CN1250692C - Formulation components resistant towards decomposition by aromatization compositions and laundry methods employing same - 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

Formulation ingredient for inhibiting breakdown by aromatization and compositions and laundry methods using same

field of invention

The present invention relates to formulation ingredients such as bleach boosting compounds having improved stability, and compositions and laundry methods employing bleach boosting compounds having increased stability. More particularly, the present invention relates to quaternary imine bleach boosters and/or oxaziridinium (Oxaziridinium) bleaching substances, using combinations of quaternary imine bleach boosters and/or oxaziridinium bleaching substances items and laundry methods.

Background of the invention

Oxygen bleaches have become increasingly popular in recent years in household and personal care products that facilitate stain and soil removal. Bleach is particularly desirable for its soil removal, fade fabric cleaning, whitening and disinfecting properties. Oxygen bleaches have been found to be particularly satisfactory in laundry products such as detergents, in automatic dishwashing products and in hard surface cleaners. However, oxygen bleach is somewhat limited in its effectiveness. Some frequently encountered disadvantages include color damage to fabrics and damage to laundry appliances, especially the rubber hoses these appliances may contain. Furthermore, oxygen bleaches tend to be particularly temperature rate dependent. Therefore, the cooler the solution in which they are used, the less effective the bleaching action will be. The effectiveness of oxygen bleaches in solution generally requires temperatures in excess of 60°C.

To address the above-mentioned temperature-rate dependence, a class of compounds known as "bleach activators" has been developed. Bleach activators are typically perhydrolyzable acyl compounds such as hydroxybenzenesulfonates having a leaving group that reacts with active oxygen groups to form more effective peroxyacid oxidizers, usually perhydrolyzable Hydrogen oxide or its anion. It is this peroxyacid compound that subsequently oxidizes the stained or contaminated matrix material. However, bleach activators are also somewhat temperature dependent. Bleach activators are more effective in warm water of about 40-60°C. At water temperatures below about 40°C, the peroxyacid compound loses some of its bleaching effect.

Several attempts have been made to develop bleach systems that are effective under low temperature water conditions, as disclosed in US Patent Nos. 5,360,568, 5,360569, and 5,370,826, all to Madison et al. However, the dihydroisoquinolinium bleach boosters disclosed in these references, when combined with peroxygen compounds, undergo undesired decomposition, including the formation of inactive aromatic isoquinoliniums, which results in the builder Reduced efficiency.

For the above reasons, researchers have devoted great efforts to the development of effective bleach boosters which do not cause decomposition.

Accordingly, there remains a need for effective bleach boosting compounds and compositions containing bleach boosting compounds that provide effective bleaching even at lower temperatures and provide improved stability against decomposition of unwanted bleach boosting compounds.

Summary of the invention

This need is met by the present invention, wherein longer duration bleach boosting compounds, especially bleach boosters and/or bleaching substances are provided. The bleach boosting compounds of the present invention provide excellent bleaching benefits even at lower water temperatures and prevent harmful decomposition.

In a first embodiment there is provided a bleaching composition comprising a bleach boosting compound, with or without a peroxygen source, wherein said bleach boosting compound is selected from: (a) selected from the group consisting of aryliminium Bleach boosters of (aryliminium) cations, aryliminium zwitterions, aryliminium polyions having a net charge of about +3--3, and mixtures thereof; (b) selected from the group consisting of oxaziridines Onium cations, oxaziridinium zwitterions, oxaziridinium polyions having a net charge of about +3-3, and mixtures thereof; and (c) mixtures thereof.

According to another embodiment of the present invention there is provided a cationic or zwitterionic laundry bleach boosting compound.

According to another aspect of the present invention there is provided a method of laundering fabrics in need of laundering comprising contacting the fabrics with a laundry solution comprising a bleaching composition according to the invention as described herein.

According to yet another aspect of the present invention, there is provided a laundry additive product comprising a bleach boosting compound selected from the group consisting of: (a) selected from the group consisting of aryliminium cations, aryliminium zwitterions, net charges of about Bleach boosters for aryl iminium polyions of +3--3 and mixtures thereof; (b) selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, with a net charge of about Bleaching species of oxazirinium polyions of +3 - 3 and mixtures thereof; and (c) mixtures thereof.

It is therefore an object of the present invention to provide: bleach boosting compounds which exhibit improved performance even in lower temperature solutions and which prevent harmful aromatization; comprising quaternary imine bleach boosters and/or or a bleaching composition of an oxazirinium bleaching substance; a method of laundering fabrics by using a quaternary imine bleach booster and/or an oxazirinium bleaching substance; and a bleach booster containing a quaternary imine detergent and/or oxazirinium bleaching substances in laundry additive products. These and other objects, features and advantages of the present invention will be apparent to those of ordinary skill in the art from the following description and appended claims.

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

Detailed description of the invention

The present invention discloses novel high-efficiency bleach boosting compounds ("bleach boosters", "bleach substances" and mixtures thereof), compositions and methods for using the novel bleach boosting compounds. The bleach boosting compounds of the present invention provide enhanced bleaching even in lower temperature applications while preventing deleterious decomposition resulting from aromatization, resulting in improved performance. The bleach boosting compounds of the present invention are used with or without conventional sources of peroxygen bleach, preferably in combination, to provide the enhanced bleaching benefits described above and to prevent aromatization.

definition

"Peroxygen source" as used herein means a material from which a peroxygen compound is generated, which may include the peroxygen compound itself. Examples include, but are not limited to, bleach activators, peracids, percarbonates, perborates, hydrogen peroxide, bleach boosting compounds and/or bleaching substances (eg, oxaziriniums).

"Peroxy compound" as used herein includes peracids and peroxides (eg, hydrogen peroxide, alkyl hydroperoxides, etc.).

"Peracid" as used herein refers to peroxyacids, such as peroxycarboxylic acid and/or peroxymonosulfuric acid (trade name OXONE) and salts thereof.

Bleach Boosters - The bleach boosters of the present invention are preferably quaternary imine bleach boosters. More preferably, the bleach boosters of the present invention are selected from the group consisting of aryliminium cations, aryliminium zwitterions, and/or aryliminium polyions having a net charge of about +3 - 3 and their wherein the bleach booster has the formulas [I] and [II]:

Wherein, t is 0 or 1; R ¹ -R ⁴ are substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, heterocycle, nitro, halo, cyano, sulfonate (sulfonato), alkoxy, keto, carboxyl, and carboalkoxy; any two adjacent R ¹ -R ⁴ can be combined to form a condensed aromatic ring, fused carbocyclic ring or fused heterocyclic ring; R ⁵ is A substituted or unsubstituted group selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, nitro, halo, cyano, sulfonate, alkoxy, Keto, carboxyl, and alkoxycarbonyl; ^R can be substituted or unsubstituted, saturated or unsaturated, selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and a group represented by the following formula:

-T ₀ -(Z ^- ) _a

Here, Z ^- is covalently bound to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- and a is 1 or 2; T ₀ Selected from: (1)-(CH(R ¹² ))- or -(C(R ¹² ) ₂ )-, wherein R ¹² is independently selected from H or C ₁ -C ₈ alkyl; (2)-CH ₂ (C ₆ H ₄ )-;

(5)-(CH ₂ ) _d (E)(CH ₂ ) _f -, wherein, d is 2-8, f is 1-3, E is -C(O)O-; (6)-C(O ) NR ¹³ -, wherein, R ¹³ is H or C ₁ -C ₄ alkyl;

和

and

wherein, x is equal ^to 0-3; J, when present, is independently selected from -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 -R ²³ is a substituted or unsubstituted group selected from H, C ₁ -C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, aryl Linear or branched chain groups of acyl, carboxyalkyl and amido groups; wherein, R ⁷ -R ¹⁰ are substituted or unsubstituted groups independently selected from H, straight chain or branched C ₁ -C ₁₂ alkyl groups , alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl, and heterocycle, with the further premise that, when t is 0, neither ^R7 nor ^R8 can be H , when t is 1, or both R ⁷ and R ⁸ , or both R ⁹ and R ¹⁰ are not H; wherein, any one of R ¹ -R ¹⁰ can be combined with any other of R ¹ -R ¹⁰ to form Common ring part.

Preferred bleaching substances include, but are not limited to: (1) Oxazirinium cations of formula [III], wherein R ²⁵ is H or methyl, and R ²⁶ is selected from linear or branched C ₁ -C ₁₄ Substituted or unsubstituted groups of alkyl, C ₃ -C ₁₄ cycloalkyl and C ₆ -C ₁₄ aryl; (2) oxaziridinium zwitterions of formula [IV], wherein R ²⁵ is H or Methyl, R ²⁶ has the following formula:

-T ₀ -(Z ^- ) _a

Preferred bleach boosters include, but are not limited to: (1) aryl iminium ions of formula [I], wherein, R ⁵ is H or methyl, R ⁶ is selected from linear or branched C ₁ -C ₁₄ Substituted or unsubstituted groups of alkyl, C ₃ -C ₁₄ cycloalkyl and C ₆ -C ₁₄ aryl; (2) aryl iminium zwitterions of formula [II], wherein R ⁵ is H or form Base, ^R6 has the following formula:

-T ₀ -(Z ^- ) _a

Here, Z ^- is covalently bonded to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- and -OSO ₃ ^- , a is 1 or 2; (3) Arylimine of formula [I] Onium cation, wherein, R ⁶ is selected from linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl, or the aryl iminium zwitterion of formula [II], wherein, R ⁶ is the following The base represented by the formula:

-T ₀ -(Z ^- ) _a

Wherein, Z ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- , a is 1, T ₀ is selected from:

Wherein, p is an integer of 2-4, R ⁴⁵ is independently selected from H and linear or branched C ₁ -C ₁₈ substituted or unsubstituted alkyl groups; and (4) aryl imines having a net negative charge Onium polyion, wherein R ⁵ is H, Z ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- and a is 2.

More preferred bleach boosters include, but are not limited to: (1) aryliminium cations of formula [I], wherein R ¹ -R ⁵ are H, R ⁶ are straight or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl groups; (2) aryl iminium zwitterions of formula [II], wherein R ¹ -R ⁵ are H, and R ⁶ has the following formula:

-T ₀ -(Z ^- ) _a

Here, Z ^- is covalently bonded to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- and a is 1.

Additionally, it is desired that all aryliminium cations of formula [I] and [II], aryliminium zwitterions, and aryliminium polyions having a net charge of about +3--3 be formed into Geminally substituted. The pairwise substituted bleach boosters of the present invention inhibit or prevent the decomposition of said cations, zwitterions and polyions via aromatization. The aromatization (decomposition) reaction of 6-membered ring builders is well known in the art, as exemplified without being bound by theory by Hanquet et al. in Tetrahedron, 1993, 49, pp. 423-438 and as follows :

Pairwise substituted bleach boosters increase the turnover number of active bleach boosters by "blocking" base-induced aromatization. as described in detail above. Such substitutions, without being bound by theory, may also inhibit or prevent decomposition of the cations, zwitterions and polyions by other decomposition pathways. Other decomposition pathways include, but are not limited to, attack by nucleophiles on bleach boosting compounds and/or on bleach species, including but not limited to, by hydroxide anions, perhydroxide anions, carboxylate anions, percarboxylate anions and attack by other nucleophiles present under wash conditions.

The quaternary imine bleach boosters of the present invention act in combination with a peroxygen source to provide a more effective bleaching system. Peroxygen sources are well known in the art, and peroxygen sources used in the present invention may comprise any of these well-known sources, including peroxygen compounds and those capable of providing in situ an effective amount of peroxygen under user use conditions. compound of. The peroxygen source may comprise a hydrogen peroxide source, a peracid anion formed in situ by the reaction of the hydrogen peroxide source with a bleach activator, a preformed peracid compound or a mixture of suitable peroxygen sources. Of course, one of ordinary skill in the art will identify other sources of peroxygen that may be used without departing from the scope of the present invention.

The source of hydrogen peroxide may be any suitable source of hydrogen peroxide present in an amount as fully described in US Patent No. 5,576,282. For example, the source of hydrogen peroxide may be selected from perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof.

The bleach activator may be selected from tetraacetylethylenediamine, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium lauroyloxybenzenesulfonate, (6 -octanoylamino-caproyloxy)benzenesulfonate, (6-nonanoylamino-caproyloxy)benzenesulfonate, (6-decanoylamino-caproyloxy)benzenesulfonate, and their mixture.

Preferred activators are selected from tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C ₁₀ -OBS), benzoylvalerolactam (BZVL), octanoyl Acyloxybenzenesulfonate (C ₈ -OBS), perhydrolyzable esters, 4-[N-(nonanoyl)aminocaproyloxy]benzenesulfonic acid sodium salt (NACA-OBS), Examples are described in U.S. Patent No. 5,523,434, lauroyloxybenzenesulfonate or dodecanoyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzenesulfonic acid Salt (UDOBS or C ₁₁ -OBS with an unsaturated bond at the 10th position), decanoyloxybenzoic acid (DOBA) and mixtures thereof, most preferably benzoyl caprolactam and benzoyl valerolactam . Particularly preferred bleach activators in the pH range of about 8-9.5 are selected bleach activators having an OBS or VL leaving group.

Other preferred bleach activators are U.S. 5,698,504 issued December 16, 1997 to Christie et al, U.S. 5,695,679 issued December 9, 1997 to Christie et al, U.S. 5,686,401, U.S. 5,686,014 issued Nov. 11, 1997 by Hartshorn et al., U.S. 5,405,412 issued April 11, 1995 by Willey et al., U.S. 5,405,413 issued April 11, 1995 by Willey et al. Bleach activators described in U.S. 5,130,045, issued July 14, 1992, U.S. 4,412,934, US 5,998,350, and EP 699,233A1, issued November 1, 1983 to Chung et al., all of which are incorporated herein by reference middle.

Quaternary substituted bleach activators may also be included. The detergent compositions of the present invention preferably comprise a Quaternary-Substituted Bleach Activator (QSBA) or a Quaternary-Substituted Peracid (QSP); more preferably the former. Preferred QSBA structures are described in U.S. 5,686,015 issued November 11, 1997 by Willey et al, U.S. 5,654,421 issued August 5, 1997 by Taylor et al, U.S. 5,460,747 issued October 24, 1995 by Gosselink et al. U.S. 5,584,888, issued December 17, 1996 to Miracle et al., and U.S. 5,578,136, issued November 26, 1996 to Taylor et al.; all of which are incorporated herein by reference.

Highly preferred bleach activators useful herein are amide substituted as described in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, all of which are incorporated hereinbefore. Preferred examples of such bleach activators include: (6-octanoylaminocaproyloxy)benzenesulfonate, (6-nonanoylaminocaproyloxy)benzenesulfonate, (6-decanoylaminocaproyloxy)benzenesulfonate, (6-decanoylaminocaproyloxy)benzenesulfonate, acyloxy)benzenesulfonates and mixtures thereof.

Other useful activators, disclosed in US 5,698,504, US 5,695,679, US 5,686,014 already cited above, and US 4,966,723 issued October 30, 1990 to Hodge et al, include benzoxazine-type Activators such as _{a C6H4} ring fused with a --C(O)OC( ^R1 )=N- moiety at the 1,2 position.

Depending on the activator and the exact application, good bleaching results can be obtained with the bleaching system at an in-use pH of about 6-13, preferably about 9.0-10.5. Typically, for example, for near-neutral or near-neutral pH ranges, activators with electron-withdrawing moieties are used. Alkalis and buffers can be used to maintain such a pH.

As described in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, all of which have been cited above, acyl lactam activators are very useful in the present invention, especially acyl caprolactams (see, for example, WO 94-28102A) and acyl valerolactams. Lactams (see U.S. 5,503,639, Willey et al., issued April 2, 1996, incorporated herein by reference).

A preformed peracid compound as used herein is any convenient compound that is stable and provides an effective amount of a peracid anion under conditions of user use. The bleach boosters of the present invention may of course be used in combination with preformed peracid compounds selected from the group consisting of percarboxylic acids and percarboxylates, percarbonic acids and percarbonates, perimino acids and perimino acids. Amino acid salts, peroxymonosulfates and peroxymonosulfates, and mixtures thereof, examples of which are described in US Patent No. 5,576,282 to Miracle et al.

One class of suitable organic peroxycarboxylic acids has the general formula:

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

Organic peroxyacids suitable for use in the present invention may contain one or two peroxy groups and may be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the general formula for the unsubstituted acid is:

Here, Y may be, for example, H, CH ₃ , CH ₂ Cl, C(O)OH or C(O)OOH; n is an integer of 0-20. When the organic peroxycarboxylic acid is aromatic, the general formula for the unsubstituted acid is:

Wherein, Y can be, for example, hydrogen, alkyl, alkyl halide, halogen, C(O)OH or C(O)OOH.

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

(i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamidoperoxy Caproic acid (sodium salt);

(ii) Aliphatic, substituted aliphatic and aralkyl monoperoxyacids, for example, peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-( 3-octylsuccinyl)aminoperoxycaproic acid (SAPA) and N,N-phthaloylaminoperoxycaproic acid (PAP);

(iii) Amidoperoxyacids, such as monononyl peroxysuccinic acid amide (NAPSA) or monononyl peroxyadipic acid amide (NAPAA).

Typical diperoxyacids useful herein include alkyl diperoxyacids and aryl diperoxyacids such as:

(iv) 1,12-diperoxydodecanedioic acid;

(v) 1,9-diperoxyazelaic acid;

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

(vii) 2-decyl diperoxybutane-1,4-dioic acid;

(viii) 4,4'-sulfonylbisperoxybenzoic acid.

Such bleaching agents are described in U.S. Patent 4,483,781 issued November 20, 1984 to Hartman, U.S. Patent 4,634,551 to Burns et al., European Patent Application 0,133,354 issued February 20, 1985 to Banks et al., and Chung et al. Disclosed in US Patent 4,412,934, issued November 1. Peroxygen sources also include 6-nonylamino-6-oxoperoxycaproic acid, as described in detail in US Patent 4,634,551, issued January 6, 1987 to Burns et al. Persulfate compounds such as OXONE manufactured by E.I. DuPont de Nemours of Wilmington, DE can also be used as a suitable source of peroxymonosulfuric acid.

A bleach activator as used herein is any compound which, when used in combination with hydrogen peroxide, results in the in situ generation of a peracid corresponding to such a bleach activator. Various non-limiting examples of activators are described in detail in US Patent 5,576,282, US Patent 4,915,854, and US Patent 4,412,934. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

The quaternary imine bleach boosters of the present invention act in combination with a peroxygen source to increase bleaching effectiveness. Without being bound by any theory, it is believed that the bleach booster reacts with the peroxygen source to form a more active bleaching species, the quaternary oxaziridinium compound. Oxazirinium compounds exhibit increased activity at lower temperatures relative to peroxy compounds. Oxazirinium compounds are represented by formulas [III] and [IV]:

Wherein, t is 0 or 1; R ³¹ -R ³⁴ are substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, heterocycle, nitro, halo, cyano, sulfonate alkoxy, keto, carboxyl and alkoxycarbonyl; any two adjacent R ³¹ -R ³⁴ can be combined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is substituted or unsubstituted A radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl and alkoxycarbonyl, ^R can be a substituted or unsubstituted, saturated or unsaturated group selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and a group represented by the formula:

-T ₀ -(Z-) _a

Here, Z ^- is covalently bound to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- and a is 1 or 2; T ₀ Selected from: (1)-(CH(R ¹² ))- or -(C(R ¹² ) ₂ )-, wherein R ¹² is independently selected from H or C ₁ -C ₈ alkyl; (2)-CH ₂ (C ₆ H ₄ )-;

(5)-(CH ₂ ) _d (E)(CH ₂ ) _f -, wherein, d is 2-8, f is 1-3, E is -C(O)O-; (6)-C(O ) NR ¹³ -, wherein, R ¹³ is H or C ₁ -C ₄ alkyl;

and

wherein, x is equal to 0-3; J, when present, is independently selected from -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} -R ⁴⁴ is a substituted or unsubstituted group selected from H, C ₁ -C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, Linear or branched groups of aroyl, carboxyalkyl and amido groups; wherein, R ²⁷ -R ³⁰ are substituted or unsubstituted groups, independently selected from H, linear or branched C ₁ -C ₁₂ Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle, with the further proviso that, when t is 0, neither ^R27 nor ^R28 is possible is H, when t is 1, or both R ²⁷ and R ²⁸ , or both R ²⁹ and R ³⁰ are not H; wherein, any one of R ²⁵ -R ³⁴ can be combined with any other of R ²⁵ -R ³⁴ One combines to form a common ring moiety. In addition, R ²⁵ -R ³⁰ and R ³¹ -R ³⁴ may be the same as R ⁵ -R ¹⁰ and R ¹ -R ⁴ of the bleach boosters of formulas [I] and [II], respectively. Such oxaziridinium compounds can be produced from the quaternary imines of the present invention using the following reactions:

and

Bleach Substances - Bleaching substances (oxaziriniums) may also be used directly in accordance with the present invention. The bleaching species of the present invention are preferably selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyions with a net charge of about +3 - 3, and mixtures thereof, The oxaziridinium compound has the molecular formulas [III] and [IV]:

and

Wherein, t is 0 or 1; R ³¹ -R ³⁴ are substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, heterocycle, nitro, halo, cyano, sulfo Acido, alkoxy, keto, carboxyl and alkoxycarbonyl; any two adjacent R ³¹ -R ³⁴ can be combined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is substituted or unsubstituted A group selected from H, alkyl, alkaryl, aryl, aralkyl, heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl and alkoxycarbonyl , R ²⁶ may be a substituted or unsubstituted, saturated or unsaturated group selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and represented by the following formula Group:

-T ₀ -(Z ^- ) _a

Here, Z ^- is covalently bound to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- and a is 1 or 2; T ₀ Selected from: (1)-(CH(R ¹² ))- or -(C(R ¹² ) ₂ )-, wherein R ¹² is independently selected from H or C ₁ -C ₈ alkyl; (2)-CH ₂ (C ₆ H ₄ )-;

(5)-(CH ₂ ) _d (E)(CH ₂ ) _f -, wherein, d is 2-8, f is 1-3, E is -C(O)O-; (6)-C(O ) NR ¹³ -, wherein, R ¹³ is H or C ₁ -C ₄ alkyl;

和

and

wherein, x is equal to 0-3; J, when present, is independently selected from -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} -R ⁴⁴ is a substituted or unsubstituted group selected from H, C ₁ -C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, aryl Linear or branched groups of acyl, carboxyalkyl and amido groups; wherein, R ²⁷ -R ³⁰ are substituted or unsubstituted groups independently selected from H, linear or branched C ₁ -C ₁₂ Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle, with the further proviso that, when t is 0, neither ^R27 nor ^R28 is possible is H, when t is 1, or both R ²⁷ and R ²⁸ , or both R ²⁹ and R ³⁰ are not H; wherein, any one of R ²⁵ -R ³⁴ can be combined with any other of R ²⁵ -R ³⁴ One combines to form a common ring moiety. In addition, R ²⁵ -R ³⁰ and R ³¹ -R ³⁴ may be the same as R ⁵ -R ¹⁰ and R ¹ -R ⁴ of the bleach boosters of formulas [I] and [II], respectively.

Preferred bleaching substances include, but are not limited to: (1) Oxazirinium cations of formula [III], wherein R ²⁵ is H or methyl, and R ²⁶ is selected from linear or branched C ₁ -C ₁₄ Alkyl, C ₃ -C ₁₄ cycloalkyl and C ₆ -C ₁₄ aryl substituted or unsubstituted groups; (2) oxaziridinium zwitterions of formula [IV], wherein R ²⁵ is H or methyl, ^R has the formula:

-T ₀ -(Z ^- ) _a

Here, Z ^- is covalently bonded to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- and -OSO ₃ ^- , a is 1 or 2; (3) oxaziridine of formula [III] Pyridinium cations, wherein, R ²⁶ is selected from linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl groups, or aryl iminium oxaziridiniums of formula [IV], wherein R ²⁶ is a group represented by the following formula:

-T ₀ -(Z ^- ) _a

Wherein, Z ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- , a is 1, T ₀ is selected from:

Wherein, p is an integer of 2-4, R ⁴⁵ is independently selected from H and linear or branched C ₁ -C ₁₈ substituted or unsubstituted alkyl groups; and (4) aryl imines having a net negative charge Onium polyion, wherein R ²⁵ is H, Z ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- and a is 2.

The bleach boosting compounds of the present invention may be used in combination with or without, preferably with, a peroxygen source in bleaching compositions. In the bleaching compositions of the present invention, the peroxygen source may range from about 0.01% to about 60%, preferably from about 0.1% (1 ppm) to about 60% (600 ppm), more preferably from about 1% ( 10ppm) to 40% (400ppm), the bleach boosting compound and/or bleaching material may be present in an amount of from about 0.00001% (0.0001ppm) to about 10% (100ppm) by weight of the composition, preferably about 0.0001 % (0.001ppm) - about 2% (20ppm), more preferably about 0.005% (0.05ppm) - about 0.5% (5ppm), even more preferably about 0.01% (0.1ppm) - about 0.2% (2ppm ), most preferably from about 0.02% (0.2ppm) to about 0.1% (1ppm).

Preferably, the bleaching composition of the bleaching compositions of the present invention comprises an amount of bleach boosting compound and/or bleaching material such that the resulting concentration of the bleach boosting compound in the wash solution is from about 0.001 ppm to about 5 ppm.

Additionally, the bleaching compositions of the present invention preferably comprise a peroxygen compound and an amount of bleach boosting compound and/or bleaching material such that, when a peroxygen compound is present, the resulting peroxygen compound and bleach boosting compound And/or the molar ratio of bleaching species in the wash solution is preferably greater than 1:1, more preferably greater than 10:1, even more preferably greater than 50:1. The preferred molar ratio of peroxygen compound to bleach boosting compound ranges from about 30,000:1 to 10:1, even more preferably from about 10,000:1 to 50:1, still more preferably from about 5,000:1 to 100: 1, still more preferably about 3,500:1-150:1. in-use product concentration. A 1000 ppm wash solution of a product containing 0.2% by weight of a bleach boosting compound yields a bleach boosting compound concentration of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% by weight of a bleach boosting compound yields a bleach boosting compound concentration of 6.5 ppm.

Particularly useful methods of administering the bleach boosting compounds of the present invention and methods of administering bleach compositions (products) containing such bleach boosting compounds in the methods of the present invention are those satisfying the use of a peroxygen source and using the methods defined herein. BLEACH BOOSTING COMPOUNDS OF THE STRUCTURE BLEACH BOOSTING COMPOUNDS AND BLEACHING COMPOSITIONS CONTAINING THE PREFERRED METHOD OF BLEACHING A SPOILED SUBSTRATE IN AQUEOUS MEDIA, WHEREIN, said medium contains about 0.05-250 ppm per liter of medium Active oxygen from peroxygen compounds, and about 0.001 ppm-5 ppm, preferably about 0.01-3 ppm, more preferably about 0.1-2 ppm, most preferably about 0.2-1 ppm of said bleach boosting compound.

This preferred method of bleaching a soiled substrate in an aqueous medium with a peroxygen source and with a bleach boosting compound is of particular value for those applications where the color safety of the soiled substrate to be cleaned is of concern. In such applications, this preferred embodiment (eg, 0.01 to about 3 ppm) is especially important in achieving acceptable fabric color safety. For applications where color safety of the contaminated substrate requiring cleaning is less critical, higher use concentrations may be preferred.

The bleaching compositions of the present invention may be advantageously used in laundry applications including, but not limited to, stain bleaching, dye transfer inhibition, and whitening, hard surface cleaning, automatic dishwashing applications, and cosmetic applications such as dentures, teeth, hair and skin. However, due to the unique advantage of enhanced bleaching in lower temperature solutions, the bleach boosting compounds of the present invention are ideally suited for laundry applications such as the bleaching of fabrics using bleach-containing detergents or laundry bleach additives. Additionally, the bleach boosting compounds of the present invention may be used in both granular and liquid compositions.

Accordingly, the bleaching compositions of the present invention may contain a variety of additional ingredients as desired for laundry use. These ingredients include detersive surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other ingredients. Compositions comprising any of these various additional ingredients preferably have a pH of about 6-12, preferably about 8-10.5 in a 1% solution of the bleaching composition.

The bleaching composition preferably comprises at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme, and preferably has about 6-12, preferably about pH of 8-10.5.

According to another aspect of the invention there is provided a cationic or zwitterionic laundry bleach boosting compound. Such bleach boosting compounds are preferably selected from:

and mixtures thereof; wherein, for formulas [I] and [II], t is 0 or 1; R ¹ -R ⁴ are substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl , heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and alkoxycarbonyl; any two adjacent R ¹ -R ⁴ can be combined to form a fused aromatic ring, fused Carbocycle or condensed heterocycle; ^R is a substituted or unsubstituted group selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and alkoxycarbonyl; ^R can be substituted or unsubstituted, saturated or unsaturated group selected from H, alkyl, cycloalkyl , alkaryl, aryl, aralkyl, heterocycle, and a group represented by the following formula:

-T ₀ -(Z ^- ) _a

Here, Z ^- is covalently bound to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- and a is 1 or 2; T ₀ Selected from: (1)-(CH(R ¹² ))- or -(C(R ¹² ) ₂ )-, wherein R ¹² is independently selected from H or C ₁ -C ₈ alkyl; (2)-CH ₂ (C ₆ H ₄ )-;

(5)-(CH ₂ ) _d (E)(CH ₂ ) _f -, wherein, d is 2-8, f is 1-3, E is -C(O)O-; (6)-C(O ) NR ¹³ -, wherein, R ¹³ is H or C ₁ -C ₄ alkyl;

和

and

wherein, x is equal to 0-3; J, when present, is independently selected from -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 -R ²³ is a substituted or unsubstituted group selected from H, C ₁ -C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy , aroyl, carboxyalkyl, and amido straight-chain or branched chain groups; wherein, R ⁷ -R ¹⁰ are substituted or unsubstituted groups independently selected from H, straight-chain or branched C ₁ -C ₁₂ Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle, with the further proviso that, when t is ⁰ , neither R nor ^R May be H, when t is 1, or both R ⁷ and R ⁸ , or both R ⁹ and ¹⁰ are not H; wherein, any one of R ¹ -R ¹⁰ can be combined with any other of R ¹ -R ¹⁰ combined to form a common ring moiety; and wherein, for formulas [III] and [IV], t is 0 or 1; R ³¹ -R ³⁴ are substituted or unsubstituted groups selected from H, alkyl, cycloalkyl , aryl, heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl and alkoxycarbonyl; any two adjacent R ³¹ -R ³⁴ can be combined to form a condensed aromatic ring , fused carbocyclic or fused heterocyclic; R ²⁵ is a substituted or unsubstituted group selected from H, alkyl, alkaryl, aryl, aralkyl, heterocycle, nitro, halo, cyano group, sulfonate, alkoxy, keto, carboxyl and alkoxycarbonyl, ^R can be substituted or unsubstituted, saturated or unsaturated group selected from H, alkyl, cycloalkyl, alkaryl group, aryl group, aralkyl group, heterocycle, and a group represented by the following formula:

-T ⁰ -(Z ^- ) _a

Here, Z ^- is covalently bound to T ₀ , Z ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- and a is 1 or 2; T ₀ Selected from: (1)-(CH(R ¹² ))- or -(C(R ¹² ) ₂ )-, wherein R ¹² is independently selected from H or C ₁ -C ₈ alkyl; (2)-CH ₂ (C ₆ H ₄ )-;

(5)-(CH ₂ ) _d (E)(CH ₂ ) _f -, wherein, d is 2-8, f is 1-3, E is -C(O)O-; (6)-C(O ) NR ¹³ -, wherein, R ¹³ is H or C ₁ -C ₄ alkyl;

和

and

wherein, x is equal to 0-3; J, when present, is independently selected from -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 -R ⁴⁴ is a substituted or unsubstituted group selected from H, C ₁ -C ₁₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy , aroyl, carboxyalkyl, and amido straight-chain or branched chain groups; wherein, R ²⁷ -R ³⁰ are substituted or unsubstituted groups independently selected from H, straight-chain or branched C ₁ -C ₁₂ Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle, with the further proviso that, when t is 0, neither ^R27 nor ^R28 It may be H, when t is 1, or both of R ²⁷ and R ²⁸ , or both of R ²⁹ and R ³⁰ are not H; wherein, any one of R ²⁵ -R ³⁴ can be combined with any other of R ²⁵ -R ³⁴ One combines to form a common ring moiety. In another embodiment of the present invention, a method of laundering fabrics in need of laundering is provided. A preferred method involves contacting the fabric with a laundry solution. The fabric can include most any fabric that can be laundered under typical consumer use conditions. The laundry solution comprises a bleach composition as fully described herein. The temperature of the water used in this washing method is preferably about 0-50°C. The ratio of water to fabric is preferably from about 1:1 to about 15:1.

The laundry solution may also comprise at least one additional ingredient selected from the group consisting of detersive surfactants, chelating agents, detersive enzymes, and mixtures thereof. Preferably, the laundry solution has a pH of about 6-12, preferably about 8-10.5 in a 1% solution of the bleaching composition.

According to another aspect of the present invention, there is provided a laundry additive product. The laundry additive product comprises a bleach boosting compound as fully described above. Such laundry additive products are ideally suited for incorporation into the wash process when additional bleaching benefits are desired. Such situations may include, but are not limited to, laundry applications of low temperature solutions.

It is desirable that the laundry additive product also comprises a peroxygen source as fully described above. Laundry additive products may also comprise powdered or liquid compositions containing a source of hydrogen peroxide or a source of peroxygen as defined in detail above.

Additionally, if the laundry additive product comprises a source of hydrogen peroxide, it is desirable that the laundry additive product also comprises a bleach activator as detailed above.

Preferably, the laundry additive product is packaged in dosage form for incorporation into laundry processes where a peroxygen source is used and where enhanced bleaching is desired. Such single dosage forms may comprise pills, tablets, gelcaps or other single dosage units such as pre-measured powders or liquids. If desired, filler or carrier materials can be included to increase the bulk of the composition. Suitable filler or carrier materials may be selected from, but not limited to, various salts of sulfates, carbonates and silicates, as well as talc, clay and the like. The filler or carrier material for liquid compositions can be water or low molecular weight primary and secondary alcohols, including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Monohydric alcohols can also be used. The composition may contain from about 5% to about 90% of such materials. Acidic fillers may be used to lower the pH.

When the bleach boosting compound of the present invention is not an aryliminium zwitterion or an oxaziridinium zwitterion, a suitable bleach-compatible charge-balancing counterion may also be present.

Bleaching compositions comprising bleach boosting compounds

In addition to the use of the bleach boosting compounds discussed above, the bleach boosting compounds of the present invention can also be used in combination with or without, preferably with, a peroxygen source in other bleaching compositions, regardless of their form. For example, the bleach boosting compounds can be used in laundry additive products. In the bleaching compositions of the present invention, the source of peroxygen may be present at a level of from about 0.1% to about 60% by weight of the composition, preferably from about 1% to about 40% by weight of the composition. In the compositions, the bleach boosters are present in an amount of about 0.001-10% by weight of the composition, more preferably about 0.005-5% by weight of the composition. In the bleaching compositions of the present invention, the peroxygen source is present in an amount of about 0.1% (1ppm) to 60% (600ppm) by weight of the composition, preferably about 1% (10ppm) to 40% (400ppm) by weight of the composition. ), the content of the bleach boosting compound is about 0.00001% (0.0001ppm)-10% (100ppm) by weight of the composition, preferably about 0.0001% (0.001ppm)-2% (20ppm) by weight of the composition, more Preferred is about 0.005% (0.05 ppm) to 0.5% (5 ppm), and even more preferred is about 0.01% (0.1 ppm) to 0.2% (2 ppm). Most preferred is about 0.02% (0.2 ppm) to 0.1% (1 ppm).

For purposes of illustration, converted values (expressed in ppm) are provided based on a used product concentration of 1000 ppm. A 1000 ppm wash solution of a product containing 0.2% by weight of a bleach boosting compound yields a bleach boosting compound concentration of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% by weight of a bleach boosting compound yields a bleach boosting compound concentration of 6.5 ppm.

The preferred bleach boosting compound concentration is based on a molecular weight of the bleach boosting compound of about 300 g/mole, although the bleach boosting compound may preferably have a molecular weight of about 150-1000 g/mole, or for oligomeric or Polymeric bleach boosting compounds with even higher molecular weights. For example, when the bleach boosting compound content is more preferably about 0.005% (0.05ppm) to 0.5% (5ppm) in the bleach boosting composition of the present invention, the molar (M) concentration of the bleach boosting compound will be between In the range of 1.7×10 ^-8 -1.7×10 ^-5 M. If higher molecular weight bleach boosting compounds are used in the bleaching compositions of the present invention, the preferred molar concentration will remain the same, while the preferred weight concentration (expressed in ppm) will accordingly increase. For example, a bleach boosting compound having a molecular weight of about 600 g/mole will more preferably be present at a level of from about 0.01% (0.1 ppm) to 1.0% (10 ppm). For oligomeric or polymeric bleach boosting compounds, the more preferred molar concentrations will be based on the monomeric units associated with the iminium or oxaziridinium active sites.

The bleaching compositions of the present invention can be advantageously used in laundry applications, hard surface cleaning, automatic dishwashing applications and cosmetic applications such as dentures, teeth, hair and skin. However, due to the unique advantages of enhanced color safety and increased efficacy in cold and possibly warm aqueous solutions resulting from possible increased stability, the bleach boosting compounds of the present invention are ideally suited for laundry applications, such as utilizing bleach containing detergent or laundry bleach additives to bleach fabrics. Additionally, the bleach boosting compounds of the present invention may be used in both granular and liquid compositions.

The bleach boosting compounds and bleaching compositions containing the bleach boosting compounds are useful as antimicrobial agents and disinfectants.

Accordingly, the bleaching compositions of the present invention may contain a variety of additional ingredients as desired in laundry applications. Such ingredients include detersive surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other ingredients. Compositions comprising any of these various additional ingredients preferably have a pH of about 6-12, preferably about 8-10.5 in a 1% solution of the bleaching composition.

The bleaching composition preferably comprises at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme, preferably at a pH of about 6-12, preferably about 8, in a 1% solution of the bleaching composition -10.5.

In another embodiment of the present invention, a method of laundering fabrics in need of laundering is provided. A preferred method involves contacting the fabric with a laundry solution. The fabric may comprise most any fabric capable of being laundered under normal consumer use conditions. The laundry solution comprises a bleach composition as fully described herein. The water temperature is preferably about 0-50°C or higher. The ratio of water to fabric is preferably from about 1:1 to about 15:1.

The laundry solution may also comprise at least one additional ingredient selected from the group consisting of detersive surfactants, chelating agents, detersive enzymes, and mixtures thereof. Preferably, the laundry solution has a pH of about 6-12, preferably about 8-10.5 in a 1% solution of the bleaching composition.

According to another aspect of the present invention, there is provided a laundry additive product. The laundry additive product comprises a bleach boosting compound as fully described above. Such laundry additive products are ideally suited for incorporation into the wash process when additional bleaching benefits are desired. Such situations may include, but are not limited to, laundry applications of low and medium temperature solutions.

It is desirable that the laundry additive product also comprises a peroxygen source as fully described above. Laundry additive products may also comprise powdered or liquid compositions comprising a source of hydrogen peroxide or a source of peroxygen as fully described above.

Furthermore, if the laundry additive product comprises a source of hydrogen peroxide, it is desirable that the laundry additive product also comprises a bleach activator as fully described above.

Preferably, the laundry additive product is packaged in a dosage form for incorporation into laundry processes where a source of peroxygen is used and where enhanced bleaching is desired. Such unit dosage forms may comprise pills, tablets, capsules or other single dosage units such as pre-measured powders or liquids. If desired, filler or carrier materials can be included to increase the bulk of the composition. Suitable filler or carrier materials may be selected from, but not limited to, various salts of sulfates, carbonates and silicates, as well as talc, clay and the like. The filler or carrier material for liquid compositions can be water or low molecular weight primary and secondary alcohols, including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Monohydric alcohols can also be used. The composition may contain from about 5% to about 90% of such materials. Acidic fillers may be used to lower the pH.

A preferred bleaching composition is one comprising the following ingredients:

(a) a source of peroxygen; and

(b) bleach boosting compounds;

wherein the bleach boosting compound becomes active in a wash solution containing said bleaching composition within a period of time after said peroxygen source becomes active. The peroxygen source, as discussed above, is preferably selected from:

and their mixture, and

(ii) A source of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and a bleach activator.

Bleach System - In addition to the bleach booster of the present invention, the bleaching compositions of the present invention preferably comprise a bleaching system. Bleaching systems generally contain a source of peroxygen. Peroxygen sources are well known in the art, and peroxygen sources used in the present invention may comprise any of these well-known sources, including peroxygen compounds as well as compounds which provide an effective amount of peroxygen in situ under user use conditions. The peroxygen source may comprise a hydrogen peroxide source, a peracid anion formed in situ by the reaction of the hydrogen peroxide source with a bleach activator, a preformed peracid compound or a mixture of suitable peroxygen sources. Of course, one of ordinary skill in the art may identify other sources of peroxygen that may be used without departing from the scope of the present invention. Preferably, the source of peroxygen is selected from:

(i) preformed peracid compounds selected from the group consisting of percarboxylic acids and percarboxylates, percarbonates and percarbonates, perimino acids and perimino acid salts, peroxomonosulfates and peroxomonosulfates and their a mixture of, and

(ii) A source of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and a bleach activator.

Typical levels of peroxygen sources (peracids and/or hydrogen peroxide sources), when present, are from about 1%, preferably from about 5% to 30%, preferably from about 20% by weight of the composition. %. If present, the amount of bleach activator is generally from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40%, by weight of the bleaching composition comprising bleach plus bleach activator.

a. Preformed Peracids - As used herein, a preformed peracid compound is any convenient compound that is stable and provides an effective amount of peracid anion under user use conditions. The bleach boosting compounds of the present invention may of course be used in combination with preformed peracid compounds selected from the group consisting of percarboxylic acids and percarboxylates, percarbonic acids and percarbonates, perimino acids and Perimino acid salts, peroxymonosulfates and peroxymonosulfates, and mixtures thereof, examples are described in US Patent No. 5,576,282 to Miracle et al.

One class of suitable organic peroxycarboxylic acids has the general formula:

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

Organic peroxyacids suitable for use in the present invention may contain one or two peroxy groups and may be aliphatic or aromatic. When the organic peroxycarboxylic acid is an aliphatic peroxycarboxylic acid, the unsubstituted peracid has the general formula:

Here, Y may be, for example, H, CH ₃ , CH ₂ Cl, C(O)OH or C(O)OOH; n is an integer of 0-20. When the organic peroxycarboxylic acid is an aromatic peroxycarboxylic acid, the unsubstituted peracid has the general formula:

Wherein, Y can be, for example, hydrogen, alkyl, alkyl halide, halogen, C(O)OH or C(O)OOH.

Typical monoperoxyacids that can be used herein include alkyl and aryl peroxyacids such as:

(i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamidoperoxy Caproic acid (sodium salt);

(ii) Aliphatic, substituted aliphatic and aralkyl monoperoxyacids, for example, peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N -(3-octylsuccinyl)aminoperoxycaproic acid (SAPA) and N,N-phthaloylaminoperoxycaproic acid (PAP);

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

Typical diperoxyacids useful herein include alkyl diperoxyacids and aryl diperoxyacids such as:

(iv) 1,12-diperoxydodecanedioic acid;

(v) 1,9-diperoxyazelaic acid;

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

(vii) 2-decyl diperoxybutane-1,4-dioic acid;

(viii) 4,4'-sulfonylbisperoxybenzoic acid.

These bleaching agents are described in U.S. Patent 4,483,781 issued November 20, 1984 to Hartman, U.S. Patent 4,634,551 to Burns et al., European Patent Application 0,133,354 issued February 20, 1985 to Banks et al., and Chung et al. Disclosed in U.S. Patent 4,412,934 issued on January 1. Bleach sources also include 6-nonylamino-6-oxoperoxycaproic acid, as fully described in US Patent 4,634,551, issued January 6, 1987 to Burns et al. Persulfate compounds such as OXONE manufactured by E.I. DuPont de Nemours of Wilmington, DE can also be used as a suitable source of peroxymonosulfuric acid.

b. Source of Hydrogen Peroxide - The source of hydrogen peroxide may be any suitable source of hydrogen peroxide,

Its content is as fully described in US Patent No. 5,576,282. For example, the source of hydrogen peroxide may be selected from perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof.

The source of hydrogen peroxide is described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, Fourth Edition (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleach (Overview)", incorporated herein, and Included are sodium perborate and sodium percarbonate in various forms, including various coated and modified forms.

A preferred source of hydrogen peroxide for use herein may be any convenient source, including hydrogen peroxide itself. For example, perborates such as sodium perborate (any hydrate, but monohydrate and tetrahydrate are preferred), sodium carbonate peroxyhydrate or equivalent percarbonates, sodium pyrophosphate perborate, etc. may be used herein. Oxyhydrate, urea peroxyhydrate, or sodium peroxide. Also useful are sources of available oxygen such as persulfate bleaches (eg OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient sources of hydrogen peroxide may also be used.

Preferred percarbonate bleaches comprise dry particles having an average particle size of about 500 microns to 1,000 microns, wherein no more than about 10% by weight of the particles is less than about 200 microns and no more than about 10% by weight of the particles is greater than About 1,250 microns. Optionally, the percarbonate may be coated with silicates, borates or water soluble surfactants. Percarbonate can be obtained from various commercial sources such as FMC, Solvay and Tokai Denka.

The compositions of the present invention may also contain chlorine-type bleaching materials as bleaching agents. Such bleaching agents are well known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions containing enzymes.

c. Bleach Activators - Preferably, the peroxygen source in the composition is formulated with an activator (peracid precursor). The content of activator is from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition . As used herein, a bleach activator is any compound which, when used in combination with a source of hydrogen peroxide, results in the in situ generation of a peracid corresponding to the bleach activator. Various non-limiting examples of activators are fully described in US Patent Nos. 5,576,282, 4,915,854, and 4,412,934. See also US 4,634,551 for other typical bleaches and activators useful herein.

Preferred activators are selected from tetraacetylethylenediamine (TAED), benzoyl caprolactam (BzCL), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C ₁₀ -OBS), benzoylvalerolactam (BZVL), octanoyl Acyloxybenzenesulfonates ( _C8 -OBS), perhydrolyzable esters and mixtures thereof, most preferred are benzoyl caprolactam and benzoyl valerolactam. Particularly preferred bleach activators in the pH range of about 8-9.5 are selected from bleach activators having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS), 4-[N-(nonanoyl)aminocaproyloxy]benzenesulfonic acid sodium salt (NACA-OBS), examples of which Described in U.S. Patent No. 5,523,434, lauroyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C 12 -OBS with an unsaturated bond at the 10-position C ₁₁ -OBS), decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are U.S. 5,698,504 issued December 16, 1997 to Christie et al, U.S. 5,695,679 issued December 9, 1997 to Christie et al, U.S. 5,686,401, U.S. 5,686,014 issued Nov. 11, 1997 by Hartshorn et al., U.S. 5,405,412 issued April 11, 1995 by Willey et al., U.S. 5,405,413 issued April 11, 1995 by Willey et al. Bleach activators described in U.S. 5,130,045 issued July 14, 1992, U.S. 4,412,934 issued November 1, 1983 by Chung et al., US 5,998,350 and EP699,233 A1, all of which are incorporated by reference to In this article.

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

Quaternary substituted bleach activators may also be included. The bleaching compositions of the present invention preferably comprise either a quadruple substituted bleach activator (QSBA) or a quadruple substituted peracid (QSP); more preferably the former. Preferred QSBA structures are described in U.S. 5,686,015 issued November 11, 1997 by Willey et al, U.S. 5,654,421 issued August 5, 1997 by Taylor et al, U.S. 5,460,747 issued October 24, 1995 by Gosselink et al. Further described in U.S. 5,584,888, Miracle et al., issued December 17, 1996, and U.S. 5,578,136, issued November 26, 1996, Taylor et al.; all of which are incorporated herein by reference.

Highly preferred bleach activators for use herein are amide substituted as described in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, all of which are cited above. Preferred examples of such bleach activators include: (6-octanoylaminocaproyloxy)benzenesulfonate, (6-nonanoylaminocaproyloxy)benzenesulfonate, (6-decanoylaminocaproyloxy)benzenesulfonate, (6-decanoylaminocaproyloxy)benzenesulfonate, acyloxy)benzenesulfonates and mixtures thereof.

Other useful activators, disclosed in US 5,698,504, US 695,679, US 5,686,014 already cited above, and US 4,966,723 issued October 30, 1990 to Hodge et al, include benzoxazine-type Activators such as _{a C6H4} ring fused with a --C(O)OC( ^R1 )=N- moiety at the 1,2 position.

Depending on the activator and the exact application, good bleaching results can be obtained with bleaching systems having an in-use pH of about 6-13, preferably about 9.0-10.5. Typically, for example, for near-neutral or near-neutral pH ranges, activators with electron-withdrawing moieties are used. Alkalis and buffers can be used to maintain such a pH.

As described in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, all of which have been cited above, acyl lactam activators are very useful herein, especially acyl caprolactams (see, for example, WO 94-28102 A) and acyl valerolactams. Lactams (see U.S. 5,503,639, Willey et al., issued April 2, 1996, incorporated herein by reference).

d. Organic Peroxides, especially Diacyl Peroxides - In addition to the above bleaching agents, the bleaching compositions of the present invention may optionally contain organic peroxides. Organic peroxides are described extensively in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley & Sons, 1982, pp. 27-90, especially pp. 63-72, all of which are incorporated by reference to this article. If a diacyl peroxide is used, it is preferably one that has the least adverse effect on spotting/filming.

e. Metal-Containing Bleach Catalysts - The bleach compositions may also optionally contain metal-containing bleach catalysts, preferably manganese-containing and cobalt-containing bleach catalysts.

One class of metal-containing bleach catalysts is a catalyst system comprising transition metal cations such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations with defined bleach catalytic activity, with little or no auxiliary bleaching activity. Metal cations such as zinc or aluminum cations, and chelating agents with defined stability constants for the catalyst metal cation and auxiliary metal cation, in particular ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and water-soluble salts thereof. Catalysts of this type are disclosed in U.S. 4,430,243, issued February 2, 1982 to Bragg.

i. Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by manganese compounds. Such compounds and amounts are well known in the art and include, for example, US5,576,282 issued November 19, 1996 by Miracle et al; US5,246,621 issued September 21, 1993 by Favre et al; 5,244,594 issued September 14, 1993 to Jureller et al., US 5,194,416 issued March 16, 1993 to Jureller et al., US 5,114,606 issued May 19, 1992 to van Vliet et al., and European Patent Application Publication Manganese-based catalysts disclosed in 549,271 A1, 544,440 A2 and 544,490 A1. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(PF ₆ ) ₂ , Mn ^III ₂ ( uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1, 4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ -(1,4,7-trimethyl-1,4,7 -Triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ) and their mixtures. Other metal-based bleach catalysts include those disclosed in US 4,430,243, herein incorporated by reference, and in US 5,114,611, issued May 19, 1992 to van Kralingen. The use of manganese with various complexing ligands to enhance bleaching has also been reported in US 4,728,455 issued March 1, 1988 to Rerek, US 5,284,944 issued February 8, 1994 to Madison, US246,612 issued September 21, 1993 to van Dijk et al., US5,256,779 issued October 26, 1993 to Kerschner et al., US5,280,117 issued January 18, 1994 to Kerschner et al. US Pat.

ii. Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known and described in, for example, US 5,597,936 issued Jan. 28, 1997 by Perkins et al., 1997 by Miracle et al. US5,595,967 issued on December 21, 5,703,030 issued December 30, 1997 by Perkins et al., and ML Tobe's "Alkali Hydrolysis of Transition Metal Complexes", Adv.Inorg.Bioinorg.Mech., (1983), 2 , pp. 1-94. The most preferred cobalt catalyst for use in the present invention is cobalt acetate pentaammine cobalt having the formula [Co( _NH3 ) _5OAc ]Ty, where "OAc" denotes the acetate moiety and "Ty" is an anion, especially chloride Pentaammine cobalt acetate [Co(NH ₃ ) ₅ OAc]Cl ₂ ; and [Co(NH ₃ ) ₅ OAc](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 (referred to herein as "PAC") .

These cobalt catalysts are produced by known methods such as US5,597,936, US5,595,967, US5,703,030 cited above, the article by Tobe and the references cited therein, US Patent 4,810,410 issued March 7, 1989 to Diakun et al. , Journal of Chemical Education (J.Chem.Ed.) (1989), 66(12), pp. 1043-1045, The Synthesis and Characterization of Inorganic Compounds (The Synthesis and Characterization of Inorganic Compounds), WLJolly (Prentice-Hall; 1970) , pp. 461-463, Inorganic Chemistry (Inorg. Chem.) , 18, pp. 1497-1502 (1979), Inorganic Chemistry (Inorg.Chem.) , 21, pp. 2881-2885 (1982), Inorganic Chemistry ( Inorg.Chem. , 18, pp. 2023-2025 (1979), Inorg.Synthesis, pp. 173-176 (1960), and Journal of Physical Chemistry ( Journal of Physical Chemistry ) 56, pp. 22-25 It is readily prepared by known experimental procedures as described in Page (1952).

iii. Transition Metal Complexes of Macropolycyclic Rigid Ligands - The compositions herein may also suitably comprise transition metal complexes of macropolycyclic rigid ligands as bleach catalysts. The phrase "macrocyclic rigid ligand" is sometimes abbreviated "MRL" in the discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, such as up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm (where "ppb" means parts per billion by weight, "ppm" means parts per million by weight).

Suitable transition metals, such as Mn, are described below. "Macrocyclic" refers to MRL, which is macrocyclic and is polycyclic. "Polycyclic" means at least two rings. The term "rigid" is used herein to include "having a superstructure" and "cross-bridged". "Rigidity" has been defined as the limited antonym of flexibility; see DH Busch., Chemical Reviews. , (1993), 93, 847-860, which is incorporated herein by reference. More specifically, "rigid" as used herein means that the MRL must be measurably more rigid than the macrocycle (the "parent macrocycle"), which is otherwise identical (with the same ring size and type and atomic number) but lacks the superstructure found in MRLs (particularly linking moieties, or preferably cross-linking bridging moieties). In determining the comparative rigidity of macrocycles with and without superstructure, the practitioner will use the free form (not the metal bound form) of the macrocycle. It is well known that stiffness can be used to compare macrocycles, and suitable tools for determining, measuring or comparing stiffness include computational methods (see for example Zimmer, Chemical Reviews, (1995), 95(38), pp. 2629-2648 or Hancock et al. Inorganica Chimica Acta, (1989), 164, pp. 73-84).

The preferred MRLs of the invention are specific types of cross-bridged ultra-rigid ligands. "Crosslink bridges" are non-limitingly described in 1.11 below. In _1.11 , the crosslink bridge is a _-CH2CH2- moiety. It bridges ^N1 and ^N8 in the illustrated structure. In comparison, "same-side" bridges, eg if introduced on ^N1 and ^N12 in 1.11, do not adequately constitute "crosslinked bridges" and are therefore not preferred.

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

More generally, MRLs (and corresponding transition metal catalysts) herein suitably include:

(a) at least one macrocyclic main ring containing four or more heteroatoms; and

(b) a covalently bonded non-metallic superstructure capable of increasing the rigidity of the macrocycle, preferably selected from

(i) bridging superstructure, such as linked parts;

(ii) the superstructure of the cross-link bridge, such as the linking part of the cross-link bridge; and

(iii) Combinations of them.

The term "superstructure" is used herein as defined in Busch et al., see, eg, Busch in "Chemical Reviews".

The preferred superstructure here not only increases the rigidity of the parent macrocycle, but also facilitates the folding of the macrocycle so that it coordinates the metal in the cleft. A suitable superstructure can be very simple, for example linking sections, as shown in either of Figures 1 and 2, can be used.

figure 1

Wherein, n is an integer, such as 2-8, preferably less than 6, typically 2-4, or

figure 2

Wherein, m and n are about 1-8, more preferably an integer of 1-3; Z is N or CH;

T is a compatible substituent such as H, alkyl, trialkylammonium, halo, nitro, sulfonate, and the like. The aromatic ring in 1.10 may be substituted by a saturated ring, where the atom attached to the ring at the Z position may contain N, O, S or C.

Suitable MRLs are further illustrated, without limitation, by the following compounds:

image 3

This is the MRL according to the invention, which is a highly preferred crosslinked bridged, methyl substituted (all nitrogen atoms are tertiary nitrogen atoms) derivative of cyclam. Formally, using the generalized von Baeyer system, this ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane. See "IUPAC Nomenclature Guidelines for Organic Compounds:

Recommendations 1993 (A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993), R. Panico, W.H. Powell and J-C Richer (eds.), Blackwell Scientific Publications, Boston, 1993; see especially Section R-2.4.2.1.

Transition metal bleach catalysts suitable for macrocyclic rigid ligands for use in the compositions of the present invention may generally include known compounds meeting the definitions herein, and more preferably a number of compounds specifically designed for the laundry or cleaning use at hand. Any of the novel compounds, and illustrated, without limitation, by any of the following:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II)

Dihydrate-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanomanganese(II) hexafluorophosphate

Hydrated-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanomanganese(III) hexafluorophosphate

Dihydrate-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanomanganese(II) tetrafluoroborate

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanomanganese(III) hexafluorophosphate

Dichloro-5,12-di-n-butyl-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-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II)

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanomanganese(II).

(f) Other Bleach Catalysts - The compositions herein may contain one or more other bleach catalysts. Preferred bleach catalysts are zwitterionic bleach catalysts as described in US Patent No. 5,576,282 (particularly 3-(3,4-dihydroisoquinolinium)propane sulfonate). Other bleach catalysts include the cationic bleach catalysts described in US Pat.

Indeed, without limitation, the compositions and cleaning methods herein can be adjusted to provide active bleach catalyst species on the order of at least parts per million in the aqueous wash medium, and preferably about 0.01 ppm- 25 ppm, more preferably from about 0.05 ppm to 10 ppm, most preferably from about 0.1 ppm to 5 ppm bleach catalyst material. To achieve such levels in automatic laundering wash liquors, typical compositions of the present invention will contain from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, by weight of the cleaning composition, of bleach Catalysts, especially manganese or cobalt catalysts.

Preferably, the source of peroxygen is selected from sources of hydrogen peroxide and bleach activators, the source of hydrogen peroxide being selected from perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof.

Preferably, the bleach activators are selected from hydrophobic bleach activators as disclosed herein.

The purpose of such bleaching compositions is to moderate the detrimental decomposition of the bleach booster and to allow the peracid to achieve bleaching performance on fabrics to be cleaned, such as stained fabrics, in the wash solution before the bleach boost is achieved.

The time between the peracid becoming active in the wash solution and the bleach boosting compound becoming active may be from about 1 second to about 24 hours. Additionally, since the bleach boosting compounds are relatively stable in the wash solution, the peracids can become active in the wash solution after the bleach boosting compound has become active or incorporated.

The purpose of the delayed addition of the bleaching composition (which may or may not be used in conjunction with the present invention) is to allow the peracid to achieve maximum bleaching performance on the fabrics to be cleaned in the wash solution prior to the introduction of the bleach boosting compound. In other words, bleaching compositions comprise bleach boosting compounds which become active in the wash solution after the fabric to be cleaned has been added to the wash solution. Process for Delayed (Controlled) Addition of Bleach Boosting Compounds Co-pending and co-owned U.S. Provisional Patent Application entitled "Controlled Acquisition of Formulation Components, Compositions Using It, and Washing Methods," filed August 27, 1999 More fully described in (P&G Attorney Docket Number 7749P).

Additionally, since the bleach boosting compound may have increased stability, it is possible to use a bleaching composition comprising a bleach boosting compound which becomes active in the wash solution before the fabric to be cleaned is added to the wash solution. .

In addition to one or more of the above-described bleach boosting compounds, the bleaching compositions of the present invention preferably comprise one or more cleaning adjunct materials, preferably in combination with the bleach boosters present in the bleaching composition. and/or any enzyme compatible. The term "compatible", as used herein, means not reducing the bleaching activity of the bleach booster and/or the enzymatic activity of any enzyme present in the bleaching composition to such an extent that the bleach booster and/or enzyme is inferior to Bleaching composition materials which are as effective under normal use. The term "cleaning adjunct material", as used herein, refers to the specific type of bleaching composition and product form (e.g., liquid, granule, powder, stick, paste, spray, tablet, gel, foam composition) desired. Any liquid, solid or gaseous material that is selected is preferably also compatible with the protease(s) and bleach(s) used in the composition. Granular compositions may also be in "briquette" form and liquid compositions may be in "concentrate" form.

The specific choice of cleaning adjunct materials can readily be made by considering the surface, object or fabric to be cleaned, and the desired form of the composition for the cleaning conditions during use (eg by detergent use). Examples of suitable cleaning adjunct materials include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilization systems, chelating agents, optical brighteners, soil release polymers, dyes Dye transfer agent, dispersant, foam suppressor, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescer, fabric conditioner, hydrolyzable surface active preservatives, antioxidants, anti-shrinkage agents, anti-wrinkle agents, bactericides, fungicides, color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity source , solubilizers, carriers, process aids, pigments, and pH control agents, as described in US Pat. Specific bleach composition materials are exemplified in detail hereinafter.

If the cleaning adjunct material is incompatible with the protease variant(s) in the bleaching composition, then a cleaning aid that keeps the cleaning adjunct material and the protease variant(s) separate (out of contact with each other) can be used Proper approach until the combination of the two components is appropriate. A suitable method may be any method known in the art, such as gelcaps, encapsulation, tablets, physical isolation, and the like.

Such bleaching compositions include detergent compositions for cleaning hard surfaces, in any form (such as liquids, granules, pastes, foams, sprays, etc.); detergent compositions for cleaning fabrics, in any form (such as Granular, liquid, stick formulations, etc.); dishwashing compositions (in any form and including granular and liquid autodishwashers); oral bleaching compositions, in any form (such as dentifrice, toothpaste and mouthwash formulations) ; A denture bleaching composition, in any form (eg, liquid, tablet).

The fabric bleaching compositions of the present invention are primarily intended for use in the wash cycle of a washing machine; however, other uses are also contemplated, such as pretreatment products for heavily soiled fabrics, or soaking products; use is not necessarily limited to washing machines, the present invention The compositions can be used alone or in combination with compatible handwash compositions.

The bleaching compositions can comprise from about 1% to about 99.9% by weight of the composition of cleaning adjunct materials.

As used herein, "non-fabric bleaching compositions" include hard surface bleaching compositions, dishwashing compositions, oral bleaching compositions, denture bleaching compositions and personal cleansing compositions.

When the bleaching compositions of the present invention are formulated as compositions suitable for use in a washing machine, the compositions of the present invention preferably contain surfactant and builder compounds, and additionally one or more cleaning adjuncts Materials, preferably selected from organic polymers, bleaching agents, additional enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional cleaning adjunct materials.

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

When formulating compositions for use in manual dishwashing, the compositions of the present invention preferably contain a surfactant and preferably contain a surfactant selected from the group consisting of organic polymers, suds boosters, Group II metal ions, solvents, water-soluble Accelerators and additional cleaning aids for enzymes.

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

The "compact" form of the bleaching compositions herein is best reflected by density and compositionally by the amount of inorganic filler salts, which are conventional ingredients of detergent compositions in powder form; In detergent compositions of the present invention, the filler salt is usually present in a substantial amount of 17-35% by weight of the total composition. In the briquette composition, the filler salt is present in an amount not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. Inorganic filler salts, as referred to in the present composition, are selected from alkali metal and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.

Liquid bleaching compositions according to the invention may also be in "concentrated form", in which case the liquid bleaching compositions according to the invention will contain a lower amount of water compared to conventional liquid detergents. Typically, concentrated liquid bleaching compositions preferably have a water content of less than 40%, more preferably less than 30%, most preferably less than 20%, by weight of the bleaching composition.

cleaning aids

Although not essential for the purposes of the present invention, several conventional additives, described below, are suitable for use in the present bleaching compositions and may be worth incorporating in the preferred embodiments of the present invention, for example to facilitate or enhance cleaning performance, treatment The substrate to be cleaned, or to improve the aesthetics of the bleaching composition as in the case of perfumes, colorants, dyes and the like. The precise nature of these additional ingredients and the amount of their incorporation will depend upon the physical form of the composition and the type of cleaning operation in which the composition is used. Unless otherwise stated, the bleaching compositions of the present invention may, for example, be formulated as full- or "boost" detergents, in particular laundry detergents, in granular or powder form; liquid, gel or cream full-purpose detergents, especially the so-called Heavy-duty liquid types; liquid delicate fabric detergents; hand dishwashing detergents or light-duty dishwashing detergents, especially high-foaming types; machine dishwashing detergents including various tablets, granules, liquids, and rinses for domestic and institutional use Auxiliary forms; liquid cleaning and sanitizing agents, including antiseptic hand washes, laundry bars, mouthwashes, denture cleaners, car or carpet cleaners, bathroom cleaners; shampoos and hair rinses; shower gels and foam baths and metal cleaning and cleaning aids such as bleach additives and "stain-stick" or pre-treatment types.

Surfactant - The compositions of the present invention preferably contain a detersive surfactant. Detersive surfactants are generally selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. By selection of the type and level of detersive surfactants, and other adjunct ingredients as described herein, the detergent compositions of the present invention can be formulated for use in the laundry cleaning range or in various other detersive applications, particularly including dishwashing. Therefore, the particular surfactant employed can vary widely depending on the particular intended end use. Suitable surfactants are described below. Examples of suitable nonionic, anionic, cationic, amphoteric and zwitterionic surfactants are listed in "Surface Active Agents and Detergents" (Surface Active Agents and Detergents) ( Schwartz, Perry and Berch, Volumes I and II). Many such surfactants are also generally described in US Patent 3,929,678, issued December 30, 1975 to Laughlin at column 23, line 58 through column 29, line 23.

The surfactant content is generally from about 0.1%, preferably about 1%, more preferably about 5% by weight of the bleaching composition to about 99.9%, preferably about 80% by weight of the bleaching composition, More preferably about 35%, most preferably about 30%.

Anionic surfactants - the anionic surfactants useful in the present invention are preferably selected from the group consisting of linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkanes Alkyl sulfates, alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates, sarcosinates, taurates and mixtures thereof . Anionic detersive surfactants can be used herein in effective amounts, generally from about 0.5% to 90%, preferably from about 5% to 60%, more preferably from about 10% to 30%, by weight.

Alkyl sulfate surfactants are another important class of anionic surfactants useful in the present invention. In addition to providing excellent all-around cleaning power when used in combination with polyhydroxy fatty acid amides (see below), including good fat/oil cleaning over a wide range of temperatures, wash concentrations and wash times, alkyl Dissolution of sulfates, and improved formulation performance in liquid detergent formulations, alkyl sulfates are water-soluble salts or acids of formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbon group, preferably is an alkyl group or a hydroxyalkyl group having a C ₁₀ -C ₂₀ alkyl component, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl group, and M is H or a cation such as an alkali (Group IA) metal cation (such as sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methylammonium, dimethylammonium, and trimethylammonium ions, and quaternary ammonium cations such as tetramethylammonium ion and dimethylpiperidinium, and Cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, mixtures thereof, and the like. Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for lower wash temperatures (e.g., below about 50°C), and C ₁₆ -C 16 for higher wash temperatures (e.g., above about 50°C). An alkyl chain of ₁₈ is preferred.

Alkyl alkoxylated sulfate surfactants are another class of useful anionic surfactants. These surfactants are water-soluble salts or acids of the general formula RO(A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkane with a C ₁₀ -C ₂₄ alkyl component A group, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl group, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl group. A is an ethoxy or propoxy unit, m is greater than 0, usually about 0.5-6, more preferably about 0.5-3, M is H or a cation, such as a metal cation (such as sodium, potassium, lithium, etc.) , ammonium or substituted ammonium cations. The present invention contemplates the use of alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methylammonium, dimethylammonium, trimethylammonium, and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium, and alkanolamines such as monoethanolamine, diethanolamine, Triethanolamine-derived cations, and mixtures thereof. Examples of surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate Oxygenate (3.0) sulfates and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfates, wherein M is conveniently selected from sodium and potassium. The surfactants used in the present invention can be manufactured from natural or synthetic alcohol feedstocks. Chain lengths represent the average hydrocarbon distribution, including branches.

Additionally and preferably, the surfactant may be 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 PCT Published Applications WO99/19434, WO99/18929, WO99/19435, WO99/18928, WO99/19448 and WO99/19449. Other suitable mid-chain branched surfactants can be found in US Patent Applications 6,008,181, 6,060,443, 6,020,303, 6,093,856, PCT Published Application WO 97/38972, US Patent Applications 6,046,152 and 6,015,781. Mixtures of these branched chain surfactants with conventional linear surfactants are also suitable for use in the compositions of the present invention.

Another preferred anionic surfactant is the so-called modified alkylbenzene sulfonate surfactant, or MLAS. Some suitable MLAS surfactants, methods of making them, and typical compositions are in U.S. Patent Application Nos. 6,274,540, 6,593,285, 6,306, 817, 6,602,840, PCT Published Application WO99/05084, U.S. Patent Application Nos. 6,566,319, 6,525,233, 6,514,926, and 6,583,096 described further.

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

Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are listed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 13, line 14 to column 16, line 6 is generally described in , which is incorporated herein by reference. Typical, non-limiting classes of useful nonionic surfactants include: amine oxides, alkyl ethoxylates, alkanoyl glucamides, alkyl betaines, sultaines, and mixtures thereof.

Amine oxides are semi-polar nonionic surfactants and include an alkyl moiety containing about 10-18 carbon atoms and two moieties selected from alkyl and hydroxyalkyl groups containing about 1-3 carbon atoms Partial water-soluble amine oxides; water-soluble phosphine oxides containing an alkyl moiety of about 10-18 carbon atoms and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups of about 1-3 carbon atoms; containing a Alkyl moieties of about 10-18 carbon atoms and water-soluble sulfoxides of moieties selected from alkyl and hydroxyalkyl moieties of about 1-3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants having the following formula:

Wherein, ^R3 is alkyl, hydroxyalkyl, or alkylphenyl or mixtures thereof containing about 8-22 carbon atoms; ^R4 is alkylene or hydroxyalkylene containing about 2-3 carbon atoms or mixtures thereof; x is 0 to about 3; each ^R is an alkyl or hydroxyalkyl group containing about 1 to 3 carbon atoms or a polyepoxide containing about 1 to 3 oxirane groups ethane. R ⁵ may be linked to each other, for example via an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides. Preferably, the amine oxide is present in the composition in an effective amount, more preferably from about 0.1% to 20%, more preferably from about 0.1% to 15%, still more preferably from about 0.5% to 10% by weight. %.

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols. Polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkylphenols with alkylene oxides having alkyl groups containing from about 6 to about 12 carbon atoms in a linear or branched structure. In a preferred embodiment, the ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include ^Igepal® CO-630, sold by GAF Corporation; and ^Triton® X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company . These compounds are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Condensation products of fatty alcohols with about 1 to 25 moles of ethylene oxide. The alkyl chain of the fatty alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having alkyl groups containing about 10-20 carbon atoms with about 2-18 moles of ethylene oxide per mole of alcohol. Commercially available nonionic surfactants of this type include ^Tergitol® 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear secondary alcohols with 9 moles of ethylene oxide), Tergitol® ²⁴ -L-6 NMW (condensation product of a C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution), both sold by Union Carbide Corporation; ^Neodol® 45-9 (C ₁₄ -C ₁₅ linear alcohol with Condensation product of 9 moles of ethylene oxide), Neodol ^® 23-6.5 (condensation product of C ₁₂ -C ₁₃ straight chain alcohol and 6.5 moles of ethylene oxide), Neodol ^® 45-7 (C ₁₄ -C ₁₅ straight chain alcohol with 7 moles of ethylene oxide), ^Neodol® 45-4 (a condensation product of a C ₁₄ -C ₁₅ linear alcohol with 4 moles of ethylene oxide), sold by Shell Chemical Company, and ^Kyro® EOB ( Condensation product of a _C13 - _C15 alcohol with 9 moles of ethylene oxide), sold by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8 ^(R) sold by Shell Chemical Co. and Genapol UD-080( ^R) sold by Hoechst. Such nonionic surfactants are generally referred to as "alkyl ethoxylates".

The molecular formula of preferred alkyl polyglucosides is:

R ² O(C _n H _2n O) _t (glycosyl) _x

Wherein, R ^is selected from alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains about 10-18, preferably about 12-14 carbon atoms; n is 2 or 3, preferably 2; t is 0-about 10, preferably 0; x is about 1.3-10, preferably about 1.3-3, most preferably about 1.3-2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxylated alcohol is first formed and then reacted with glucose or a source of glucose to form the glycoside (attachment at the 1 position). Additional glycosyl units may then be attached between position 1 thereof and the preceding glycosyl unit at positions 2, 3, 4 and/or 6, preferably predominantly at position 2.

The molecular formula of fatty acid amide surfactant is:

Wherein, R ⁶ is an alkyl group containing about 7-21 (preferably about 9-17) carbon atoms, and each R ⁷ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl , and -(C ² H ₄ O) _x H, where x is about 1-3.

Preferred amides are C ₈ -C ₂₀ aminoamides, monoethanolamides, diethanolamides and isopropanolamides.

It is preferred that when a nonionic surfactant is present in the composition, it is present in an effective amount, more preferably from about 0.1% to 20% by weight, more preferably from about 0.1% to 15%, even more About 0.5%-10% is preferred.

Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions herein can also contain an effective amount of a polyhydroxy fatty acid amide surfactant. "Effective amount"means that amount of polyhydroxy fatty acid amide that the formulator of the composition may choose to incorporate into the composition will improve the cleaning performance of the detergent composition. In general, the incorporation of about 1% by weight of polyhydroxy fatty acid amide will enhance detergency for conventional use levels.

The detergent compositions herein generally comprise about 1% by weight of the polyhydroxy fatty acid amide surfactant, preferably from about 3% to about 30% of the polyhydroxy fatty acid amide. Polyhydroxy fatty acid amide surfactant ingredients include compounds of the following structural formula:

Wherein: R ¹ is H, C ₁ -C ₄ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ Alkyl, most preferably C ₁ alkyl (ie methyl); R ² is C ₅ -C ₃₁ hydrocarbyl, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₅ alkyl or alkenyl, or mixtures thereof; Z is a polyhydroxyl hydrocarbon having a straight alkyl chain, and at least The 3 hydroxyl groups are attached directly to the straight hydrocarbyl chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Preferably, Z is obtained from a reducing sugar in a reductive amination reaction; more preferably, Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, high maltose corn syrup as well as the various sugars listed above can be used. These corn syrups can create a mixture of Z's sugar components. It should be understood that other suitable starting materials are not meant to be excluded. Z is preferably selected from _-CH2- (CHOH) _n - _CH2OH , -CH( _CH2OH )-(CHOH) _{n-1 -CH2OH} , _-CH2- (CHOH) ₂ (CHOR') (CHOH)-CH ₂ OH, and their alkoxylated derivatives, where n is an integer of 3-5, including 3 and 5, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are alditol groups where n is 4, specifically _-CH2- (CHOH) ₄ - _CH2OH .

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

R ² —CO—N< can be, for example, cocamide, stearylamide, oleylamide, laurylamide, lactamide, capricamide, palmitamide, tallowamide, and the like.

Z can be 1-deoxyglucitol (1-deoxyglucityl), 2-deoxyfructitol (2-depxyfructityl), 1-deoxymaltitol (1-deoxymaltityl), 1-deoxylactitol (1-deoxylactityl), 1-deoxygalactityl (1-deoxygalactityl), 1-deoxymannitol (1-deoxymannityl), 1-deoxymaltotriitol (1-deoxymaltotriotityl) and the like.

Methods of making polyhydroxy fatty acid amides are known in the art. In general, they can be obtained by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkylpolyhydroxylamine, and then reacting the N-alkylpolyhydroxylamine with fatty esters of fatty acids or triglycerides The esters are prepared by reacting in a condensation/amidation step to form N-alkyl, N-polyhydroxy fatty acid amide products. Methods for making compositions containing polyhydroxy fatty acid amides are described, for example, in British Patent Specification 809,060, issued February 18, 1959, by Thomas Hedley & Co., Ltd., in U.S. Patent Specification 809,060, issued December 20, 1960, by E.R. Wilson Patent 2,965,576, US Patent 2,703,798 issued March 8, 1955 to Anthony M. Schwartz, and US Patent 1,985,424 issued December 25, 1934 to Piggott, each of which is incorporated herein by reference.

Diamines - Preferred liquid detergent compositions useful in the method of the present invention, such as light duty liquid LDL compositions, may also contain one or more diamines, preferably in an amount such that the anionic surface active The ratio of agent to diamine is about 40:1-2:1. The diamines enhance the removal of grease and fatty foods while maintaining the right amount of foam.

Diamines suitable for use in the compositions of the present invention have the following formula:

Wherein, each R ²⁰ is independently selected from hydrogen, C ₁ -C ₄ linear or branched chain alkyl, alkylene oxygen having the following molecular formula:

-(R ²¹ O) _y R ²²

Wherein, R ²¹ is C ₂ -C ₄ linear or branched alkylene, and mixtures thereof; R ²² is hydrogen, C ₁ -C ₄ alkyl, and mixtures thereof; y is 1 to about 10; X is A unit selected from the following substances:

i) C ₃ -C ₁₀ straight chain alkylene, C ₃ -C ₁₀ branched chain alkylene, C ₃ -C ₁₀ cycloalkylene, C ₃ -C ₁₀ branched cycloalkylene, and the following molecular formula Alkyloxyalkylene:

-(R ²¹ O) _y R ²¹ -

Wherein, R ²¹ and y are the same as defined above;

ii) C ₃ -C ₁₀ straight chain alkylene, C ₃ -C ₁₀ branched straight chain alkylene, C ₃ -C ₁₀ cycloalkylene, C ₃ -C ₁₀ branched cycloalkylene, C ₆ -C ₁₀ arylene, wherein said unit comprises one or more electron donating or electron withdrawing moieties that provide said diamine with a pK _a of greater than about 8; and

iii) A mixture of i) and ii), provided that the diamine has a pK _a of at least about 8.

The _pK1 and _pK2 of the preferred diamines of this invention are both in the range of about 8-11.5, preferably about 8.4-11, more preferably about 8.6-10.75. For the purposes of the present invention, the term "pK _a " likewise stands alone or collectively for the terms "pK ₁ " and "pK ₂ ". The term _pKa as used herein is used throughout the specification in the same manner as it is used by those skilled in the art. pKa _values are readily obtained from standard literature sources such as "Critical Stability Constants: Volume 2, Amines" Smith and Martel eds., Plenum Press, New York and London (1975).

As a definition used herein, the _pKa value of a diamine is specified as the value measured in an aqueous solution at 25°C with an ionic strength of about 0.1-0.5M. As used herein, pKa is an equilibrium constant that depends on temperature and ionic strength, so values reported by references other than those measured in the above manner may not be entirely consistent with values and ranges encompassing the invention. To eliminate uncertainty, relevant conditions and/or references for the pK _a values of the present invention are as defined herein, or in "Critical Stability Constants: Volume 2, Amines" Described in. A typical measurement method is the potentiometric titration of acid and sodium hydroxide and by the method as described in "The Chemist's Ready Reference Handbook", edited by Shugar and Dean, McGraw Hill, New York, 1990 The _pKa was determined by an appropriate method as described and cited.

For performance and availability reasons, the preferred diamines are 1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane (pK ₁ =10.5; pK ₂ =8.8), 1,6- Diaminohexane (pK ₁ =11; pK ₂ =10), 1,3-diaminopentane (Dytek EP) (pK ₁ =10.5; pK ₂ =8.9), 2-methyl-1,5-di Aminopentane (Dytek A) (pK ₁ =11.2; pK ₂ =10.0). Other preferred materials are primary/primary diamines with C ₄ -C ₈ alkylene spacers. In general, primary diamines are preferred over 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, the molecular formula is:

1,6-Diaminohexane, the molecular formula is:

1,3-diaminopropane, the molecular formula is:

2-Methyl-1,5-diaminopentane, the molecular formula is:

1,3-Diaminopentane, available under the tradename Dytek EP, has the formula:

1,3-Diaminobutane, the molecular formula is:

Jeffamine EDR 148, a diamine with an alkyleneoxy backbone with the formula:

3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine), the molecular formula is:

and

1,3-bis(methylamino)cyclohexane, the molecular formula is:

additional detergent ingredients

The following are non-limiting examples of additional detergent ingredients (adjunct ingredients) that may be used in the bleaching compositions of the present invention, particularly laundry detergent compositions, including builders, optical brighteners, Soil polymers, dye transfer agents, dispersants, enzymes, foam suppressors, dyes, fragrances, colorants, filler salts, hydrotropes, photosensitizers, fluorescers, fabric conditioners, hydrolyzable surfactants, Preservatives, antioxidants, chelating agents, stabilizers, anti-shrinkage agents, anti-wrinkle agents, bactericides, fungicides, anti-corrosion agents, and mixtures thereof.

Builders - The bleaching compositions of the present invention preferably contain one or more detergent builders or builder systems. When present, the compositions generally contain at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably is to about 30% by weight of detergent builder.

The builder level can vary widely depending on the end use of the composition and its desired physical form. When present, the compositions generally contain at least about 1% of builders. Formulations generally contain from about 5% to 50%, more typically from about 5% to 30%, by weight of detergent builder. Granular formulations generally contain from about 10% to 80%, more typically from about 15% to 50%, by weight, of detergent builder. However, lower or higher levels of builder are not meant to be excluded.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, polyphosphates (represented by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acids, silicates, carbon Alkali metal, ammonium and alkanolammonium salts of acid salts (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in some places. Importantly, even in the presence of so-called "weak" builders (as compared to phosphates) such as citrates, or in the presence of so-called "underbuilt" builders that can occur with zeolite or layered silicate builders The compositions herein also work surprisingly well in "underbuilt" situations.

Examples of silicate builders are alkali metal silicates, especially those with a _SiO2 : _Na2O ratio of 1.6:1 to 3.2:1, and layered silicates as described in Rieck, 1987. Layered sodium silicates described in US 4,664,839, issued May 12, 2009. NaSKS-6 is the trade designation for a crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has the δ-Na ₂ SiO ₅ morphological form of phyllosilicates. It can be prepared by methods such as those described in German patents DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred phyllosilicate for use in the present invention, but other such phyllosilicates may also be used in the present invention, such as phyllosilicates of the general formula _{NaMSixO2x +1 yH2O} A silicate 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 include NaSKS-5, NaSKS-7 and NaSKS-11, in the alpha, beta and gamma forms. As noted above, delta- _Na2SiO5 (NaSKS-6 form) is most preferred for _use in the present invention. Other silicates can also be used, such as magnesium silicate, which can be used as an embrittler in granular formulations, as a stabilizer for oxygen bleaches, and as an ingredient in foam control systems.

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

Aluminosilicate builders are useful herein. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and are also a builder ingredient of interest in liquid detergent formulations. Aluminosilicate builders include those of the following experimental formula:

[M _z (zAlO ₂ ) _y ] _x H ₂ O

wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, and x is an integer of about 15-264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetic. A method of producing aluminosilicate ion exchange materials is disclosed in U.S. 3,985,669, issued October 12, 1976 to Krummel et al. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the designations Zeolite A, Zeolite P(B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na1 ₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O

Wherein, x is about 20-30, especially about 27. This material is called Zeolite A. Dehydrated zeolites (x=0-10) can also be used in the present invention. Preferably, the particle size of the aluminosilicate is about 0.1-10 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 a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders can generally be incorporated into the compositions in acid form, but can also be incorporated in neutral salt form. When used in salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred.

Included in polycarboxylate builders are many types of useful materials. An important class of polycarboxylate builders includes ether polycarboxylates, including oxydisuccinates, as described in U.S. 3,128,287, Berg, April 7, 1964; Lamberti et al., 1972 U.S. 3,635,830 issued January 18, 1976 and U.S. 3,936,448 issued February 3, 1976 to Lamberti. See also U.S. 4,663,071, Bush et al., issued May 5, 1987 for "TMS/TDS" builders. Suitable ether polycarboxylates also include cyclic compounds, especially cycloaliphatic compounds, such as U.S. 3,923,679 issued December 2, 1975 to Rapko, U.S. 4,158,635 issued June 19, 1979 to Crutchfield et al. As described in U.S. 4,120,874, Crutchfield et al., issued October 17, 1978, and U.S. 4,102,903, Crutchfield et al., issued July 25, 1978.

Other useful detergency builders include ether hydroxy polycarboxylates; copolymers of maleic anhydride and ethylene or vinyl methyl ether; 1,3,5-trihydroxybenzene-2,4,6-trisulfonate and carboxymethyl hydroxysuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; and polycarboxylates such as mellitic acid, butanedioic acid acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyl hydroxysuccinic acid, and their soluble salts.

Citrate builders such as citric acid and its soluble salts (especially the sodium salt) are particularly important polycarboxylates for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability salt builder. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

Also suitable in the bleaching compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compound. Useful succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this class is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, etc. Laurylsuccinate is a preferred builder of this group and is described in European Patent Application 86200690.5/0,200,263, published November 5,1986.

Other suitable polycarboxylates are described in U.S. 4,144,226, Crutchfield et al., March 13, 1979 and U.S. 3,308,067, Diehl, March 7, 1967. See also U.S. Patent 3,723,322 to Diehl.

Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids may also be incorporated into the compositions alone or with the above-mentioned builders, especially citrate and/or succinate builders, to provide additional builder activity . Such use of fatty acids generally results in a reduction in foam and should be considered by the formulator.

Where phosphorus-based builders can be used, particularly in the formulation of bar soaps for use in hand laundry operations, the 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 (see, eg, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137) can also be used.

Chelating Agents - The bleaching compositions herein may also optionally contain one or more iron and/or manganese chelating agents. These chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without intending to be bound by theory, it is believed that the benefits of these materials are due in part to their particular ability to remove iron and manganese ions from wash liquors by forming soluble chelates.

Examples of suitable chelating agents and their amounts are described in US Patent Nos. 5,576,282 and 5,728,671.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly the [S,S] isomer, as published November 3, 1987 by Hartman and Perkins described in US Patent 4,704,233.

The compositions herein may also contain water-soluble methylglycine diacetic acid (MGDA) salts (or in the acid form) as chelating agents or co-builders which may be used with insoluble builders such as zeolites and layered silicates and the like.

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the bleaching compositions of the present invention, more preferably 3.0% by weight of the bleaching compositions of the present invention.

Dye Transfer Inhibiting Agents - The bleaching compositions of the present invention may also contain one or more compounds, dye transfer inhibiting agents, for inhibiting the transfer of dissolved and suspended dyes from a fabric during fabric laundering and conditioning operations involving colored fabrics. Dye transfer to another fabric.

Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone and polyvinyl imidazole or their mixtures. Examples of such dye transfer inhibiting agents are described in US Patent Nos. 5,707,950 and 5,707,951.

Other suitable dye transfer inhibiting agents include, but are not limited to, crosslinked polymers. Cross-linked polymers are polymers whose main chains are connected to each other in some way; these connections can be chemical or physical in nature, and there may be reactive groups on the main chain or on the branches. Cross-linked polymers have been described in Journal of Polymer Science Vol. 22, pp. 1035-1039.

In one embodiment, the cross-linked polymers are fabricated in such a way that they form a three-dimensional rigid structure which can trap the dye in the pores formed in the three-dimensional structure.

In another embodiment, the crosslinked polymer entraps the dye by swelling.

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

The addition of such polymers also enhances the performance of the enzymes within the bleaching compositions herein.

Dye transfer inhibiting agents have the ability to complex or adsorb fugitive dyes that are washed from colored fabrics in the wash before the dye has a chance to attach to other items.

When present in the bleaching compositions of the present invention, the level of dye transfer inhibiting agents ranges from about 0.0001%, more preferably about 0.01%, most preferably about 0.05% by weight of the bleaching composition to about 0.0001% by weight of the bleaching composition. 10%, more preferably about 2%, most preferably about 1%.

Dispersants - The bleaching compositions of the present invention may also contain dispersants. Suitable water-soluble organic salts are homo- or co-polymeric acids or their salts, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, these copolymers having a molecular weight of 1,000-100,000.

In particular, copolymers of acrylate and methacrylate, such as 480N with a molecular weight of 4000, can be added in the detergent composition of the present invention at a level of 0.5-20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptiser compound having a Lime Soap Dispersing Power (LSDP) as defined below of no greater than 8, preferably no greater than 7, most preferably no greater than 6. The preferred content of lime soap peptizer is 0-20% by weight.

A numerical measure of the effect of lime soap peptizers is given by lime soap dispersing power (LSDP), which uses HC Borghetty and CA Bergman in J.Am.Oil.Chem.Soc., Vol. 27, No. 88 - Lime soap dispersant test determination described in the article on page 90 (1950). This lime soap dispersion test is widely used by those skilled in the art and is mentioned, for example, in the following review articles: WN Linfield, Surfactant science Series, Vol. 7, p. 3; WN Linfield, Tenside Surf .det. Vol. 27, pp. 159-163 (1990); and MK Nagarajan, WF Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73, (1989). LSDP is the weight percent ratio of dispersant to sodium oleate required to disperse lime soap deposits formed from 0.025 g of sodium oleate in 30 ml of 333 ppm CaCO ₃ (Ca:Mg=3.2) equivalent hardness water.

Surfactants with good lime soap peptizing capabilities would include certain amine oxides, betaines, sultaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Exemplary surfactants having an LSDP of no greater than 8 for use in accordance with the present invention include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C ₁₈ alkyl ethoxy sulfates having an average degree of ethoxylation of 1-5, especially is a C ₁₂ -C ₁₅ alkyl ethoxylated sulfate with a degree of ethoxylation of 3 (LSDP=4), and an average degree of ethoxylation of 12 (LSDP=6) sold under the trade names Lutensol A012 and Lutensol A030, respectively, by BASF GmbH or 30 C ₁₄ -C ₁₅ ethoxylated alcohols.

Polymeric lime soap peptizers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, available in Cosmetics and Cosmetics, Vol. 104, pp. 71-73 (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-nonanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-decanoyl- 6-aminocaproyl]benzenesulfonate and mixtures thereof; and nonanoyloxybenzenesulfonate for use with hydrophilic/hydrophobic bleach formulations can also be used as lime soap peptizing compounds.

Enzymes - In addition to the amylases of the present invention, the bleaching compositions may comprise one or more detergent enzymes which provide cleaning and/or fabric care benefits. Such enzymes may include proteases, amylases, cellulases and lipases. They may be introduced into the non-aqueous liquid bleaching compositions of the present invention in the form of suspensions, "marumes" or "pellets". Another suitable type of enzyme includes enzymes in the form of a slurry of the enzyme in a non-ionic surfactant, such as the enzymes sold under the trade name "SL" by Novo Nordisk or the enzymes sold under the trade name "LDP" by Novo Nordisk Microencapsulated enzymes. Suitable enzymes and their amounts are described in US Patent 5,576,282.

Enzymes incorporated into the compositions herein in the form of conventional enzyme pellets are particularly preferred for use in the present invention. Such small particles will generally be about 100-1,000 microns in size, more preferably about 200-800 microns, and will be suspended throughout the non-aqueous liquid phase of the composition. Compared to other enzyme forms, it has been found that the granules in the compositions of the present invention exhibit particularly desirable enzyme stability, the latter being indicated by the maintenance of enzyme activity over time. Thus, compositions utilizing enzyme prills do not need to contain conventional enzyme stabilizers as is usually necessary when enzymes are incorporated into aqueous liquid detergents.

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, pullulanases, tannases, pentosanases, maltosanases Carbohydrases (malanases), beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, known amylases, mannanases, xyloglucanases and their mixture. A preferred combination is a bleaching composition having a cocktail of conventionally suitable enzymes such as proteases, lipases, cutinases and/or cellulases in combination with amylases of the invention.

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

Suitable proteases are the subtilisins (subtilisins BPN and BPN') obtained from specific strains of B. subtilis and B. licheniformis. A suitable protease is obtained from a strain of bacillus having maximum activity in the pH range of 8-12, developed and sold under the trade name ^ESPERASE® by Novo Industries A/S of Denmark, hereinafter Called "Novo". The preparation of this and similar enzymes is described in GB 1,243,784 to Novo. Other suitable enzymes include ALCALASE® ^{, DURAZYM®} and ^SAVINASE® from Novo, and ^MAXATASE® , ^MAXACAL® , PROPERASE® ^{and MAXAPEM®} (Maxacal for protein control) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, as described in European Patent Application EP251 446 (particularly pages 17, 24 and 98), referred to herein as "Protease B", and Venegas 1986 A modified bacterial serine proteolytic enzyme described in European Patent Application 199,404 published on October 29, 1999, referred to herein as "Protease A". More preferred is the enzyme referred to herein as "Protease C", which is a variant of the alkaline serine protease from Bacillus in which a lysine is substituted for arginine at position 27 and a tyrosine is at position 104 Substituting valine, serine at position 123 for asparagine, alanine at position 274 for threonine. Protease C is published on May 16, 1991 in EP90915958:4 corresponding to WO 91/06637. Genetically modified variants, particularly variants of Protease C, are also included herein. See also the high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Where desired, proteases which have reduced adsorption and increased hydrolysis are available as described in WO 95/07791 to Procter & Gamble. Recombinant trypsin-like proteases suitable for use in the detergents herein are described in WO 94/25583 to Novo.

In more detail, the protease designated "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature by substituting a different amino acid at the position corresponding to position +76 in said carbonyl hydrolase Multiple amino acid residues obtained from precursor carbonyl hydrolases, preferably also combined with one or more amino acid residue positions corresponding to the numbering of Bacillus amyloliquefaciens subtilisin Selected from +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 positions, as in WO 95, published April 20, 1995 by Genencor International /10615. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/06637 and the protease BLAP ^(R) described in WO 91/02792. The introduction amount of proteolytic enzyme in the bleaching composition of the present invention is 0.0001%-2%, preferably 0.001%-0.2%, more preferably 0.005%-0.1% pure enzyme by weight of the composition.

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

Other particularly useful proteases are multiple substitution protease variants comprising substitution of an amino acid residue at the amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin with another naturally occurring amino acid residue , and bind at 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, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, One or more amino acid residues of 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274, and 275 Substituting an amino acid residue at a position with another naturally occurring amino acid residue; wherein, when the protease variant includes substitutions of amino acid residues at positions corresponding to positions 103 and 76, there are also Position 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisin Substitution of amino acid residues at one or more amino acid residue positions other than amino acid residue positions and/or inclusion at positions 62, 212, 230, 232, 252 corresponding to Bacillus amyloliquefaciens subtilisin Multiple substitution protease variants in which amino acid residues are substituted with another naturally occurring amino acid residue at one or more amino acid residue positions of 257 and 257, as in PCT Published Application WO 99/20727, all owned by The Procter & Gamble Company , WO 99/20726 and WO 99/20723.

More preferably, the protease variant comprises a group of substitutions selected from the following positions:

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

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

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;

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 preferably, said protease variant comprises a group of substitutions selected from the following positions:

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

  62D/103A/104I/159D/232V/236H/245R/248D/252K;

62D/103A/104I/159D/213R/232V/236H/245R/248D/252K;

  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/252K;

68A/103A/104I/159D/183D/232V/236H/245R/248D/252K;

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

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

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

68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;

68A/103A/1041/159D/185D/232V/236H/245R/248D/252K;

68A/103A/104I/159D/185D/210L/232V/236H/245R/248D/252K;

68A/103A/104I/159D/210L/232V/236H/245R/248D/252K;

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

98L/103A/104I/159D/232V/236H/245R/248D/252K;

98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K;

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

    102A/103A/104I/159D/232V/236H/245R/248D/252K;

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

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

    103A/1041/159D/217E/232V/236H/245R/248D/252K;

    103A/104I/130G/159D/232V/236H/245R/248D/252K;

    103A/104I/131V/159D/232V/236H/245R/248D/252K;

  103A/104I/159D/213R/232V/236H/245R/248D/252K; and

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

Most preferably, said protease variant comprises the substitution group 101/103/104/159/232/236/245/248/252, preferably 101G/103A/104I/159D/232V/236H/245R/248D/252K .

Cellulases useful in the present invention include bacterial or fungal cellulases. Preferably, they have a pH optimum of 5-9.5. Suitable cellulases are described in US Patent 4,435,307 to Barbesgoard et al., which discloses fungal cellulases derived from Humicola insolens. Suitable cellulases are also described 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 (Humicolagrisea var. thermoidea), especially strains of Humicola strain DSM 1800.

Other suitable cellulases are cellulase derived from Humicola insolens, with a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~43 kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; preferred endoglucanase components have the amino acid sequence disclosed in PCT patent application WO91/17243. Also suitable cellulases are the EGIII cellulases from Trichodermal longibrachiatum described in WO 94/21801, published September 29, 1994, Genencor. Particularly suitable cellulases are cellulases with color care action. Examples of such cellulases are the cellulases described in European Patent Application 91202879.2 (Novo), filed November 6, 1991 . Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful. See also WO 91/17243.

Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloroperoxidase and bromoperoxidase oxidase. Peroxidase-containing bleaching compositions are e.g. described in U.S. Patents 5,576,282, 5,728,671 and 5,707,950, PCT International Applications WO 89/099813, WO 89/09813 and European Patent Application EP 91202882.6 filed on November 6, 1991 and European Patent Application EP540 784 described. Also suitable are laccases.

Preferred enhancers are substituted phenothiazines and phenoxasines (phenoxasines) 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazine propionate acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C ₃ -C ₅ substituted alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

The peroxidase is incorporated into the bleaching composition at an active enzyme level of 0.0001-2% by weight of the bleaching composition.

Other preferred enzymes that may be included in the bleaching compositions of the present invention include lipases. Suitable lipases for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in British Patent 1,372,034. Suitable lipases include those that exhibit positive immunological cross-reactivity with antibodies to lipase (produced by Pseudomonas fluorescent IAM 1057). This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, a lipase obtained from Chromobacter viscosum, such as Chromobacter viscosum var. lipolyticum NRRLB 3673 available from Toyo Jozo Co., Tagana, Japan; available from US Biochemical Corp., ), Chromobacter viscosum lipase from the United States and Disoynth Co., The Netherlands, and lipase from Pseudomonas gladioli. Particularly suitable lipases are M1 ^LIPASE® and ^LIPOMAX® (Gist-Brocades) and ^LIPOLASE® and ^{LIPOLASEULTRA®} (Novo), which have been found to be very effective when used in combination with the compositions of the present invention.

Also suitable are cutinases [EC 3.1.1.50], which can be considered as a specific type of lipase, ie lipases that do not require interfacial activation. The addition of cutinase to bleaching compositions has been described, for example, in WO 88/09367 (Genencor).

Lipase and/or cutinase are usually incorporated into the bleaching composition in an amount of 0.0001-2% active enzyme by weight of the bleaching composition.

Known amylases (alpha and/or beta) may be included to remove carbohydrate based stains. WO 94/02597, Novo Nordisk A/S, published February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO 94/18314 published August 18, 1994 to Genencor and WO 95/10603 published April 20, 1995 to Novo Nordisk A/S. Other amylases for use in bleaching compositions include alpha-amylases and beta-amylases. Alpha-amylases are known in the art and are included 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 Specification No. 1,296,839 (Novo) The disclosed alpha-amylase. Other suitable amylases are stability-enhanced amylases including PURAFACT OX AM® as described in WO 94/18314, published August 18, 1994, and WO 96/05295, published February 22, 1996 ^, by Genencor and the amylase variants disclosed in WO 95/10603, published April 95 from Novo Nordisk A/S.

Examples of commercial alpha-amylase products are ^TERMAMYL® , ^BAN® , FUNGAMYL® ^{and DURAMYL®} , all commercially available from Novo Nordisk A/S Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized by a specific activity ratio measured by the Phadebas ^® α-amylase activity assay compared to TERMAMYL ^® at 25-55° C. and a pH value of 8-10. At least 25% higher specific activity. Other amylolytic enzymes with improved performance in terms of activity level and the combination of thermostability and higher activity are described in WO 95/35382.

Compositions of the invention may also comprise a mannanase. Preferably, the mannanase is selected from the group consisting of: trimannan-degrading enzymes: EC 3.2.1.25: β-mannosidase, EC 3.2.1.78: endo-1,4-β-mannosidase, hereinafter referred to as " Mannanase" and EC 3.2.1.100: 1,4-beta-mannobiosidase and mixtures thereof. (IUPAC Taxonomy-Enzyme Nomenclature, 1992 ISBN 0-12-227165 Academic Press).

More preferably, when a mannanase is present, the treatment composition of the invention comprises a beta-1,4-mannosidase (E.C. 3.2.1.78) known as mannanase. The term "mannanase" or "galactomannanase" means a mannanase as defined in the art, formally named endomannan-1,4-beta-mannosidase, other names are β-mannanases and endo-1,4-mannanases that catalyze the 1,4-β- Random hydrolysis of mannosidic linkages of D-mannose.

In particular, mannanases (EC 3.2.1.78) constitute a group of glycanases which degrade mannan and denote enzymes capable of breaking down glycan chains containing mannose units, i.e. capable of breaking down mannan, glucomannan Enzyme of glycosidic linkages in glycans, galactomannan and galactoglucomannan. Mannan is a polysaccharide with a backbone consisting of β-1,4-linked mannose; glucomannan is a polysaccharide with more or less regularly alternating β-1,4-linked mannose and glucose Glycans of the main chain; galactomannans and galactoglucomannans are mannans and glucomannans with alpha-1,6 linked galactose side chains. These compounds can be acetylated.

Degradation of galactomannan and galactoglucomannan is facilitated by total or partial removal of galactose side chains. In addition, the degradation of acetylated mannans, glucomannans, galactomannans and galactoglucomannans is facilitated by total or partial deacetylation. Acetyl groups can be removed by base or by mannan acetylesterase. Oligomers released by mannanase or the combination of mannanase and α-galactosidase and/or mannan acetylesterase can be produced by β-mannosidase and/or β-glucosidase Further degradation releases free maltose.

Mannanases have been identified in several Bacillus organisms. For example, Talbot et al. in Appl. Environ. Microbiol., Vol. 56, No. 11, pp. 3505-3510 (1990) describe a dimer form with a molecular weight of 162 kDa and an optimum pH value of 5.5-7.5 β-mannanase from Bacillus stearothermophilus. Mendoza et al. described in World J.Microbiol.Biotech., Vol. 10, No.5, pp. 551-555 (1994) that the molecular weight is 38 kDa, pH is 5.0 and 55C and pI is 4.8. Active beta-mannanase obtained from Bacillus subtilis. JP-03047076 describes a β-mannanase of Bacillus origin, with a molecular weight of 373 kDa as determined by gel filtration, an optimum pH of 8-10, and a pi of 5.3-5.4. JP-63056289 describes the production of alkaline, thermostable β-mannanases which hydrolyze, for example, β-1,4-D-mannopyranoside linkages of mannans and produce mannooligosaccharides (manno-oligosaccharides). JP-63036774 relates to a microorganism of the genus Bacillus, FERMP-8856, which produces β-mannanase and β-mannosidase at alkaline pH. JP-08051975 discloses an alkaline mannanase from the alkaliphilic Bacillus sp. AM-001. Refined mannanases from Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and methods for their preparation are disclosed in WO97/11164. WO 91/18974 describes hemicellulases such as dextranases, xylanases or mannanases which are active at extremes of pH and temperature. WO 94/25576 discloses an enzyme from Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity useful for the degradation or modification of plant or algal cell wall material. WO93/24622 discloses a mannanase isolated from a strain of Trichoderma reseei useful for bleaching lignocellulosic pulp. Hemicellulases capable of degrading mannan-containing hemicelluloses are described in WO 91/18974 and refined mannanases from Bacillus amyloliquefaciens are described in WO 97/11164.

Preferably the mannanase is an alkaline mannanase as defined below, more preferably a mannanase originating from a bacterial source. In particular, the laundry detergent composition of the invention comprises a mannanase selected from the group consisting of a mannanase from strain Bacillus agaradhaerens NICMB 40482, a mannanase from Bacillus subtilis strain 168, gene yght, Alkaline mannanase from mannanase from Bacillus sp. 1633 and/or mannanase from Bacillus sp. AAI12. The most preferred mannanase for incorporation into the detergent compositions of the present invention is a mannanase derived from Bacillus sp. 1633 as described in co-pending Danish patent application PA 1998 01340.

The term "alkaline mannanase" refers to an enzymatic activity of at least 10%, preferably at least 25%, more preferably is at least 40% enzymes.

Alkaline mannanases from Bacillus agaradhaerens NICMB 40482 are described in co-pending US Patent Application Serial No. 09/111,256. More specifically, this mannanase is:

i) a polypeptide produced by Bacillus agaradhaerens, NCIMB40482; or

ii) a polypeptide comprising the amino acid sequence shown in positions 32-343 of SEQ ID NO: 2, as shown in U.S. Patent Application Serial No. 09/111,256; or

iii) an analogue of the polypeptide as defined in i) or ii), which is at least 70% homologous to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or are derived by immunologically reacting multi-cell lineage antibodies raised against the purified form of the polypeptide.

Also included are corresponding isolated polypeptides having mannanase activity selected from the group consisting of:

(a) A polynucleotide molecule encoding a polypeptide having mannanase activity and comprising a series of nucleosides from nucleoside 97 to nucleoside 1029 as shown in SEQ ID NO: 1, such as U.S. Patent Application Serial No. 09 Shown in /111,256;

(b) Species congeners of (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity, which is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343, as described in U.S. Patent Application No. As shown in 09/111,256;

(d) a complementary molecule to (a), (b) or (c); and

(e) The degenerated nucleotide sequence of (a), (b), (c) or (d).

Plasmid pSJ1678 comprising the polynucleotide molecule (DNA sequence) encoding the mannanase has been transformed into an Escherichia coli (Escherichia coli) bacterial strain, which has been deposited by the inventors under deposit number DSM 12180 on May 1998. Deposited at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode Weg 1b, D-38124 Braunschweig, Federal, on 18th April in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure.

A second more preferred enzyme is the mannanase from Bacillus subtilis strain 168, which is described in US Patent Application No. 6,060,299. More specifically, this mannanase is:

i) encoded by the coding portion of the DNA sequence shown in SED ID No. 5 shown in U.S. Patent Application 6,060,299, or an analog of said sequence; and/or

ii) a polypeptide comprising the amino acid sequence of SEQ ID NO: 6 shown in U.S. Patent Application 6,060,299; or

iii) A homologue of the polypeptide as defined in ii), which is at least 70% homologous to said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or by counteracting the refined form Antibodies derived from the polypeptides are immunologically reacted by multiple cell lines.

Also included are corresponding isolated polypeptides having mannanase activity selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide having mannanase activity and comprising a series of nucleosides as shown in SEQ ID NO: 5 as shown in U.S. Patent Application 6,060,299;

(b) (a) species congeners;

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 shown in U.S. Patent Application 6,060,299;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerated nucleotide sequence of (a), (b), (c) or (d).

A third more preferred mannanase is described in co-pending US patent application 6,566,114. More specifically, this mannanase is

i) a polypeptide produced by Bacillus sp. I633;

ii) a polypeptide comprising the amino acid sequence shown in positions 33-340 of SEQ ID: 2 as shown in U.S. Patent Application 6,566,114; or

iii) An analogue of the polypeptide defined in i) or ii), which is at least 65% homologous to said polypeptide, derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or by antagonizing A purified form of the polypeptide is derived from which antibodies are immunologically reacted by multiple cell lines.

Also included are corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) a polynucleotide encoding a polypeptide having mannanase activity and comprising a series of nucleotides shown in SEQ ID NO: 1 from nucleotide 317 to nucleotide 1243 in U.S. Patent Application 6,566,114 molecular;

(b) Species congeners of (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity at least 65% identical to SEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 in Danish patent application PA 1998 10340 have the same amino acid sequence;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerated nucleotide sequence of (a), (b), (c) or (d).

The plasmid pBXM3 comprising the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention has been transformed into an Escherichia coli (Escherichia coli) bacterial strain, which was prepared by the inventor according to Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under deposit number DSM 12197.

A fourth more preferred mannanase is described in US Patent Application No. 6,566,114. More specifically, this mannanase is:

i) a polypeptide produced by Bacillus sp. AAI 12;

ii) a polypeptide comprising the amino acid sequence shown in positions 25-362 of SEQ ID NO: 2 as shown in U.S. Patent Application 6,566,114; or

iii) an analogue of the polypeptide defined in i) or ii), which is at least 65% homologous to said polypeptide, derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or Derived by a multi-lineage antibody immune response raised against a purified form of the polypeptide.

Also included are corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) a polynucleotide encoding a polypeptide having mannanase activity and comprising a series of nucleotides shown in SEQ ID NO: 1 from nucleotide 225 to nucleotide 1236 in U.S. Patent Application 6,566,114 molecular;

(b) Species congeners of (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity which is at least 65% identical to SEQ ID NO: 2 from amino acid residue 25 to amino acid residue 362 in Danish patent application PA 1998 10341 Amino acid sequence is the same;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerated nucleotide sequence of (a), (b), (c) or (d).

The plasmid pBXM1 comprising the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention has been transformed into an Escherichia coli (Escherichia coli) bacterial strain, which was prepared by the inventor according to Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under deposit number DSM 12433.

When present, mannanase is preferably incorporated into the treatment compositions of the present invention at a concentration of 0.0001-2%, more preferably 0.0005-0.1%, most preferably 0.001-0.02% by weight of the composition. pure enzymes.

The composition of the invention may also comprise xyloglucanase enzyme. Suitable xyloglucanases for the purposes of the present invention are enzymes specific for xyloglucan that exhibit endoglucanase activity, preferably in an amount of about 0.001 to 1 by weight of the composition. %, more preferably about 0.01-0.5%. As used herein, the term "endoglucanase activity" means that the enzyme has the ability to hydrolyze any cellulosic material such as cellulose, cellulose derivatives, moss flour, β-D-glucan or xyloglucan The capacity for the presence of 1,4-β-D-glycosidic linkages. Endoglucanase activity can be assayed by methods known in the art, examples of which are described in WO 94/14953 and subsequent patent literature. One unit of endoglucanase activity (e.g. CMCU, AVIU, XGU or BGU) is defined as the production of 1 micromole of reducing sugar per minute from a dextran matrix such as CMC (CMCU), acid-swellable Avicell (AVIU), xyloglucan (XGU), or cereal beta-glucan (BGU). Reducing sugars are measured as described in WO 94/14953 and below. The specific activity of endoglucanase towards substrate is defined as units/mg protein.

Suitable is an enzyme exhibiting its highest activity XGU endoglucanase activity (hereinafter referred to as "specificity for xyloglucan"), which:

i) encoded by a DNA sequence comprising at least one of the following partial sequences or contained in at least one of the following partial sequences

(a) 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) TTAACATCTTTTCACCATGA (SEQ ID NO: 5)

(f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6)

(g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7)

(h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8)

(i) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9)

(j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10)

(k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11)

(l) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12)

(m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13)

(n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14)

(o) GGCGCAGAGTTTGGCCAGGC (SEQ 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 ACACCATCGC

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

CCTG TACATA

CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA

(SEQ ID NO: 18)

Or a homologous sequence thereof encoded by a polypeptide specific for xyloglucan with endoglucanase activity,

ii) react immunologically against antibodies produced by the highly purified endoglucanase derived from Aspergillus aculeatus (Aspergillus aculeatus), which is encoded by the DNA sequence defined in i), and is xyloglucan specific.

More specifically, the term "specific for xyloglucan" as used herein means that the endoglucanase exhibits its highest activity for xyloglucan substrates, and for other cellulose-containing substrates such as Carboxymethylcellulose, cellulose, or other dextran, exhibits preferably less than 75% activity, more preferably less than 50% activity, most preferably less than about 25% activity.

Preferably, the specificity of endoglucanase to xyloglucan is further defined as the reducing sugar released under optimal conditions obtained by incubating the enzyme with xyloglucan and other substrates to be tested, respectively. Relative activity determined. For example, specificity can be defined as xyloglucan to β-glucan activity ratio (XGU/BGU), xyloglucan to carboxymethylcellulose activity ratio (XGU/CMCU), or xyloglucan activity ratio The sugar to acid swelling Avicell activity ratio (XGU/AVIU), which is preferably greater than about 50, such as 75, 90 or 100.

As used herein, the term "derived from" not only refers to the endoglucanase produced by bacterial strain CBS 101.43, but also refers to the encoding of the DNA sequence isolated from bacterial strain CBS 101.43 and producing in the host organism transformed by said DNA sequence endoglucanase. As used herein, the term "homologue" means a polypeptide encoded by a DNA that hybridizes to the same probe as the DNA encoding the endoglucanase specific for xyloglucan under certain specific conditions (e.g. Presoak in 5×SSC and prehybridize in a solution of 5×SSC, 5×Denhardt’s solution, and 50 μg denatured sonicated calf thymus DNA at -40°C for 1 hour before labeling with 50 μCi 32-P-dCTP Hybridized at -40°C for 18 hours in the same solution supplemented with probes, washed three times in 2×SSC, kept in 0.2% SDS at 40°C for 30 minutes). More specifically, the term is used to refer to a DNA sequence that is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%, at least 80% , at least 85%, at least 90%, even at least 95% homologous to any of the sequences shown above. The term is intended to include modifications of any of the DNA sequences indicated above, such as nucleotide substitutions that do not result in another amino acid sequence of the polypeptide encoded by the sequence, but which are equivalent to introducing into it a DNA sequence comprising any The codon usage of the host organism for the DNA structure, or nucleotide substitutions that do result in a different amino acid sequence and thus possibly a different amino acid sequence and thus a different protein structure that may produce a protein structure with a different Properties of endoglucanase mutants. Other examples of possible modifications are insertion of one or more nucleotides into the sequence, addition of one or more nucleotides at either end of the sequence, or deletion of one or more nucleotides at either end or within the sequence.

The endoglucanase specific for xyloglucan that can be used in the present invention is preferably that its XGU/BGU, XGU/CMU and/or XGU/AVIU ratio (as defined above) is greater than 50, such as 75, 90 or 100 endoglucanase.

In addition, the endoglucanase specific to xyloglucan is preferably substantially inactive on β-glucan and/or has substantially no activity on carboxymethyl when the activity on xyloglucan is 100%. Cellulose and/or Avicell exhibit up to 25%, such as up to 10% or about 5%, of the activity. In addition, the endoglucanase specific for xyloglucan of the present invention preferably has substantially no transferase activity, which is most glucan specific for plant-derived xyloglucan An activity that has been observed for endonucleases.

Endoglucanases specific for xyloglucan can be obtained from the fungal species A. aculeatus as described in WO 94/14953. Microbial endoglucanases specific for xyloglucan have also been described in WO 94/14953. Endoglucanases specific for xyloglucan from plants have been described, but these enzymes have transferase activity, so they must be considered inferior to xyloglucan when substantial degradation of xyloglucan is desired. Glycan-specific microbial endoglucanases. An additional advantage of microbial enzymes is that they can generally be produced in larger quantities in microbial hosts compared to enzymes from other sources.

When present, xyloglucanase is preferably incorporated into the treatment compositions of the invention at a level of 0.0001-2%, more preferably 0.0005-0.1%, most preferably about 0.001-0.02% pure enzyme by weight of the composition.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Refined or unrefined forms of these enzymes can be used. Also included by the definition are mutants of the native enzyme. Mutants can be obtained, for example, by natural enzyme protein and/or genetic engineering, chemical and/or physical modification. It is common practice to express the enzyme by a host organism in which the genetic material responsible for the production of the enzyme has been cloned.

Said enzymes are typically incorporated into said bleaching compositions at levels of active enzyme of from 0.0001 to 2% by weight of the bleaching composition. Enzymes can be added as separate single components (pellets, granules, stabilized liquids, etc. containing one enzyme) or as a mixture of two or more enzymes (eg cogranulates).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers. An example of such an enzyme oxidation scavenger is ethoxylated tetraethylenepolyamine.

Certain enzymatic materials and their incorporation into synthetic bleach compositions are also in WO 93/07263 and WO 93/07260 by Genencor International, WO 89/08694 by Novo, and U.S. 3,553,139, Jan. 5, 1971 by McCarty et al. public. Enzymes are further disclosed in U.S. 4,101,457, Place et al., July 18, 1978, and U.S. 4,507,219, March 26, 1985, Hughes. Enzyme materials useful in liquid detergent formulations and their incorporation into such formulations are disclosed in U.S. 4,261,868, April 14, 1981, to Hora et al.

Enzyme Stabilizers - Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US 3,600,319, August 17, 1971 to Gedge et al., EP 199,405, October 29, 1986, and EP 200,586 to Venegas. Enzyme stabilization systems are also disclosed eg in US 3,519,570. Useful Bacillus sp. AC13 producing proteases, xylanases and cellulases is described in WO 9401532 to Novo. The enzymes used in the present invention can be stabilized by the presence of a water-soluble source of calcium and/or magnesium ions in the final composition which provides such ions to the enzyme. Suitable enzyme stabilizers and their amounts are described in US Patent 5,576,282.

Other Detergent Ingredients - The bleaching compositions of the present invention may also optionally contain one or more of the following: polymeric dispersants, clay soil release/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, Structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. Suitable examples of such other detergent ingredients and their amounts can be found in US Patent No. 5,576,282.

Cleaning Method - In addition to the cleaning of fabrics, dishware and other hard surfaces, and personally cleansed body parts described herein, the present invention also includes a method of laundry pretreatment of soiled or soiled fabrics comprising the use of conventional aqueous washing solutions The stains and/or stains are contacted with the high concentration forms of the bleaching compositions set forth above directly prior to laundering of these fabrics. Preferably, the bleaching composition is left in contact with the stain/spot for about 30 seconds to 24 hours prior to washing the pretreated soiled/stained substrate by conventional means. More preferably, the pretreatment time is about 1-180 minutes.

The following examples are intended to illustrate the compositions of the invention, but are not meant to limit or define the scope of the invention.

In the following examples, some abbreviations known to those of ordinary skill in the art are used, consistent with the disclosure presented herein.

Synthetic example

Example I

Preparation of 1-(4,4-dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate (7):

Step 1: Preparation of dimethyl benzyl cyanide (2)

Into a 1 L three necked round bottom flask equipped with two addition funnels, a side arm adapter, ammonium hydroxide trap, reflux condenser, mechanical stirrer, thermometer and fittings, and glass fritted gas diffuser, charge two Methyl sulfoxide (200 mL) and cooled in an ice bath. The methyl chloride gas was diffused into the dimethyl sulfoxide with stirring. After 15 minutes, sodium hydroxide (50% in water, 32.9 g) and benzyl cyanide (1, 11.7 g, 1 equiv) were added simultaneously as separate solutions through two addition funnels at such a rate that the temperature did not exceed 35 °C . After the addition of sodium hydroxide and benzyl cyanide was complete, the reaction was stirred at room temperature while the methyl chloride continued to diffuse into the solution. After 1 hour, the flow of methyl chloride was stopped (38.8 g total, 3.8 eq) and the reaction was extracted with toluene (3 x 100 mL) and ether (100 mL). The combined organic layers were washed with saturated sodium bicarbonate (2 x 100 mL), brine (100 mL), dried over sodium sulfate, and concentrated to give 2. The preparation is represented by the following reaction:

Step 2: Preparation of 1-amino-2,2-dimethyl-2-phenylethane (3):

In a 250 mL three necked round bottom flask equipped with a pressure equalization dropping funnel, argon inlet and reflux condenser, was charged with anhydrous diethyl ether (100 mL) and cooled in an ice bath. Lithium aluminum hydride powder (3.68 g, 2 equiv) was slowly added to the reaction mixture. When the addition was complete, dimethylbenzyl cyanide ( 2 , 7.00 g, 1 equiv) was added dropwise over 15 minutes. The reaction was allowed to warm slowly to room temperature overnight with stirring. Water (7.0 mL) was added over 15 minutes, followed by sodium hydroxide (15% in water, 7.0 mL). The mixture was stirred for about 1 hour and additional water (21.0 mL) was added. The reaction was diluted with diethyl ether (100 mL) and vacuum filtered. The filter cake was washed with diethyl ether (8 x 50 mL), and the combined organic layers were dried over magnesium sulfate and concentrated in vacuo to give 3 . The preparation is represented by the following reaction:

Step 3: Preparation of 4,4-dimethyl-3,4-dihydroisoquinoline ( 4 ):

A 50 mL round bottom flask equipped with a magnetic stir bar and distillation apparatus was charged with 1-amino-2,2-dimethyl-2-phenylethane (4.15 g, 1 equiv) and formic acid (6.65 g, 3.5 equiv) in Stir at 100°C for 1 hour, at which time, another portion of formic acid (2 mL, 0.9 equiv) is added. After stirring for an additional hour, the mixture was heated to 200°C and vacuum was applied. When unreacted formic acid and water were removed, the residual oil, N-formyl-β,β-dimethyl-β-phenethylamine, was cooled to room temperature.

A 100 mL round bottom flask equipped with a sidearm connector, addition funnel and mechanical stirrer was charged with polysulfuric acid (29.7 g) and phosphorus pentoxide (4.74 g). This mixture was stirred and heated to 180°C for about 1 hour and cooled to about 150°C. N-Formyl-β,β-dimethyl-β-phenethylamine (5.31 g, 1 eq.) was melted and added to the acid mixture in a stream. The reaction was heated to 180°C and allowed to stir overnight. The reaction mixture was cooled to about 60°C and mixed slowly with ice water (250 mL). The diluted reaction mixture was washed with diethyl ether (2 x 100 mL). The aqueous solution was stirred and kept cooled in an acetone/dry ice bath while saturated aqueous potassium hydroxide was added. When the pH of the mixture reached 9, the mixture was extracted with diethyl ether (4 x 100 mL). The organic layer was washed with pH 10 buffer solution (200 mL), dried over magnesium sulfate, and concentrated in vacuo to give 4 . The preparation is represented by the following reaction:

Step 4: Preparation of 1,2-decanediol cyclic sulfate ( 6 ):

A 500 mL three necked round bottom flask equipped with a mechanical stirrer, pressure equalization addition funnel and reflux condenser was charged with 1,2-decanediol (5, 8.72 g, 50.5 mmol) and 50 mL of carbon tetrachloride. When 1,2-decanediol was dissolved, thionyl chloride (5.5 mL, 75 mmol) was added dropwise at room temperature and the reaction was heated to 60°C. After 2 hours, the reaction was cooled by an ice bath. Water (50 mL) and acetonitrile (75 mL) were added. 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 at room temperature for 1 hour. The mixture was extracted with diethyl ether (4 x 175 mL), the organic layer was washed with water (5 x 100 mL), saturated sodium bicarbonate (3 x 100 mL), brine (2 x 100 mL), filtered through celite/silica gel, and washed with magnesium sulfate dry. The supernatant was concentrated to give 6 as a clear oil. The preparation is represented by the following reaction formula:

Step 5: Preparation of 1-(4,4-dimethyl-3,4-dihydroisoquinoline)decane-2-sulfonate ( 7 ):

A 100 mL round bottom flask equipped with a magnetic stir bar was charged with 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 ( 4 , 3.78 g, 16.0 mmol) in one portion. The reaction mixture thickened within 5 minutes and additional acetonitrile (60 mL) was added. The reaction was stirred overnight. The precipitate was collected, washed with acetone and allowed to air dry to give 7 . The preparation is represented by the following reaction:

Example II

Preparation of 1-(3,3-dimethyl-3,4-dihydroisoquinoline)decane-2-tetrafluoroborate ( 11 ):

Step 1: Preparation of N-formyl-α,α-dimethyl-β-phenylethylamine ( 9 )

A 1 L three necked round bottom flask equipped with a thermometer and adapter, mechanical stirrer, reflux condenser, ammonium hydroxide trap, and pressure equalization addition funnel was charged with glacial acetic acid (83.0 mL) and cooled in an ice bath. Sodium cyanide (16.3 g, 1 equiv) and concentrated sulfuric acid in acetic acid (160 g/83.0 mL) were added at a rate slow enough to keep the temperature below 20 °C (Warning: extreme care must be taken to avoid exposure to toxic gases). 2-Methyl-1-phenyl-2-propanol ( 8 , 50.0 g, 1 equiv) was slowly added to the reaction mixture, and the mixture was stirred overnight at room temperature. The solution was gassed with argon for 3 hours and poured into ice water (300 mL). A layer of oil forms, separate it and save it. The aqueous layer was neutralized to pH 7 with sodium carbonate and extracted with diethyl ether (3 x 200 mL). The organic layer was combined with the previously separated oil, dried over magnesium sulfate, and concentrated to afford 9 . The preparation is represented by the following reaction:

Step 2: Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline ( 10 ):

A 1 L three-necked round bottom flask equipped with a side arm adapter, addition funnel and mechanical stirrer was charged with polysulfuric acid (378 g) and phosphorus pentoxide (60.4 g). This mixture was stirred and heated to 180°C for 1 hour and cooled to about 150°C. N-formyl-α,α-dimethyl-β-phenethylamine is melted and added in a liquid stream to the acid mixture. The reaction was heated to 180°C and allowed to stir overnight. The reaction mixture was cooled to about 100°C and mixed slowly with ice water (2 L). The diluted reaction mixture was then filtered through Celite ^(R) . The filtrate was washed with diethyl ether (2 x 100 mL). The aqueous solution was stirred and kept cooled in an acetone/dry ice bath while saturated aqueous potassium hydroxide was added. When the pH of the mixture reached 9, the mixture was extracted with diethyl ether (4 x 100 mL). The organic layer was washed with pH 10 buffer solution (200 mL), dried over magnesium sulfate, and concentrated in vacuo to afford 4 . The preparation is represented by the following reaction:

Step 3: Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline tetrafluoroborate (11):

A 100 mL round bottom flask equipped with a magnetic stir bar at 0°C was charged with trimethyloxonium tetrafluoroborate (Meerwein salt, 1.13 g, 7.7 mmol) and dichloromethane (15 mL). To the stirred solution was added a solution of 3,3-dimethyl-3,4-dihydroisoquinoline (1.11 g, 7.0 mmol) in dichloromethane (40 mL) over a period of 5 minutes. The heterogeneous solution was allowed to warm to room temperature and stirred overnight. The solution was concentrated and ethanol was added to the resulting oil, causing crystallization to give 11 . The preparation is represented by the following reaction:

Example III

Preparation of 1,1-diphenyl-3-duryl indolinium (pseudoisoindolinium) hexane sulfate ( 15 ):

Step 1: Preparation of 1,1-diphenyl-3-durylindoindole ( 12 ) In the art, such as Fuson, RC et al., in Journal of Organic Chemistry (J.Org.Chem.) 1951, 16, 648 described.

Step 2: Preparation of 1,2-hexanediol cyclic sulfate ( 14 ):

A 500 mL three-necked round bottom flask equipped with a mechanical stirrer, a pressure-balanced addition funnel, and a reflux condenser was charged with 1,2-hexanediol ( 13 , 5.91 g, 50.0 mmol) and 50 mL of carbon tetrachloride. When 1,2-hexanediol was dissolved, thionyl chloride (5.5 mL, 75 mmol) was added dropwise at room temperature, and the reaction was heated to 60°C. After 2 hours, the reaction was cooled by an ice bath. Water (50 mL) and acetonitrile (75 mL) were added. 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 at room temperature for 1 hour. The mixture was extracted with diethyl ether (4 x 175 mL), the organic layer was washed with water (5 x 100 mL), saturated sodium bicarbonate (3 x 100 mL), brine (2 x 100 mL), filtered through celite/silica gel, and washed with magnesium sulfate dry. Concentration of the supernatant yielded 7, a clear oil. The preparation is represented by the following reaction formula:

Step 3: Preparation of 1,1-diphenyl-3-duryl isoindolinium (pseudoisoindolinium) hexane sulfate ( 15 ):

To a 200 mL round bottom flask equipped with a magnetic stir bar was added 1,1-diphenyl-3-durylindoindole ( 12 , 5.55 g, 20.0 mmol) and acetonitrile (30 mL). To this solution was added 1,2-hexanediol cyclic sulfate ( 14 , 2.60 g, 22.0 mmol) in one portion. The reaction mixture thickened within 5 minutes and additional acetonitrile (60 mL) was added. The reaction was stirred overnight. The precipitate was collected, washed with acetone and allowed to air dry to give 15 . The preparation is represented by the following reaction:

recipe example

Example IV

A bleach detergent composition in the form of a granular laundry detergent is exemplified by the following formulation.

A A B B C D D E

Bleach Boosting Compound* 0.05 0.01 0.13 0.04 0.07

Conventional Activator (NOBS) 0.00 2.00 1.20 0.70 0.00

Conventional Activator (TAED) 3.00 0.00 2.00 0.00 0.00

Conventional 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 alkylbenzene sulfonate 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 Cocamidopropyl Betaine 1.50 0.00 1.50 0.00 0.00

Palm N-Methyl Glucamide 1.70 2.00 1.70 2.00 0.00

C12 dimethyl hydroxyethyl ammonium chloride 1.50 0.00 1.50 0.00 0.00

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/maleic acid copolymer 0.00 0.00 0.00 0.00 1.00

Partially neutralized polyacrylic acid 3.00 3.00 3.00 3.00 0.00

Detergent 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

Savinase(4T) 1.00 1.00 1.00 1.00 0.60

Termamyl(60T) 0.40 0.40 0.40 0.40 0.40

Lipase (100T) 0.12 0.12 0.12 0.12 0.12

Carezyme(5T) 0.15 0.15 0.15 0.15 0.15

Diethylenetriaminepenta(methylenephosphine 1.60 1.60 1.60 1.60 0.40

acid)

Brightener 0.20 0.20 0.20 0.05 0.20

Sulfonated zinc phthalocyanine photobleach 0.50 0.00 0.25 0.00 0.00

MgSO ₄ 2.20 2.20 2.20 2.20 0.64

Na ₂ SO ₄ balance balance balance balance balance

*1-(4,4-Dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate prepared according to Example 1.

Any of the above compositions are used to launder fabrics in water at a concentration of 3500 ppm at 25°C and a water:clothes ratio of 15:1. Typical pH is about 9.5, but can be adjusted by varying the ratio of acid to alkylbenzenesulfonate in the sodium salt form.

Example V

A bleach detergent composition in the form of a granular laundry detergent is exemplified by the following formulation.

A B C D E

Bleach Boosting Compound* 0.26 0.38 0.04 0.03 0.01

Conventional Activator (NOBS) 0.00 0.00 0.00 0.50 0.00

Conventional Activator (TAED) 1.80 1.00 2.50 3.00 1.00

Conventional 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 alkylbenzene sulfonate 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 Cocamidopropyl Betaine 0.00 1.50 0.00 1.50 1.50

Palm N-Methyl Glucamide 0.00 1.70 2.00 1.70 1.70

C12 Dimethyl Hydroxyethyl Ammonium Chloride 1.00 1.50 0.00 1.50 1.50

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/maleic acid copolymer 0.00 0.00 0.00 0.00 0.00

Partially neutralized polyacrylic acid 0.00 3.00 3.00 3.00 3.00

Detergent 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

Savinase(4T) 0.60 1.00 1.00 1.00 1.00

Termamyl(60T) 0.40 0.40 0.40 0.40 0.40

Lipase (100T) 0.12 0.12 0.12 0.12 0.12

Carezyme(5T) 0.15 0.15 0.15 0.15 0.15

Diethylenetriaminepenta(methylenephosphine 0.40 0.00 1.60 0.00 0.00

acid)

Brightener 0.20 0.30 0.20 0.30 0.30

Sulfonated zinc phthalocyanine photobleach 0.25 0.00 0.00 0.00 0.00

MgSO ₄ 0.64 0.00 2.20 0.00 0.00

Na ₂ SO ₄ balance balance balance balance balance

*1-(4,4-Dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate prepared according to Example 1.

Any of the above compositions are used to wash fabrics at a concentration of 3500 ppm in water, 25°C and a water:clothes ratio of 15:1. Typical pH is about 9.5, but can be adjusted by varying the ratio of acid to alkylbenzenesulfonate in the sodium salt form.

Example VI

A bleach detergent powder comprising the following ingredients:

Ingredient weight %

Bleach Boosting Compound* 0.07

TAED 2.0

Sodium perborate tetrahydrate 10

C ₁₂ linear alkylbenzene sulfonate 8

Phosphate (calculated as sodium tripolyphosphate) 9

Sodium Carbonate 20

Talc 15

Whitening agent, fragrance 0.3

Sodium chloride 25

Water and trace ingredients Balance to 100%

*1-(4,4-Dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate prepared according to Example 1.

Example VII

A laundry bar suitable for hand washing soiled fabrics is prepared by standard extrusion and contains the following ingredients:

Ingredient weight %

Bleach booster compound* 0.2

TAED 1.7

NOBS 0.2

Sodium perborate tetrahydrate 12

C ₁₂ linear alkylbenzene sulfonate 30

Phosphate (calculated as sodium tripolyphosphate)                                                   

Sodium Carbonate 5

Sodium pyrophosphate 7

Coconut Monoethanolamide 2

Zeolite A (0.1-10 microns) 5

Carboxymethylcellulose 0.2

Polyacrylate (molecular weight 1400) 0.2

Whitening agent, fragrance 0.2

Protease 0.3

CaSO ₄ 1

MgSO ₄ 1

Water 4

Filling ² to 100% margin

¹ 1-(4,4-Dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate prepared according to Example 1.

² can be selected from suitable materials such as CaCO ₃ , talc, clay, silicates and the like. Acidic fillers may be used to lower the pH.

Example VIII

A laundry detergent composition suitable for machine use is prepared by standard methods and consists of:

Ingredient weight %

Bleach booster compound* 0.82

TAED 7.20

Sodium perborate tetrahydrate 9.2

Sodium Carbonate 23.74

Anionic surfactants 14.80

Aluminum silicate 21.30

Silicate 1.85

Diethylenetriaminepentaacetic acid 0.43

Polyacrylic acid 2.72

Brightener 0.23

Polyethylene glycol solid 1.05

Sulfates 8.21

Spices 0.25

Water 7.72

Processing aids 0.10

Others 0.43

*1-(4,4-Dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate prepared according to Example 1.

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

Example IX

Ingredient weight %

Bleach Boosting Compound* 1.0

TAED 10.0

Sodium perborate tetrahydrate 8.0

Sodium Carbonate 21.0

Anionic surfactants 12.0

Aluminum silicate 18.0

Diethylenetriaminepentaacetic acid 0.3

Non-ionic surfactant 0.5

Polyacrylic acid 2.0

Brightener 0.3

Sulfate 17.0

Spices 0.25

Water 6.7

Others 2.95

*1-(4,4-Dimethyl-3,4-dihydroisoquinoline)decane-2-sulfate prepared according to Example 1.

The composition is useful as a laundry aid for laundering fabrics at a solution concentration of about 850 ppm at 20-40°C and a water to fabric ratio of about 20:1.

While particular embodiments of the present invention have been described, it will be apparent to those skilled in the art that various changes and modifications of the invention can be made without departing from the spirit and scope of the invention. It is intended to cover in the appended claims all such modifications within the scope of this invention.

The compositions of the present invention may be suitably prepared by any method selected by the formulator, non-limiting examples of which are described in US Patent Nos. 5,691,297, 5,574,005, 5,569,645, 5,565,422, 5,516,448, 5,489,392 and 5,486,303.

In addition to the above examples, the bleach systems of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are described in U.S. Patent Nos. .

Having described the present invention in detail with reference to preferred embodiments and examples, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the present invention, and the present invention should not be construed as being limited to what is described in the specification. The content of the description.

Sequence Listing

<110>The Procter & Gamble Company

Miracle, Gregory

Dykstra, Robert

<120> Formulation ingredients for preventing aromatization, compositions and laundry methods using the same

<130>7754

<150>60/151,175

<151>1999-08-27

<160>18

<170>Patentln version 3.0

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<213> Asperglllus aculeatus

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<213> Asperglllus aculeatus

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<213> Asperglllus aculeatus

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<213> Asperglllus aculeatus

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<213> Asperglllus aculeatus

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Claims (15)

1. bleaching composition, comprise with or not with the bleaching potentiating compounds of peroxygen source associating, wherein, described bleaching potentiating compounds is selected from:

(a) bleach boosters, it is selected from the have following formula compound of [I] and [II]:

Wherein, t is 0 or 1; R ¹-R ⁴Be H; R ⁵Be selected from H, methyl, alkaryl and aryl; R ⁶Be selected from the C of H, straight or branched ₁-C ₁₄Alkyl, or R ⁶Be the base of representing with following formula:

-T ₀-(Z-) _a

Wherein, Z ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a is 1, T ₀Be the base of representing with following formula:

Wherein, p is the integer of 2-4, R ⁴⁵Be independently selected from the C of H, straight or branched ₁-C ₁₈Alkyl and cycloalkyl; Wherein, R ⁷-R ¹⁰Be selected from H, straight or branched C ₁-C ₁₂Alkyl, aryl and alkaryl, X It is negatively charged ion; Further prerequisite is when t is 0, R ⁷And R ⁸The both can not be H, when t is 1, and perhaps R ⁷And R ⁸The two, perhaps R ⁹And R ¹⁰The two non-H;

(b) albic material, it is selected from the compound of formula [III] and [IV] expression:

Wherein, t is 0 or 1; R ³¹-R ³⁴Be H; R ²⁵Be selected from H, methyl, alkaryl and aryl; R ²⁶Be selected from the C of straight or branched ₁-C ₁₄Alkyl and cycloalkyl, or R ²⁶Be the base of representing with following formula:

-T ₀-(Z ^-) _a

Wherein, Z ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a is 1, T ₀Be the base of representing with following formula:

Wherein, p is the integer of 2-4, R ⁴⁵Be independently selected from the C of H, straight or branched ₁-C ₁₈Alkyl and cycloalkyl; Wherein, R ²⁷-R ³⁰Be H, straight or branched C ₁-C ₁₂Alkyl or aryl; X It is negatively charged ion; Further prerequisite is, when t is 0, and R ²⁷And R ²⁸The both can not be H, when t is 1, and perhaps R ²⁷And R ²⁸The two, perhaps R ²⁹And R ³⁰The two non-H; With

(c) their mixture.

2. according to the bleaching composition of claim 1, wherein, described bleaching potentiating compounds accounts for the 0.001%-10% of described composition weight, and described peroxygen source accounts for the 0.01%-60% of described composition weight when existing.

3. according to the bleaching composition of claim 1, wherein, described peroxygen source is selected from when existing:

(a) preformed peracid compound is selected from percarboxylic acids and percarboxylic acids salt, percarbonic acid and percarbonate, crosses imino-acid and crosses imino-hydrochlorate, permonosulphuric acid and permonosulphuric acid salt and their mixture;

(b) hydrogen peroxide cource is selected from perborate compound, percarbonate compound, superphosphate compound and their mixture; Be with or without bleach-activating agent.

4. according to the bleaching composition of claim 1, wherein, described bleaching potentiating compounds is the compound of formula [I] or [II], wherein, and R ⁵Be H or methyl, a equals 1.

5. according to the bleaching composition of claim 1, wherein, described albic material is the compound of formula [III] or [IV] expression, wherein, and R ²⁵Be hydrogen or methyl, Z ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a equals 1.

6. according to the bleaching composition of claim 1, wherein, described bleaching composition also comprises surfactant.

7. according to the bleaching composition of claim 6, wherein, described tensio-active agent is an aniorfic surfactant.

8. according to the bleaching composition of claim 1, wherein, described bleaching composition also comprises enzyme.

9. according to the bleaching composition of claim 1, wherein, described bleaching composition also comprises sequestrant.

10. cationic or amphoteric ion type laundry bleaching potentiating compounds is selected from:

With

With

With their mixture; Wherein, for formula [I] and [II], t is 0 or 1; R ¹-R ⁴Be H; R ⁵Be selected from H, methyl, alkaryl and aryl; R ⁶Be selected from the C of H, straight or branched ₁-C ₁₄Alkyl, or R ⁶Be the base of representing with following formula:

-T ₀-(Z ^-) _a

Wherein, Z ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a is 1, T ₀Be the base that following formula is represented:

Wherein, p is the integer of 2-4, R ⁴⁵Be independently selected from the C of H and straight or branched ₁-C ₁₈Alkyl and cycloalkyl; Wherein, R ⁷-R ¹⁰Be selected from H, straight or branched C ₁-C ₁₂Alkyl, aryl and alkaryl, X Be negatively charged ion, further prerequisite is, when t is 0, and R ⁷And R ⁸Neither may be H, when t is 1, perhaps R ⁷And R ⁸The two, perhaps R ⁹And R ¹⁰The two non-H;

Wherein, for molecular formula [III] and [IV], t is 0 or 1; R ³¹-R ³⁴Be H; R ²⁵Be selected from H, methyl, alkaryl and aryl; R ²⁶Be selected from the C of straight or branched ₁-C ₁₄Alkyl and cycloalkyl, or R ²⁶Be the base of representing with following formula:

-T ₀-(Z ^-) _a

Wherein, Z ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a is 1, T ₀Be the base that following formula is represented:

Wherein, p is the integer of 2-4, R ⁴⁵Be independently selected from the C of H, straight or branched ₁-C ₁₈Alkyl and cycloalkyl; Wherein, R ²⁷-R ³⁰Be H, straight or branched C ₁-C ₁₂Alkyl or aryl; X It is negatively charged ion; Further prerequisite is, when t is 0, and R ²⁷And R ²⁸The both can not be H, when t is 1, and perhaps R ²⁷And R ²⁸The two, perhaps R ²⁹And R ³⁰The two non-H.

11. a method of washing the fabric that needs washing, described method comprises makes described fabric contact with the laundry solution of the bleaching composition that contains with good grounds claim 1.

12. a laundry additive product comprises the bleaching potentiating compounds that is selected from following material:

(a) bleach boosters, it is selected from the have formula compound of [I] and [II]:

With

Wherein, t is 0 or 1; R ¹-R ⁴Be H; , R ⁵Be selected from H, methyl, alkaryl and aryl; R ⁶Be selected from the C of H, straight or branched ₁-C ₁₄Alkyl and cycloalkyl, or R ⁶Be the base of representing with following formula:

-T ₀-(Z ^-) _a

Wherein, Z-is-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a is 1, T ₀Be selected from:

Wherein, p is the integer of 2-4, R ⁴⁵Be independently selected from the C of H, straight or branched ₁-C ₁₈Alkyl and cycloalkyl; Wherein, R ⁷-R ¹⁰Be selected from H, straight or branched C ₁-C ₁₂Alkyl, aryl and alkaryl, X Be negatively charged ion, further prerequisite is, when t is 0, and R ⁷And R ⁸Neither may be H, when t is 1, perhaps R ⁷And R ⁸The two, perhaps R ⁹And R ¹⁰The two non-H;

(b) albic material, it is selected from the compound of formula [III] and [IV] expression:

With

Wherein, t is 0 or 1; R ³¹-R ³⁴Be H; R ²⁵Be selected from H, methyl, alkaryl and aryl; R ²⁶Be selected from the C of straight or branched ₁-C ₁₄Alkyl and cycloalkyl, or R ²⁶Be the base of representing with following formula:

-T ₀-(Z ^-) _a

Wherein, Z ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, a is 1, T ₀Be the base that following formula is represented:

Wherein, p is the integer of 2-4, R ⁴⁵Be independently selected from the C of H, straight or branched ₁-C ₁₈Alkyl and cycloalkyl; Wherein, R ²⁷-R ³⁰Be H, straight or branched C ₁-C ₁₂Alkyl or aryl, X It is negatively charged ion; Further prerequisite is, when t is 0, and R ²⁷And R ²⁸The both can not be H, when t is 1, and perhaps R ²⁷And R ²⁸The two, perhaps R ²⁹And R ³⁰The two non-H; With

(c) their mixture.

13. according to the laundry additive product of claim 12, wherein, described laundry additive product is to be selected from ball, sheet, capsule sheet and capsular formulation.

14. according to the laundry additive product of claim 12, wherein, described laundry additive also comprises suitable carriers.

15. bleaching composition according to claim 3; wherein, described bleach-activating agent is selected from: tetraacetyl ethylene diamine; benzoyl caprolactam; 4-nitro benzoyl hexanolactam; 3-chloro benzoyl caprolactam; the benzoyloxy benzene sulfonate; nonanoly acyloxy benzene sulfonate; phenol benzoate; the last of the ten Heavenly stems acyloxy benzene sulfonate; the benzoyl Valerolactim; hot acyloxy benzene sulfonate; the amino hexylyloxy of 4-[N-(nonanoyl)] the Phenylsulfonic acid sodium salt; dodecane acyl-oxygen base benzene sulfonate; 10-hendecene acyloxy benzene sulfonate; caprinoyl aminobenzoic acid and their mixture.