium percarbonate 5.30 0.00 0.00 4.00 0.00 Sodium perborate monohydrate 0.00 5.30 3.60 0.00 4.30 Linear alkylbenzenesulfonate 12.00 0.00 12.00 0.00 21,00 C45AE0.6S 0.00 15.00 0.00 15.00 0.00 C2 dimethylamine N-oxide 0.00 2.00 0.00 2.00 0.00 C12 cocoamidopropyl betaine 1.50 0.00 1.50 0.00 0.00 Palm-N-methylglucamide 1.70 2.00 1.70 2.00 0.00 C12 dimethylhydroxyethylammonium 1.50 0.00 1.50 0.00 0.00 chloride AE23-6,5T 2.50 3.50 2.50 3.50 1.00 C25E3S 4.00 0.00 4.00 0.00 0.00 Sodium tripolyphosphate 25,00 25,00 15.00 15.00 25,00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Acrylic acid copolymer / 0.00 0.00 0.00 0.00 1.00

maleic acid • ·

106

Partially neutralized acid 3.00 3.00 3.00 3.00 0.00 polyacrylic Dirt releasing agent 0.00 0.00 0.50 0.40 0.00 Carboxymethylcellulose 0.40 0.40 0.40 0.40 0.40 Sodium carbonate 2.00 2.00 2.00 0.00 8.00 Sodium silicate 3.00 3.00 3.00 3.00 6.00 Sodium bicarbonate 5.00 5.00 5.00 5.00 5.00 Savinasa (3T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolasa (100T) 0.12 0.12 0.12 0.12 0.12 Carezym (5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriaminpenta (methylene- 1.60 1.60 1.60 1.60 0.40 phosphonic acid) Zj asňovadlo 0.20 0.20 0.20 0.05 0.20 Sulfonated zinc phthalocyanine 0.50 0.00 0.25 0.00 0.00 as a photobleach MgS0 ₄ 2.20 2.20 2.20 2.20 0.64 Na ₂ SO ₄ zby- zby- zby- zby- zby- tek tek tek tek tek

* 1- (4,4-Dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared by the procedure of Example 1.

Any of the above compositions are used for washing fabrics at a concentration of 3500 ppm in water at 25 ° C and a water to fabric ratio of 15: 1. sodium salts.

Example 5

Examples of bleaching detergent compositions in the form of granular laundry detergents are as follows.

107 «· · · · · • · • · · • · · · · • v • · · • · · • · · · • · * • · • · · · · «· · · · • «· · ······ · · • · · · • «· · · · · AND (B) C D E Effective compound 0.26 0.38 0.04 0.03 0.01 bleaching * Common Activator (NOBS) 0.00 0.00 0.00 0.50 0.00 Common Activator (TAED) 1.80 1.00 2.50 3.00 1.00 Common Activator (NACA-OBS) 3.00 0.00 0.00 2.50 0.00 Sodium percarbonate 5.30 0.00 0.00 0.00 0.00 Sodium perborate monohydrate 0.00 9.00 17.60 9.00 9.00 Linear alkylbenzenesulfonate 21,00 12.00 0.00 12.00 12.00 C45AE0.6S 0.00 0.00 15.00 0.00 0.00 C2 dimethylamine N-oxide 0.00 0.00 2.00 0.00 0.00 C12 cocoamidopropyl betaine 0.00 1.50 0.00 1.50 1.50 Palm-TV-methylglucamide 0.00 1.70 2.00 1.70 1.70 C12 dimethylhydroxyethylammonium 1.00 1.50 0.00 1.50 1.50 chloride AE23-6,5T 0.00 2.50 3.50 2.50 2.50 C25E3S 0.00 4.00 0.00 4.00 4.00 Sodium tripolyphosphate 25,00 15.00 25,00 15.00 15.00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Acrylic acid copolymer / 0.00 0.00 0.00 0.00 0.00 maleic acid Partially neutralized acid 0.00 3.00 3.00 3.00 3.00 polyacrylic Dirt releasing agent 0.30 0.50 0.00 0.50 0.50 Carboxymethylcellulose 0.00 0.40 0.40 0.40 0.40 Sodium carbonate 0.00 2.00 2.00 2.00 2.00 Sodium silicate 6.00 3.00 3.00 3.00 3.00 Sodium bicarbonate 2.00 5.00 5.00 5.00 5.00 Savinasa (3T) 0, 60 1.00 1.00 1.00 1.00 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolasa (100T) 0.12 0.12 0.12 0.12 0.12 Carezym (5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriaminpenta (methylene- 0.40 0.00 1.60 0.00 0.00

phosphonic acid)

108

Brightener 0.20 0.30 0.20 0.30 0.30 Sulfonated zinc phthalocyanine 0.25 0.00 0.00 0.00 0.00 as a photobleach MgSO ₄ 0.64 0.00 2.20 0.00 0.00 Na ₂ S0 ₄ zby- zby- zby- zby- zby- tek tek tek tek tek

* 1- (4,4-Dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared by the procedure of Example 1.

Any of the above compositions are used for washing fabrics at a concentration of 3500 ppm in water at 25 ° C and a water to fabric ratio of 15: 1. sodium salts.

Example 6

Bleaching Detergent Powder Containing Component

Bleach enhancing compound *

TAED

Sodium perborate tetrahydrate C12 linear alkylbenzene sulfonate Phosphate (as sodium tripolyphosphate) Sodium carbonate

Talc

Brightener, fragrance

Sodium chloride

Water and minor components of the following components:% by weight

0.07

2,0

0.3 to 100% by weight of 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared by the procedure of Example 1.

109

Example 7

A solid detergent suitable for handwashing soiled fabrics was prepared by a standard extrusion process and contains the following ingredients:

Component

Bleach-enhancing compound ^] TAED

NOBS

Sodium perborate tetrahydrate C12 linear alkylbenzenesulfonate Phosphate (as sodium tripolyphosphate)

Sodium carbonate

Sodium pyrophosphate

Monoethanolamid. of coconut oil

Zeolite A (0.1 micrometer to 10 micrometer)

Carboxymethylcellulose

Polyacrylate (MW 1400)

Brightener, fragrance

Proteasa

CaSO ₄

MgSO ₄

Water

Filler ² % by weight 0.2 1.7 0.2

0.2

0.2

0.2

0,3 remainder to 100% ¹ 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according to Example 1st

² can be selected from conventional materials such as CaCO ₃ , talc, clay, silicates and the like.

Example 8

A laundry detergent composition suitable for use in an automatic washing machine was prepared by standard procedures and contains the following ingredients:

• «I

110

Component % by weight Bleach enhancing compound * 0, 82 TAED 7.20 Sodium perborate tetrahydrate 9.2 Sodium carbonate 23.47 Anionic surfactant 14.80 Aluminosilicate 21.30 Silicate 1.85 Diethylenetriaminepentaacetic acid 0.43 Polyacrylic acid 2.72 Zj asňovadlo 0.23 Solids based on polyethylene glycol 1.05 Sulphate 8.21 Fragrance 0.25 Water 7.72 Processing aids 0.10 Various minority components 0.43

* 1- (4,4-Dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared by the procedure of Example 1.

The composition is used to wash fabrics at a solution concentration of 1000 ppm at 20 ° C to 40 ° C and a water to fabric ratio of 20: 1.

Example 9

Component % by weight Bleach enhancing compound * 1.0 TAED 10.0 Sodium perborate tetrahydrate 8.0 Sodium carbonate 21.0 Anionic surfactant 12.0 Aluminosilicate 18.0 Diethylenetriaminepentaacetic acid 0.3

Nonionic surfactant

Polyacrylic acid

Zj asňovadlo

Sulphate

Fragrance

Water

Various minority components

111

0.5

2,0

0.3

17.0

0.25

6.7

2.95 * 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared by the procedure of Example 1.

The composition is used as a laundry detergent at a concentration of 850 ppm at 20 ° C to 40 ° C and a water to fabric ratio of 20: 1.

While specific examples of embodiments of the present invention have been described, it will be apparent to those skilled in the art that various changes and modifications to the nature of the present invention may be made without departing from the scope of the present invention. It is an object of the following claims to include all such modifications falling within the scope of the present invention.

Advantageously, the compositions of the present invention may be prepared by any process selected by the person making the composition, but non-limiting examples of such processes are described in U.S. Pat. U.S. Patent Nos. 5,691,297, 5,574,005, 5,569,645, 5,565,422, 5,516,448, 5,589,392 and 5,586,303.

In addition to the examples, bleach systems of the present invention may be added to any suitable laundry detergent compositions, non-limiting examples of which are described in U.S. Pat. U.S. Pat.

(+420) 565 145, 5 478 489, 5 470 507, 5 466 802,

458 810, 5 458 809 and 5 288 431.

By describing the invention in detail with reference to preferred embodiments and examples, it will be apparent to those skilled in the art

679 630, 5 460 752

It will be appreciated that various changes and modifications can be made without departing from the scope of the present invention, and the invention is not limited to the description.

Industrial applicability

The compositions of the present invention are industrially useful for the manufacture of laundry detergents.

Claims (4)

1, 15. A bleaching agent indicating a chelating agent. 121 the composition of claim 1, further comprising 16. A cationic or zwitterionic bleach-enhancing compound selected from a compound of formula I, a compound of formula II, a compound of formula III and a compound of formula IV: (IV) 122 and mixtures thereof; wherein in the compound of formula I and the compound of formula II t is 0 or 1; R ¹ to R ⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy; any of which are optionally combined to form a fused carbocycle or heterocycle; R ⁵ is substituted or a residue selected from the group consisting of cycloalkyl, alkaryl, aryl, aralkyl, two adjacent R to R fused aryl, fused unsubstituted hydrogen, alkyl, heterocycle, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboxyl groups carboalkoxyls; R ⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and radical: -T ₀ - (Z ') _and wherein Z is covalently bonded to T _o, and Z is selected from the group consisting of -C 0 ~ _2, -S0 ₃ -0S0 _3, -S0 ₂ ~ and -0S0 ₂ "AA 1 is or 2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or - (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C 8 alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3) H AND -ch ₂ -c • (4) H AND -CH ₂ -C-CH ₂ - _; OH (S) - (CH ₂ ) d (E) (CH ₂ ) f -, wherein d is 2 to 8, f is 1 to 3, and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C ₁ -C ₄ alkyl; ·· · 123 Η AND -where x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ¹⁸ R ¹⁹ -, -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ - and -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ CR ²² R ²³ R ¹⁴ to R ²³ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 -C 18 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R ⁷ -R ¹⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched Cy-C _i2 alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic rings, further provided that when t is zero, R ⁷ or R ⁸ is not hydrogen and that, if t is one, either of R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are not hydrogen; wherein any one of R ¹ to R ¹⁰ is optionally associated with any other of R ¹ to R ¹⁰ part of a common cycle; wherein in the compound of Formula III, t is 0 or 1; R ³¹ to R ³⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, carboxyl, and carboalkoxy; any optionally linked to a fused carbocycle heterocycles; R ²⁵ is a substituted radical selected from the group consisting of alkaryl, aryl, aralkyl, heterocycles to form a keto group, two adjacent R ³¹ to R fused aryl, fused unsubstituted hydrogen, alkyl, form or nitro, halogen, cyano, sulfonato , «· And R ²⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and radical: -T ₀ - _(Z) wherein Z 'is covalently bonded to T _o, and Z is selected from the group consisting of -C 0 _2', -S0 ₃ ^_ -0S0 _3, -S0 ₂ '-0S0 ₂ "AA 1 or 2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or - (C (R ¹² ) ₂ ) -, wherein R ¹² is independently alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3) H AND -CH _{2 -C-CH, R} is selected from hydrogen or C ₃ to C ₈ (4) H AND - CH _r C-CH _r OH (5) - (CH ₂ ) _d (E) (CH ₂ ) _f -, wherein d is 2 to 8, f is 1 to 3 and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl; (7) H Wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ³⁹ R ⁴⁰ -, -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² - and -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² CR ⁴³ R ⁴⁴ -; R ³⁵ to R ⁴⁴ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C ₃ to C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic, alkoxy, 125 ~ fy - éRftf 4 T * T * T * T Arylcarbonyl, carboxyalkyl and amide; wherein R ²⁷ to R ³⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 to C ₁₂ alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is zero, R ²⁷ or R ²⁸ is not hydrogen and that when t is one, either of R ²⁷ and R ²⁸ or R ²⁹ and R ³⁰ are not hydrogen; wherein any of R ²⁵ to R ³⁴ is optionally linked to any other of R ²⁵ to R ³⁴ so as to form part of a common cycle. A method of washing a fabric in need of washing, characterized in that the fabric is contacted with a laundry solution comprising a bleaching composition according to claim 1. 18. A laundry added product comprising a bleach-enhancing compound selected from the group consisting of: (a) Bleach enhancing compounds selected from the group consisting of aryliminium cations, aryliminium zwitterions, aryliminium polyions having a net charge of +3 to -3 and mixtures thereof, which are compounds of formula I and formula II: ψΐ / 125 ··· · * • <· * (II) wherein t is 0 or 1; R ¹ to R ⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycle, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; any of which are optionally combined to form a fused carbocycle or heterocycle; R ⁵ is substituted or a residue selected from the group consisting of cycloalkyl, alkaryl, aryl, aralkyl, two adjacent R to R fused aryl, fused unsubstituted hydrogen, alkyl, heterocycle, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboxyl groups carboalkoxylu; ⁶ R ⁷ is substituted or unsubstituted, saturated or unsaturated, radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and residue: -T ₀ - (Z ') _and wherein Z is covalently bonded to T _o, and Z is selected from the group consisting of -C 0 _2, -S0 ₃ ", -OSO 3 ^-, -S0 ₂ ~ and -0S0 _2" AA 1 is or R ¹ , 10 (II) wherein t is 0 or 1; R ¹ to R ⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocycle, nitro, halogen, cyano, sulfonato, alkoxy, carboxyl, and carboalkoxy; any optionally linked to a fused carbocycle heterocycles; R ⁵ is a substituted residue selected from the group consisting of cycloalkyls, alkaryl, aryl, aralkyl, keto groups, two adjacent R ¹ to R ⁴ fused aryl, fused unsubstituted hydrogen, alkyl, forms or or heterocycles, nitro, halogen, cyano, · · · 114 sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; R ⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and radical: -T ₀ - (Z) a where Z 'is covalently bonded to T _o, and Z' is selected from the group consisting of -C 0 ₂ ', -SO 3 *, -OSO 3', -S0 ₂ '-0S0 ₂ "AA 1 or A bleaching composition comprising a bleach-enhancing compound with or without a peroxide source, wherein the bleach-enhancing compound is selected from the group consisting of: (a) bleach-enhancing compounds selected from the group consisting of aryliminium cations, aryliminium zwitterions, aryliminium polyions having a net charge of +3 to -3 and mixtures thereof, which are compounds of formula I and formula II: , 9 X (i: 2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or - (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C ₈ alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3) H AND - CH, -C-CHy (4) · · 4 4 4 4 4 4 4 129 H AND _R -CH-CH-C _r H (5) - _(CH2) d (E) _(CH2) f- wherein d is from 2 to 8, f is from 1 to 3 and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl; (7) H Wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ³⁹ R ⁴⁰ -, -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² - and -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² CR ⁴³ R ⁴⁴ -; R ³⁵ to R ⁴⁴ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C ₁ to C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R ²⁷ to R ³⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched Ci to C _i2 alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic rings, further provided that when t is zero, R ²⁷ or R ²⁸ is not hydrogen and that when t is one, either of R ²⁷ and R ²⁸ or R ²⁹ and R ³⁰ are not hydrogen; wherein any of R ²⁵ to R ³⁴ is optionally linked to any other of R ²⁵ to R ³⁴ so as to form part of a common cycle; (c) mixtures thereof. of the group The product comprising added to the laundry in that according to claim 18, R ⁶ is selected from linear or branched C 1 to C 14 130 <U ^Z CXU ~ ··· v · ··· · ··· * · · · ··········· Substituted or unsubstituted alkyl and cycloalkyl, or R ⁶ is a residue -T ₀ - (Z ') _and wherein Z is -CO 2', -SO 3 "and -OSO 3, a is 1 or 2 and T _o is selected from the group consisting of: wherein p is an integer from 2 to 4 and R ⁴⁵ is independently selected from the group consisting of hydrogen and linear or branched C 1 -C 18 substituted or unsubstituted alkyl and cycloalkyl. The laundry additive product of claim 19, wherein R ¹ to R ⁴ are independently selected from the group consisting of hydrogen, alkyl and alkoxy, R ⁵ is selected from hydrogen or methyl, and R ⁶ is selected from the group consisting of linear or branched C 1 -C 14 substituted or unsubstituted alkyl and cycloalkyl or R ⁶ is a residue -T ₀ - (Z ') _a wherein Z is -SO 3 'or -OSO 3' and a is 1. The product to be added to the laundry according to claim 18, characterized in that it is in the dispenser form selected from the group consisting of powder, tablets, containers gel or other unit dosage forms. A product to be added to the laundry according to claim 18, characterized in that it further comprises a suitable carrier. 131 23. A bleaching agent selected from the group consisting of: tetraacetylethylenediamine, 4-nitrobenzoylcaprolactam, benzoyloxybenzenesulfonate, phenylbenzoate, benzoylvalerolactam, peroxyhydrolyzable according to claim 3, wherein the bleach activator is benzoylcaprolactam, 3-chlorobenzoylcaprolactam sulfonate, nonanoyloxybenzone sulphonate benzenesulfonate, 2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or - (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C 8 alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3) H AND -ch ₂ -ch (4) H AND _R -CH-CH-C _r OH (5) - (CH ₂ ) and (E) (CH ₂ ) _f -, wherein d is 2 to 8, f is 1 to 3, and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl; (7) 127 a (8) RR where x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ¹⁸ R ¹⁹ -, -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ - and -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ CR ²² R ²³ -; R ¹⁴ to R ²³ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 to C 18 alkyls, cycloalkyls, alkaryl, aryl, aralkyls, alkylenes, heterocycles, alkoxy, arylcarbonyl, carboxyalkyls and amides; wherein R ⁷ to R ¹⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is zero R ⁷ or R ⁸ is not hydrogen and that, if t is one, either of R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are not hydrogen; wherein any one of R ¹ to R ¹⁰ is optionally linked to any other of R ¹ to R ¹⁰ to form part of a common cycle; (b) bleaching particles selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyions having a net charge of +3 to -3 and mixtures thereof, being compounds of formula III and formula IV: , 32, 33. RR (III) / V 128, 34 wherein t is 0 or 1; R ³¹ to R ^J41 are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; any of which are optionally combined to form a fused carbocycle or heterocycle; R ²⁵ is substituted or a residue selected from the group consisting of alkaryl, aryl, aralkyl, heterocycle, two adjacent R ³¹ to R fused aryl, fused unsubstituted hydrogen, alkyl, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy and R ²⁶ is a substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle and radical: -T ₀ - (Z-) _and wherein Z is covalently bonded to T _o and Z "is selected from the group consisting of -CO ₂ -, -SO ₃ , -SO ₃ -, -SO ₂ - and -OSO ₂ - and a is 1 or A bleaching composition according to claim 1, wherein the bleach enhancing compound is 0.001% to 10% by weight of the composition and the peroxide source, if present, is 0.01% to 60% by weight of the composition. 2; T _o is selected from the group consisting of: (1) - (CH (R ¹² )) - or - (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C ₁ -C ₈ alkyl; (2) -CH ₂ (C ₆ H ₄ ) -; (3) H AND -CH _r C-CH _r (3) H AND - CH ₂ -C-CH _r OH (5) - _(CH2) d (E) _(CH2) f- wherein d is from 2 to 8, f is from 1 to 3 and E is -C (O) O-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C ₁ -C ₄ alkyl; (7) H Wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ³⁹ R ⁴⁰ -, -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² - and -CR ³⁹ R ⁴⁰ CR ⁴¹ R ⁴² CR ⁴³ R ⁴⁴ -; R ³⁵ to R ⁴⁴ are substituted or Unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 to C 18 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amide; wherein R ²⁷ to R ³⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is zero R ²⁷ or R ²⁸ is not hydrogen and that when t is one, either of R ²⁷ and R ²⁸ or R ²⁹ and R ³⁰ are not hydrogen; wherein any of R ²⁵ to R ³⁴ is optionally linked to any other of R ²⁵ to R ³⁴ so as to form part of a common cycle; (c) mixtures thereof. 2; T _o is selected from the group consisting of: (1) - (CH (R ¹² ) 2) - or - (C (R ¹² ) 2) -, wherein R ¹² is independently selected from hydrogen or C 1 to C 8 alkyl; (2) -CH 2 (C ₆ H ₄ ) -; (3) H AND -CH-C — CH _r (4: _R -CH-CH-C _r H (5) - _{(CH2) d} (E) (CH _{2) f} - wherein d is from 2 to 8, f is from 1 to 3 and E is -C (0) 0-; (6) -C (O) NR ¹³ -, wherein R ¹³ is hydrogen or C 1 -C ₄ alkyl; [7] H Wherein x is 0 to 3; J, if present, is independently selected from the group consisting of -CR ¹⁸ R ¹⁹ -, -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ - and -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ CR ²² R ²³ -; R ¹⁴ to R ²³ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 -C 18 alkyls, cycloalkyls, alkaryl, aryl, aralkyls, alkylenes, heterocycles, alkoxyls, phylenes; 115 arylcarbonyl, carboxyalkyl, and amide; 115; &lt; tb &gt;&gt; wherein R ⁷ to R ¹⁰ are substituted or unsubstituted radicals independently selected from the group consisting of hydrogen, linear or branched C 1 -C ₁₂ alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycles, further provided that when t is zero, R ⁷ or R ⁸ is not hydrogen and that, if t is one, either of R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are not hydrogen; wherein any one of R ¹ to R ¹⁰ is optionally linked to any other of R ¹ to R ¹⁰ to form part of a common cycle; (b) bleaching particles selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyions having a net charge of +3 to -3 and mixtures thereof, being compounds of formula III and formula IV: wherein t is 0 or 1; R ³¹ to R ³⁴ are substituted or unsubstituted radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy; any of which are optionally connected to two adjacent condensed condensed R ³¹ to R are aryl, fused carbocycle heterocycles; is a substituted form or or; • unsubstituted radical selected from the group consisting of hydrogen, alkyl, alkaryl, aryl, aralkyl, heterocycles, nitro, halogen, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy and R ²⁵ is a substituted or unsubstituted, selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycles, and the radical: -T ₀ - _(Z) wherein Z is covalently bonded to T _o, and Z 'is selected from the group consisting of -CO2', -SO 3 ', -OSO 3, -SO 2 and -0S0 ₂ ~ aa is 1 or A bleaching composition according to claim 1, wherein the peroxide source, if present, is selected from the group consisting of: (a) preformed peroxyacid compounds selected from the group consisting of peroxycarboxylic acids and salts thereof, percarbonate acids and salts thereof, perimidic acids and salts thereof, peroxymonosulfuric acids and salts thereof, and mixtures thereof; (b) hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof; and with or without bleach activator. 118 A bleaching composition according to claim 1, wherein R ⁶ is -T ₀ - _(Z) wherein 7f is covalently bonded to T _o, and Z 'is selected from the group consisting of -C 0 _2', -S0 ₃ and -0S0 ₃ '; a is 1 or 2 and T _o is wherein x is equal to 0-2; J, if present, is independently selected from the group consisting of -CR ¹⁸ R ¹⁹ -, -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ - and -CR ¹⁸ R ¹⁹ CR ²⁰ R ²¹ CR ²² R ²³ -; R ¹⁴ to R ²³ are substituted or unsubstituted radicals selected from linear or branched groups consisting of hydrogen, C 1 -C 18 alkyl, cycloalkyl, alkaryl, aryl, aralkyl and alkylene. The bleaching composition of claim 4, wherein the bleach enhancing compound is an aryliminium zwitterion wherein R ⁵ is hydrogen or methyl and is 1. Sixth bleaching composition according to claim 4 wherein said bleach booster is an aryliminium polyion having a net negative charge wherein R ⁵ is hydrogen or methyl aa is 2. The bleaching composition of claim 1, wherein the bleach enhancing compound is an arylliminium cation wherein R ⁵ is hydrogen or methyl and R ⁶ is hydrogen or a linear or branched C ₃ -C 14 substituted or unsubstituted alkyl and cycloalkyl. The bleaching composition of claim 1, wherein the bleach enhancing compound is an aryliminium cation in which R ⁶ is selected From the group consisting of linear or branched C 1 to C ₁₄ substituted or unsubstituted alkyl and cycloalkyl, or the bleach enhancing compound is an arylimino zwitterion in which R ⁶ is -T ₀ - _(Z) wherein Z 'is -C02 ~ -S0 ₃ "and -OSO 3, a is 1 and T _o is selected from the group consisting of: wherein p is an integer from 2 to 4 and R ⁴⁵ is independently selected from the group consisting of hydrogen and linear or branched C 1 -C 18 substituted or unsubstituted alkyl and cycloalkyl. A bleaching composition according to claim 1, wherein the bleaching particle is an oxaziridinium cation, wherein R ²⁶ is selected from the group consisting of linear or branched Cy to C14 substituted or unsubstituted alkyl and cycloalkyl, or the bleaching particle is an oxaziridinium zwitterion, wherein R ²⁶ is -T ₀ - (Z ') _and wherein Z "is -CO ₂ , -SO ₃ " and -OSO 3, and a 1 T _o is selected from the group consisting of: wherein p is an integer from 2 to 4 and R ⁴⁵ is independently selected from the group consisting of hydrogen and linear or branched C 6 to C 18 substituted or unsubstituted alkyl or cycloalkyl. 9 9 9 • 120 ρ / _a · · «« · · · · · · A bleaching composition according to claim 1, wherein the bleaching particle is an oxaziridinium polyion having a negative net charge in which R ²⁵ is hydrogen or methyl, Z 'is -CCk ^- , -SO ₃ - and -OSO ₃ -. aa is 2. A bleaching composition according to claim 1, wherein the bleaching particle is an oxaziridinium polyion having a negative net charge in which R ²⁵ is hydrogen or methyl and R ²⁶ is selected from the group consisting of: ₀ -T '(Z) _a where Z' is -CO ^ ^-, -SO ₃ and -OSO ₃ ", a is 1 and T _o is selected from the group consisting R -C) _p R ^{45 is a} number 2-4 and R ⁴⁵ is independently selected from hydrogen and a linear or branched C 1 wherein p is an entire group consisting of up to C 18 substituted or unsubstituted alkyl and cycloalkyl. 12. confesses The bleaching composition according to claim 1, further comprising a surfactant. 13. confess the surfactant. A bleaching composition according to claim 12, wherein the surfactant is anionic 14. confesses The bleaching composition of claim 1 further comprising an enzyme 4- [N- (nonanoyl) aminohexanoyloxy] benzenesulfonate, lauroyloxybenzenesulfonate, 10-undecenoyloxybenzenesulfonate, decanoyloxybenzoic acid and mixtures thereof.