CN1382206A - Color safe laundry methods employing zwitterionic formulation components - Google Patents

Abstract

This invention relates to bleaching systems of zwitterionic organocatalyst compounds and methods for using such bleaching systems to improve color retention, particularly in the washing of fabrics. More specifically, this invention relates to bleaching systems comprising zwitterionic quaternary imine bleaching synergist compounds, zwitterionic quaternary oxaprodione bleaching agents, and mixtures thereof, and methods for using such bleaching systems in the washing of fabrics, particularly in colored fabrics.

Description

Color protection washing method using zwitterionic formulation components

Field of Invention

This invention relates to zwitterionic organic catalyst compound bleaching systems and methods of using such bleaching systems to increase color retention during laundering of fabrics, especially colored fabrics. More particularly, the present invention relates to bleaching systems comprising zwitterionic quaternary imine bleach booster compounds, zwitterionic quaternary oxaziridinium (oxaziridinium) bleaches and mixtures thereof, and to the laundering process of fabrics, especially colored fabrics method of using this bleaching system.

Background of the Invention

Oxygen bleaches have grown in popularity in recent years in household and personal care products that facilitate descaling. Bleach is particularly desirable for its stain removal, cleaning of dull fabrics, whitening and sanitation properties. Oxygen bleaches have been found to be particularly popular in laundry products such as detergents, automatic dishwashing products and hard surface cleaners. However, oxygen bleach has limited effectiveness. Some frequently encountered disadvantages include damage to the color of the fabrics and damage to the laundering facilities, especially to the rubber hoses that may be included in these facilities. Additionally, oxygen bleaches tend to be extremely dependent on temperature gradients. Therefore, the lower the temperature of the solution using oxygen bleach, the less effective the bleaching will be. Temperatures in excess of 60°C are generally required for the effectiveness of oxygen bleach in solution.

In order to solve the above-mentioned temperature gradient dependence problem, a class of compounds known as "bleach activators" has been developed. Bleach activators, typically perhydrolyzable acyl compounds having a leaving group such as dobesylate, react with active oxygen groups (typically hydrogen peroxide or its anion) to form more effective peroxyacid oxidizing agents. It is this peroxyacid compound that then oxidizes the soiled or stained substrate material. However, bleach activators also have a certain temperature dependence. Bleach activators are more effective at water temperatures of about 40°C to about 60°C. At water temperatures below 40°C, peroxyacid compounds will lose some of their bleaching effectiveness.

US Patent Nos. 5,576,282 and 5,817,614 to Miracle et al. both disclose attempts to develop bleach systems comprising zwitterionic organic catalyst compounds that are effective at low water temperatures and provide relative color retention. Although the bleaching system disclosed in this patent provides color retention superior to conventional organocatalyst bleaching systems such as cationic organocatalyst bleaching systems, examples of conventional organocatalyst bleaching systems are disclosed in U.S. Patents 5,360,568, 5,360,569, 5,370,826 and 5,482,515, however, consumers demand better color protection bleaching products.

A serious disadvantage associated with methods using conventional organic catalysts is the use of these organic catalysts in too high concentrations, examples of which are described in US Patents 5,360,568, 5,360,569, 5,370,826 to Madison et al. and US Patents 5,576,282 and 5,817,614 to Miracle et al. For example, the method used in US Pat. No. 5,482,515 describes a method in which the oxygen transfer agent (organic catalyst compound) is present at a concentration of about 0.01 ppm to 300 ppm per liter of medium, preferably in the range of 5 ppm to about 100 ppm. Such concentrations can result in unacceptable color damage of fabric dyes. In addition, such high concentrations consume too much available oxygen ("AvO"), shifting the performance curve (ie, altering the balance between peracid bleaching and organocatalyst bleaching). It is possible to increase the concentration of organic catalysts to improve soil bleaching, but the necessary price is damage to the dye, and in some places, this damage to the dye is unacceptable. Therefore, the ratio of soil bleaching performance to dye damage of organocatalyst bleaching systems must be maximized.

As noted above, there is also a clear need for zwitterionic organocatalyst compound bleaching systems and washing methods using such zwitterionic organocatalyst compound bleaching systems which are effective at lower water temperatures and are compatible with the use of the above described This system has superior color retention compared to the washing methods of organocatalyst bleach systems disclosed in the prior art; there is also a need to maximize the soil bleaching to dye damage ratio of organocatalyst bleach systems.

Summary of Invention

The present invention satisfies the above needs. The present invention provides bleaching systems of zwitterionic organic catalyst compounds and methods of laundering fabrics, especially colored fabrics, using such bleaching systems.

The zwitterionic organic catalyst compounds and bleaching systems comprising such zwitterionic organic catalyst compounds of the present invention have improved bleaching efficacy at lower wash temperatures, while improving color retention, and are therefore superior to conventional zwitterionic and cationic organic catalyst compounds. Compared with catalyst bleaching system, it can improve bleaching efficiency and color protection. The zwitterionic organocatalyst compound bleach systems of the present invention can be used with or without, but preferably in combination with, conventional peroxygen bleach sources to produce the enhanced bleach efficacy and superior color retention of fabrics described above.

More particularly, the present invention relates to zwitterionic organic catalyst compounds such as zwitterionic quaternary imine bleach booster compounds, zwitterionic quaternary oxaziridinium bleaches, bleach systems comprising these zwitterionic organic catalyst compounds and the use of such Washing method for bleaching systems.

Non-limiting examples of advantages afforded by zwitterionic organocatalyst compounds and bleach systems employing the same include better bleach efficacy and improved color retention even at lower water temperatures.

In one aspect, the present invention provides zwitterionic organocatalyst bleaching systems that provide effective bleaching at lower water temperatures and better color retention than conventional organocatalyst bleaching systems.

In another aspect, the present invention provides zwitterionic organocatalyst bleach systems as hereinafter described comprising one or more zwitterionic organocatalyst compounds, which systems may be used in combination with or without a peroxygen source.

In another aspect, the present invention provides a zwitterionic organocatalyst bleach system comprising one or more zwitterionic organocatalyst compounds as hereinafter described for use in combination with a peracid.

In another aspect, the present invention provides a method of laundering fabrics, especially colored fabrics, in need of laundering, the method comprising: contacting the fabric with a wash solution of a bleaching system comprising one or more zwitterionic organic catalyst compounds described herein.

In another aspect, the present invention provides a bleach system of the present invention prepared according to the following steps:

a) providing a wash solution; and

b) adding a bleach composition comprising an amount of the zwitterionic organic catalyst compound of the present invention to said wash solution such that the resulting concentration of the zwitterionic organic catalyst compound in said wash solution is from about 0.001 ppm to about 5 ppm .

It is therefore an object of the present invention to provide: bleaching systems of zwitterionic organic catalyst compounds having improved performance and improved color retention even at lower aqueous solution temperatures; and using one or more zwitterionic organic catalyst compounds described herein. Process for laundering fabrics, especially colored fabrics, with bleaching systems of catalyst compounds.

These and other objects, features and advantages of the present invention will become apparent to those skilled in the art from the following description and appended claims.

All percentages, ratios and parts in this application are by weight unless otherwise specified. All documents cited in this application are hereby incorporated by reference.

                    Invention Details

The present invention discloses very useful zwitterionic organic catalyst compounds, bleaching systems comprising these zwitterionic organic catalyst compounds and methods of laundering fabrics, especially colored fabrics, using such bleaching systems.

The zwitterionic organocatalyst compounds of the present invention and bleach systems comprising these zwitterionic organocatalyst compounds have enhanced bleaching efficacy at lower wash temperatures with improved color retention and are therefore superior to conventional cationic and zwitterionic organocatalysts. It improves bleaching efficacy and color retention compared to bleaching systems. The bleaching systems of the zwitterionic organocatalyst compounds of the present invention can be used with or without, but preferably in combination with conventional peroxygen bleach sources to produce the above mentioned enhanced bleach efficacy and better fabric color retention. definition

As used herein, "peroxygen source" refers to a substance that generates a peroxygen compound, including the peroxygen compound itself. Examples include, but are not limited to, bleach activators, peracids, percarbonates, perborates, hydrogen peroxide, bleach booster compounds and/or bleaching substances such as oxaziridiniums.

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

As used herein, "peracid" refers to peroxyacids, such as peroxycarboxylic acid and/or peroxymonosulfuric acid (trade name OXONE) and salts thereof. Zwitterionic organic catalyst compounds

The zwitterionic organic catalyst compounds and bleach systems comprising these zwitterionic organic catalyst compounds according to the invention are preferably used in a method of laundering fabrics in need of laundering, especially colored fabrics. These methods generally involve bleaching soiled substrates, preferably colored fabrics, in an aqueous medium having a source of peroxygen and a zwitterionic organic catalyst compound having a structure as defined hereinafter, wherein the aqueous medium contains active activity from the peroxygen compound. The concentration of oxygen is from about 0.05 ppm to about 250 ppm per liter of medium, and the concentration of the zwitterionic organic catalyst compound contained in the aqueous medium is from 0.001 ppm to about 2 ppm, preferably from about 0.01 ppm to about 2 ppm, more preferably from about 0.1 ppm to about 1.5 ppm , most preferably from about 0.2 ppm to about 1 ppm.

In the bleaching system of the present invention, when a peroxy compound is present, the molar ratio of said peroxy compound to zwitterionic organic catalyst compound is preferably greater than 1:1, more preferably from about 30,000:1 to about 10:1, even more Preferably about 10,000:1 to about 50:1, more preferably about 5,000:1 to about 100:1, still more preferably about 3,500:1 to about 150:1.

The molar ratio of peroxy compound to zwitterionic organocatalyst compound affects the color protection properties of the bleaching system. However, the ppm concentration of the zwitterionic organocatalyst compound in the bleaching system is a major factor in determining the color protection performance of the bleaching system.

For example, the product releases a zwitterionic organic catalyst compound with a molecular weight of 300 at a concentration of 1 ppm in an aqueous medium, along with a concentration of 66 ppm of NOBS (35 ppm pernonanoic acid assuming 100% full hydrolysis) and a concentration of 66 ppm of percarbonate (21 ppm peroxide hydrogen) such that the molar ratio of peroxy compound to zwitterionic organic catalyst compound was 246:1. The product releasing 240 ppm of TAED (forming 160 ppm of peracetic acid) and 865 ppm of percarbonate (forming 281 ppm of hydrogen peroxide) resulted in a molar ratio of peroxy compound to zwitterionic organic catalyst of 3142:1. At 0.25 ppm of the zwitterionic organic catalyst compound, the molar ratio is 12568:1.

In addition to the molar ratio of peroxygen compound to zwitterionic organic catalyst compound, the bleaching system of the present invention is also characterized by the molar ratio of peracid to zwitterionic organic catalyst compound. The molar ratio of peracid to zwitterionic organic catalyst compound is preferably greater than 1:1, more preferably from about 5,000:1 to about 5:1, even more preferably from about 2,000:1 to about 10:1, still more preferably from about 1,000:1 to about 15:1.

The preferred molar ratio of peracid to zwitterionic organic catalyst compound varies with wash conditions. For example, under European wash conditions (typically containing about 4500 ppm to 5000 ppm of detergent components in the wash water), the preferred molar ratio of peracid to zwitterionic organic catalyst compound is from about 2,000:1 to about 150:1. However, under North American wash conditions (typically containing from about 850 ppm to about 1000 ppm of detergent components in the wash water), the preferred molar ratio of peracid to zwitterionic organic catalyst compound is from about 150:1 to about 5:1.

In addition to the molar ratio of peracid to zwitterionic organic catalyst compound, the bleach system of the present invention is also characterized by the molar ratio of hydrophobic peracid to zwitterionic organic catalyst compound, preferably hydrophobic zwitterionic organic catalyst compound. The molar ratio of hydrophobic peracid to zwitterionic organic catalyst compound is preferably from about 500:1 to about 15:1, more preferably from about 350:1 to about 20:1, still more preferably from about 200:1 to about 25:1, even more preferably Preferably from about 100:1 to about 35:1.

Preferably, the zwitterionic organic catalyst compounds of the present invention, more preferably, the iminium-based zwitterionic organic catalyst compounds of the present invention include, but are not limited to, bleach booster compounds.

I. Bleach Booster Compounds - Bleach booster compounds of the present invention, preferably iminium based bleach booster compounds include, but are not limited to, aryliminium zwitterions having a net charge of from about +3 to about -3 .

其中Z_p ^-与T_o形成共价键，Z_p ^-选自-CO₂ ^-，-SO₃ ^-，-OSO₃ ^-，-SO₂ ^-和-OSO₂ ^-，p为1，2或3；T_o选自取代或未取代的、饱和或不饱和的烷基，环烷基，芳基，烷芳基，芳烷基和杂环。Aryliminium Zwitterions - Aryliminium zwitterions having a net charge of about +3 to about -3 are represented by the formula [II]: Wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, Nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula:

Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle.

其中，当G存在时m为1-3，当G不存在时m为1-4；n为0-4的整数；每个R²⁶都独立地选自取代或未取代的基团，这些基团选自H，烷基，环烷基，芳基，稠合芳基，杂环，稠合杂环，硝基，卤素，氰基，磺基，烷氧基，酮基，羧基和烷氧羰基，并且任何两个相邻的R²⁶取代基可以结合形成稠合芳基，稠合碳环或稠合杂环；R²⁵可为取代或未取代的基团，这些基团选自H，烷基，环烷基，烷芳基，芳基，芳烷基，杂环，甲硅烷基，硝基，卤素，氰基，磺基，烷氧基，酮基，羧基和烷氧羰基；在该式中还存在下式表示的基团：

其中Z_p ^-与T_o形成共价键，Z_p ^-选自-CO₂ ^-，-SO₃ ^-，-OSO₃ ^-，-SO₂ ^-和-OSO₂ ^-，p为1，2或3；T_o选自下述基团：其中q为1-8的整数；R²⁹独立地选自取代或未取代的基团，这些基团选自直链或支链H，烷基，环烷基，烷芳基，芳基，芳烷基，亚烷基，杂环，烷氧基，芳羰基，羧烷基和酰胺基；G选自：(1)-O-；(2)-N(R³⁰)-；和(3)-N(R³⁰R³¹)-；R²⁷，R²⁸，R³⁰和R³¹为取代或未取代的基团，这些基团独立地选自H，氧，烷基，环烷基，烷芳基，芳基，芳烷基，亚烷基，杂环，烷氧基，芳羰基，羧烷基和酰胺基；R²⁵，R²⁶，R²⁷，R²⁸，R³⁰和R³¹中的任何一个可以和R²⁵，R²⁶，R²⁷，R²⁸，R³⁰和R³¹中的任何其它一个结合到一起形成普通环的一部分；任何孪位的R²⁷-R²⁸可以结合形成羰基；任何相邻的R²⁷-R³¹可以结合形成不饱和部分；并且其中任何一个取代基R²⁷-R³¹可以结合形成取代或未取代的稠合不饱和部分。Preferably, aryliminium zwitterions having an electrostatic charge of about +3 to about -3 are represented by the formula [XII]:

Wherein, when G exists, m is 1-3, when G does not exist, m is 1-4; n is an integer of 0-4; ^each R is independently selected from substituted or unsubstituted groups, these groups The group is selected from H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and alkoxy Carbonyl, and any two adjacent ^R26 substituents can be combined to form a fused aryl, fused carbocycle or fused heterocycle; ^R25 can be a substituted or unsubstituted group selected from H, Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; in There is also a group represented by the following formula in this formula:

Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from the following groups: Wherein q is an integer of 1-8; R ²⁹ are independently selected from substituted or unsubstituted groups selected from linear or branched H, alkyl, cycloalkyl, alkaryl, aryl, aryl Alkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido; G is selected from: (1)-O-; (2)-N(R ³⁰ )-; and (3) -N(R ³⁰ R ³¹ )-; R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ are substituted or unsubstituted groups independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl radical, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido; any of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ One can be combined with any other of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ to form a part of an ordinary ring; any twin R ²⁷ -R ²⁸ can be combined to form a carbonyl; any phase The adjacent R ²⁷ -R ³¹ may combine to form an unsaturated moiety; and any one of the substituents R ²⁷ -R ³¹ may combine to form a substituted or unsubstituted fused unsaturated moiety.

More preferred aryliminium zwitterions having a net charge of about +3 to about -3 as represented by formula [XII] include those represented by formula [XII] wherein R ^is H or methyl and the formula Represented group: Z _p ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- , and p is 1 or 2.

其中，R⁴¹-R⁴⁴可以独立地选自取代或未取代的基团，这些基团选自H，直链或支链、取代或未取代的烷基，环烷基，烷芳基，芳基，芳烷基，亚烷基、烷氧基，条件是任何一个R⁴¹-R⁴⁴可以与任何一个其它的R⁴¹-R⁴⁴结合形成普通环的一部分；更优选的是，R⁴¹-R⁴⁴中的至少一个，甚至更优选至少两个是H。最优选的是，R⁴¹和/或R⁴⁴是直链或支链C₁-C₁₆烷基或环烷基，甚至更优选的是，R⁴¹和R⁴⁴中的碳原子数之和是5-15，最优选是6-13。Most preferably, the aryliminium zwitterion is an ion represented by the following formula [XIIa]:

Among them, R ⁴¹ -R ⁴⁴ can be independently selected from substituted or unsubstituted groups, these groups are selected from H, linear or branched, substituted or unsubstituted alkyl, cycloalkyl, alkaryl, aryl radical, aralkyl, alkylene, alkoxy, provided that any one of R ⁴¹ -R ⁴⁴ can combine with any other R ⁴¹ -R ⁴⁴ to form part of an ordinary ring; more preferably, R ⁴¹ -R At least one, and even more preferably at least two of ⁴⁴ are H. Most preferably, R ⁴¹ and/or R ⁴⁴ are linear or branched C ₁ -C ₁₆ alkyl or cycloalkyl, even more preferably, the sum of the number of carbon atoms in R ⁴¹ and R ⁴⁴ is 5 -15, most preferably 6-13.

II. Bleaching Substances - Bleaching substances (oxaziridiniums) may also be used directly in the present invention. Bleaching species of the present invention include, but are not limited to, oxaziridinium zwitterions having a net charge of from about +3 to about -3.

The aryliminium zwitterions of the present invention are used in combination with a peroxygen source to enhance bleaching efficacy when a peroxygen source is present. Without being bound by theory, it is believed that the aryl iminium zwitterion reacts with a peroxygen source to form a more reactive bleaching species, the zwitterionic quaternary oxaziridinium compound, which can be represented by the reaction exemplified below:

Zwitterionic oxaziridinium compounds have increased or better activity at lower temperatures than peroxy compounds.

其中R^5′-R^7′独立地选自取代或未取代的基团，这些基团选自H，烷基，环烷基，芳基，烷芳基，芳烷基，杂环，甲硅烷基，硝基，卤素，氰基，磺基，烷氧基，酮基，羧基和烷氧羰基；在该式中也存在下式表示的基团：

其中Z′_p ^-与T′_o形成共价键，Z′_p ^-选自-CO₂ ^-，-SO₃ ^-，-OSO₃ ^-，-SO₂ ^-和-OSO₂ ^-，p为1，2或3；T′o选自取代或未取代的、饱和或未饱和的烷基，环烷基，芳基，烷芳基，芳烷基和杂环。Oxaziridinium Zwitterions - An oxaziridinium zwitterion having a net charge of about +3 to about -3 is represented by the formula [IV]:

wherein R ^5' -R ^7' are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silane radical, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula:

Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1,2 or 3; T'o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle.

Preferably, the oxaziridinium zwitterion having a net charge of about +3 to about -3 is represented by the formula [XIV]: Wherein, when G exists, m is 1-3, and when G does not exist, m is 1-4; n is an integer of 0-4; each R ^26' is independently selected from substituted or unsubstituted groups, these Groups selected from H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and alkane Oxycarbonyl, and any two adjacent R ^26' substituents can be combined to form a fused aryl, fused carbocycle or fused heterocycle; R ^25' can be a substituted or unsubstituted group selected from From H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and alkoxy Carbonyl; in this formula there are also groups represented by the formula: Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1 or 2 ; T' _o is selected from the following groups: wherein q is an integer from 1 to 8; R ^29' are independently selected from substituted or unsubstituted groups selected from linear or branched H, alkyl, cycloalkyl, alkaryl, aryl , aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido, with the proviso that not all R ^29' are independently selected from H; G is selected from: (1)-O- ; (2)-N(R ^30′ )-; and (3)-N(R ^30′ R ^31′ )-; R ^27′ , R ^28′ , R ^30′ and R ^31′ are substituted or unsubstituted groups independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and Amino group; any one of R ^25′ , R ^26′ , R ^27′ , R ^28′ , R ^30′ and R ^31′ can be combined with R ^25′ , R ^26′ , R ^27′ , R ^28′ , R ^{30 '} and any other of R ^31' are combined to form part of an ordinary ring; any twin R ^27' -R ^28' can be combined to form a carbonyl group; any adjacent R ^27' -R ^31' can be combined to form a non- a saturated moiety; and any one of the substituents R ^27' -R ^31' can be combined to form a substituted or unsubstituted condensed unsaturated moiety.

Z′_p ^-为-CO₂ ^-，-SO₃ ^-或-OSO₃ ^-，p为1或2。More preferred oxaziridinium zwitterions having a net charge of about +3 to about -3 as represented by formula [XIV] include those ions represented by formula [XIV] wherein R ^25' is H or methyl and the formula Represented group:

Z′ _p ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- , and p is 1 or 2.

Most preferably, the oxaziridinium zwitterion is an ion represented by the following formula [XIVa]: Wherein R ⁴¹ -R ⁴⁴ can be independently selected from substituted or unsubstituted groups, these groups are selected from H, linear or branched, substituted or unsubstituted alkyl, cycloalkyl, alkaryl, aryl , aralkyl, alkylene, alkoxy, provided that any one of R ⁴¹ -R ⁴⁴ can combine with any other R ⁴¹ -R ⁴⁴ to form part of an ordinary ring; more preferably, R ⁴¹ -R ⁴⁴ At least one, even more preferably at least two, of are H. Most preferably, R ⁴¹ and/or R ⁴⁴ are linear or branched C ₁ -C ₁₆ alkyl or cycloalkyl, even more preferably, the sum of the number of carbon atoms in R ⁴¹ and R ⁴⁴ is 5 -15, most preferably 6-13.

Organic Catalyst Compound Concentration - The zwitterionic organic catalyst compounds (bleach booster compounds and bleaching materials) of the present invention can and are preferably added to the wash solution, typically an aqueous wash solution, in an amount of about 0.00001% by weight of the composition (0.0001ppm) to about 10% (100ppm), preferably about 0.0001% (0.001ppm) to about 1% (10ppm) by weight of the composition, more preferably about 0.001% (0.01ppm) to about 0.5% (5ppm ), even more preferably from about 0.004% (0.04ppm) to about 0.25% (2.5ppm). Most preferably from about 0.01% (0.1 ppm) to about 0.1% (1 ppm).

For illustrative purposes, concentration conversion values (in ppm) are provided based on the product used at a concentration of 1000 ppm. The product containing 0.2 wt% of the organic catalyst compound was made into a 1000 ppm washing solution, and the concentration of the obtained organic catalyst compound was 2 ppm. Similarly, a product containing 0.2 wt% organic catalyst compound formulated as a 3500 ppm wash solution resulted in a concentration of 6.5 ppm organic catalyst compound. Decomposition of organic catalysts

The organic catalysts of the present invention, particularly the bleach booster compounds, are susceptible to decomposition via various decomposition pathways including, but not limited to, aromatization. The aromatization reaction (decomposition) of six-membered ring builders is well known in the art, without being limited by theory, and a typical example thereof appears in Hanquet et al., Tetrahedron 1993, 49, pp. 423-438. Other means of decomposition include but are not limited to attacking the bleach booster compound and/or bleaching species with nucleophiles including but not limited to hydroxide anion, perhydroxide anion, carboxylate anion, percarboxylate anion and other nucleophiles present under wash conditions. Delayed (controlled) addition of organic catalyst compounds

In the case of organic catalyst compounds with a limited service life, it has surprisingly been found that adding the organic catalyst compound to the wash solution via the delivery device after the fabric has been added to the wash solution, especially a wash solution containing a source of peroxygen, is different from adding the organic catalyst compound to the wash solution before the fabric is added to the wash solution. This organocatalyst compound has enhanced bleaching properties compared to addition to wash solutions. Without being limited by theory, it is believed that the organocatalyst compound decomposes in the wash solution prior to incorporation into the fabric. One way to improve the performance of the organocatalyst compound is to delay the addition of the organocatalyst compound of the present invention to the wash solution. Another approach to improving the performance of organocatalyst compounds is to use organocatalyst compounds with increased stability under wash conditions. The method of delayed (controlled) addition of organic catalyst compounds is described in more detail in co-pending and commonly owned U.S. Provisional Patent Application entitled "Controlled Availability of Formulation Components, Compositions and Laundry Methods Employing Same", filed August 27, 1999 ( P&G agency number is 7749P). Bleaching systems comprising zwitterionic organic catalyst compounds

In addition to the use of the zwitterionic organocatalyst compounds described above, the zwitterionic organocatalyst compounds of the present invention may or may not be used, but are preferably used in combination with other sources of peroxygen in bleaching systems, regardless of their form. For example, zwitterionic organic catalyst compounds can be used in detergent additive products. In the bleaching systems of the present invention, the peroxygen source is present in an amount of from about 0.1% to about 60%, preferably from about 1% to about 40%, by weight of the composition. In the composition, the organic catalyst compound is present in an amount of from about 0.00001% to about 10%, by weight of the system, preferably from about 0.0001% to about 1%, more preferably from about 0.001% to about 0.5%, even more From about 0.004% to about 0.25% is preferred. Most preferably from about 0.01% to about 0.1%.

The bleaching systems of the present invention are advantageously used in laundry applications, hard surface cleaning, automatic dishwashing applications and cosmetic applications such as dentures, teeth, hair and skin. However, the organocatalyst compounds of the present invention are ideally suited for laundry applications, for example by using Bleach-containing detergents or laundry bleach additives bleach fabrics. Furthermore, the bleach booster compounds of the present invention can be used in both granular and liquid compositions.

Zwitterionic organocatalyst compounds and bleach systems comprising the same are useful as antimicrobials and disinfectants.

Accordingly, the bleaching systems of the present invention may contain additional ingredients as may be desired in a variety of laundry applications. These ingredients include detersive surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric removers, brighteners and various other ingredients. Compositions comprising any of these various additional ingredients preferably have a pH in a 1% solution of the bleach system of from about 6 to about 12, preferably from about 8 to about 10.5.

The bleaching system preferably comprises at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme and preferably has a pH of from about 6 to about 12, preferably from 8 to about 10.5 in a 1% solution of the bleaching system.

In another embodiment of the present invention there is provided a method of laundering fabrics in need of laundering, especially colored fabrics. A preferred method involves contacting the fabric with a wash solution. The fabric can include most any fabric that can be laundered under normal consumer use conditions. The wash solution comprises a bleach system comprising one or more zwitterionic organic catalyst compounds of the present invention as detailed herein. The water temperature is preferably from about 0°C to about 50°C or higher. The ratio of water to fabric is preferably from about 1:1 to about 15:1.

The wash 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 wash solution has a pH of from about 6 to about 12, preferably from about 8 to about 10.5 in a 1% bleach system solution.

The bleaching systems of the present invention typically and preferably comprise a peroxygen source. Peroxygen sources are well known in the art and peroxygen sources for use in the present invention can include any of these known peroxygen sources including peroxygen compounds and peroxygen compounds that produce effective amounts of peroxygen in situ under consumer use conditions. compound of. The peroxygen source may comprise a source of hydrogen peroxide, a peracid anion formed in situ by the reaction of a source of hydrogen peroxide and a bleach activator, a preformed peracid compound or a mixture of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other sources of peroxygen may be used without departing from the scope of the present invention. Preferably, the source of peroxygen is selected from:

(i) prefabricated peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, and

(ii) A source of hydrogen peroxide selected from perborate compounds, percarbonate compounds, superphosphate compounds and mixtures thereof and bleach activators.

When present, a source of peroxygen (peracid and/or source of hydrogen peroxide) will generally be present in an amount of from about 1%, preferably from about 5% to about 30%, preferably to about 20%, by weight of the composition. Bleach activators, if present, will generally be present in an amount from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40%, by weight of the bleaching system comprising bleach plus bleach activator.

a. Preformed Peracids - As used herein, a preformed peracid compound is any convenient compound that is stable and capable of providing an effective amount of peracid anion under consumer use conditions. The organic catalysts of the present invention can of course be used with preformed peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acid and salts and mixtures thereof, which Examples are described in US Patent 5,576,282 to Miracle et al.

其中R为含有1至约22个碳原子的亚烷基或取代亚烷基，或亚苯基或取代亚苯基，Y为氢，卤素，烷基，芳基，-C(O)OH或-C(O)OOH。One class of suitable organic peroxycarboxylic acids has the general formula:

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

其中Y例如可以是氢，烷基，烷基卤，卤素，C(O)OH或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 unsubstituted peracid has the general formula: Where Y can be, for example, H, CH ₃ , CH ₂ Cl, C(O)OH, or C(O)OOH; n is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

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

Typical monoperoxyacids suitable for use in the present invention include alkyl and aryl peroxyacids such as:

(i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids such as peroxy-alpha-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and o-carboxybenzamidoperoxycaproic acid ( sodium salt);

(ii) Aliphatic, substituted aliphatic and aralkyl monoperoxyacids, such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3- Octylsuccinyl)aminoperoxycaproic acid (SAPA) and N,N-phthaloylaminoperoxycaproic acid (PAP);

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

Typical diperoxyacids suitable for use in the present invention 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'-sulfonyl diperoxybenzoic acid.

These bleaching agents are disclosed in U.S. Patent 4,483,781 issued to Hartman on November 20, 1984, U.S. Patent 4,634,551 to Burns et al., European Patent Application 0,133,354 to Banks et al. published on February 20, 1985, and U.S. Patent to Chung et al., issued on November 1, 1983. 4,412,934 in. Peroxyacid sources also include 6-nonylamino-6-oxoperoxycaproic acid as described in detail in US Patent 4,634,551, Burns et al., issued January 6, 1987. Persulfate compounds such as OXONE, commercially available from E.I. DuPont de Nemours of Wilmington, DE, may 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 present in an amount as detailed in US Pat. No. 5,576,282. For example, the source of hydrogen peroxide may be selected from perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof.

Hydrogen peroxide sources are described in detail in Kirk Othmer, Encyclopedia of Chemical Technology, 4th Edition (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", which is incorporated herein by reference , which includes sodium perborate and sodium percarbonate in various forms, including various coated and modified forms.

A preferred source of hydrogen peroxide suitable for use in the present invention may be any convenient source including hydrogen peroxide itself. For example, perborates such as sodium perborate (any hydrate but preferably mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate, sodium pyrophosphate peroxyhydrate, urea Peroxyhydrate, or sodium peroxide, can be used in the present invention. An available oxygen source such as persulfuric acid bleach (such as OXONE by DuPont) may also be used. 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 in the range of about 500 microns to about 1000 microns, of which particles no more than about 10% by weight of said particles are smaller than about 200 microns and no more than about 10% by weight of The particles are larger than about 1,250 microns. Optionally, the percarbonate may be coated with a silicate, borate or water soluble surfactant. Percarbonate is commercially available from various commercial sources such as FMC, Solvay and Tokai Denka.

The compositions of the invention may also contain chlorine-type bleaching materials as bleaching agents. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are not preferred for compositions comprising enzymes.

c. Bleach Activators - Preferably, the peroxygen source in the composition is formulated with an activator (peracid precursor). The activator is present in an amount of 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. A bleach activator as used herein is any compound which, when used with a source of hydrogen peroxide, generates in situ a peracid corresponding to the bleach activator. Various non-limiting examples of activators are fully disclosed in US Patent 5,576,282, US Patent 4,915,854 and US Patent 4,412,934. See also US Patent 4,634,551 for other typical bleaches and activators useful in this application.

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 Oxybenzenesulfonates ( _C8 -OBS), their perhydrolyzable esters and mixtures, most preferably benzoyl caprolactam and benzoyl valerolactam. Particularly preferred bleach activators at a pH of from about 8 to about 9.5 are those selected to have 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) ( An example of these is described in U.S. Patent 5,523,434), lauroyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecanoyloxybenzenesulfonate (UDOBS or 10-unsaturated C ₁₁ -OBS) and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in the following patents: US Patent 5,698,504 issued to Christie et al on December 16, 1997; US Patent 5,695,679 issued to Christie et al on December 9, 1997; Willey et al issued on November 11, 1997 1997.11.11 authorized to Hartshorn et al. US Patent 5,686,014; 1995.4.11 authorized to Willey et al. US Patent 5,405,412; 1995.4.11 authorized to Willey et al. US Patent 5,405,413; 1992.7.14 authorized to US Patent 5,130,045 to Mitchel et al; and US Patent 4,412,934 to Chung et al, issued November 1, 1983, and co-pending US Patent Applications 08/709,072, 08/064,564, which are incorporated herein by reference.

The molar ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention is generally 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 system of the present invention preferably comprises a quadrat substituted bleach activator (QSBA) or a quadrature substituted peracid (QSP); more preferably the former. Preferred QSBA structures are further described in the following patents: US Patent 5,686,015 issued to Willey et al on November 11, 1997; US Patent 5,654,421 issued to Taylor et al on August 5, 1997; US Patent 5,460,747 issued to Gosselink et al on October 24, 1995; US Patent 5,584,888, Miracle et al., issued December 17, 1996; and US Patent 5,578,136, Taylor et al., issued November 26, 1996; incorporated herein by reference.

Highly preferred bleach activators for use herein are the amide substituted species described in US Patent 5,698,504, US Patent 5,695,679 and US Patent 5,686,014, each of which is cited above. Preferred examples of these bleach activators include: (6-octanoylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, (6-decanoylaminocaproyl)oxybenzene Sulfonates and mixtures thereof.

Other useful activators disclosed in U.S. Patent 5,698,504, U.S. Patent 5,695,679, U.S. Patent 5,686,014, and U.S. Patent 4,966,723 issued to Hodge et al. on October 30, 1990, cited above, include benzoxazine-type activators, such as those described in 1 , a C ₆ H ₄ ring with a -C(O)OC(R ¹ )=N- moiety fused at the 2 position.

Depending upon the activator and precise application, good bleaching results can be obtained from bleaching systems which have an in-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, activators with electron-withdrawing moieties are used, eg, in the near-neutral or sub-neutral pH range. Such a pH can be maintained with bases and buffers.

The acyl lactam activators described in U.S. Patent No. 5,698,504, U.S. Patent No. 5,695,679 and U.S. Patent No. 5,686,014 cited above are very useful in the present invention, especially useful are acyl caprolactams (see, for example, WO 94-28102A) and acyl valerolactams. Lactams (see US Patent 5,503,639, Willey et al., issued April 2, 1996, which is incorporated herein by reference).

d. Organic Peroxides, especially Diacyl Peroxides - In addition to the bleaching agents described above, the bleaching systems 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 and Sons, 1982, pp. 27-90, especially pp. 63-72, which are incorporated herein by reference in their entirety. If a diacyl peroxide is used, it will preferably be one that has the least adverse effect on spotting/filming.

e. Metal Containing Bleach Catalysts - The bleach system may also optionally contain a metal containing bleach catalyst, preferably a magnesium and cobalt containing bleach catalyst.

A metal-containing bleach catalyst is one comprising transition metal cations such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations having defined bleach catalytic activity, auxiliary metal cations such as zinc having little or no bleach catalytic activity or aluminum cations, and chelating agents having defined stability constants for the catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and their water-soluble salts. These catalysts are disclosed in US Patent 4,430,243, issued February 2, 1982 to Bragg.

i. Manganese Metal Complexes - If desired, the compositions of the present invention can be catalyzed with manganese compounds. Such compounds and their amounts are well known in the art and include manganese-based catalysts as disclosed in the following patents: U.S. Patent 5,576,282 issued to Miracle et al on November 19, 1996; U.S. Patent 5,246,621 issued to Favre et al on September 21, 1993 1993.9.14 US Patent 5,244,594 issued to Favre et al.; 1993.3.16 US Patent 5,194,416 issued to Jureller et al.; 1992.5.19 US Patent 5,114,606 issued to van Vliet et al.; 544,440A2 and 544,490A1; 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 (PF6) and mixtures thereof. Other metal-based bleach catalysts include those disclosed in US Patent 4,430,243, above referenced in this application, and US Patent 5,114,611, issued May 19, 1992 to van Kralingen. The use of manganese with various ligands for the purpose of enhancing bleaching is also reported in the following patents: US Patent 4,728,455 issued to Rerek on March 1, 1988; US Patent 5,284,944 issued to Madison on February 8, 1994; U.S. Patent 5,246,612 of van Dijk et al.; 1993.10.26 authorized to Kerschner et al. U.S. Patent 5,256,779; 1994.1.18 authorized to Kerschner et al. U.S. Patent 5,280,117; 1993.12.28 authorized to Kerschner et al. 6 US Patent 5,153,161 issued to Kerschner et al. and US Patent 5,227,084 issued to Martens et al. on July 13, 1993.

ii. Cobalt Metal Complexes - Cobalt bleach catalysts suitable for use in the present invention are known and described in, for example, U.S. Patent No. 5,597,936 issued to Perkins et al. on January 28, 1997; US Patent 5,595,967; US Patent 5,703,030, issued December 30, 1997 to Perkins et al; and ML Tobe, "Alkaline 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 the cobalt pentaamine acetate salt of the formula [Co( _NH3 ) _5OAc ] _Ty , where "OAc" denotes the acetate moiety and " _Ty " is the anion, especially chloride [Co(NH ₃ ) ₅ OAc](OAc) ₂ ; [Co(NH ₃ ) ₅ OAc](PF ₆ ) ₂ ; [Co(NH ₃ ) ₅ OAc](OAc) ₂ ; (NH ₃ ) ₅ OAc](SO ₄ ); [Co(NH ₃ ) ₅ OAc](BF ₄ ) ₂ ; and [Co(NH ₃ ) ₅ OAc](NO ₃ ) ₂ (herein written as "PAC") .

These cobalt catalysts are readily prepared by known techniques, such as those directed in the above cited U.S. Patent 5,597,936, U.S. Patent 5,595,967, U.S. Patent 5,703,030, and Tobe's articles and references cited therein and 1989.3 .7 U.S. Patent 4,810,410 granted to Diakun et al., J.Chem.Ed. (1989), 66(12), pp. 1043-45; Synthesis and Characterization of Inorganic Compounds, W.L.Jolly (Prentice-Hall; 1970), 461 -3 pages; Inorg.Chem., 18, 1497-1502 (1979); Inorg.Chem., 21, 2881-2885 (1982); Inorg.Chem., 18, 2023-2025 (1979); Inorg.Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

iii. Transition Metal Complexes with Polycyclic Rigid Ligands - The compositions of the present invention may also suitably contain transition metal complexes with polycyclic rigid ligands for use 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 higher, such as up to about 99.9%, more generally about 0.001 ppm or higher, preferably from about 0.05 ppm to about 500 ppm (where "ppb" means parts per billion One part by weight, "ppm" means parts per million by weight).

Suitable transition metals such as Mn will be described below. "Polycyclic" means that the MRL is both macrocyclic and polycyclic. "Polycyclic" means at least two rings. The term "rigid" as used in this application includes "having a superstructure" and "having cross-linking bridges". "Rigidity" is defined as the exact opposite of elasticity: see D. H. Busch., Chemical Reviews., (1993), 93, 847-860, which is hereby incorporated by reference. More specifically, "rigid" as used herein means that the MRL must be measurably more rigid than the macrocycle (the "parent macrocycle"), where both are identical in structure (having the same ring as the main ring). size and type and number of atoms), but the macrocycle (the "parent macrocycle") does not have the superstructure in the MRL (especially the linking moiety or preferably the cross-linking bridge moiety). In determining the relative rigidity of macrocycles with and without superstructures, operators use the free form (non-metal bonded form) of the macrocycle. Stiffness is well known for use in comparing macrocycles; suitable tools for determining, measuring or comparing stiffness include computational methods (see e.g. Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica Acta, (1989), 164, 73-84).

The preferred MRLs of the present invention are a special class of ultrarigid ligands with cross-linked bridges. A non-limiting description of "crosslinking bridges" is given in 1.11 below. In 1.11, the crosslink bridge is a -CH2CH2- moiety. It bridges ^N1 and ^N8 in the exemplified structure. In comparison, "same side" bridging, eg if one is introduced in 1.11 to cross-link N ¹ and N ¹² , is not sufficient to constitute a "cross-link bridge" and is therefore not preferred.

In complexes with rigid ligands, suitable metals 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 in the transition metal bleach catalysts of the present invention include manganese, iron and chromium.

More generally, MRLs (and corresponding transition metal catalysts) suitable for use in the present invention comprise:

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

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

(i) bridging superstructures, such as linking sections;

(ii) crosslinked bridge superstructures, such as crosslinked bridge connecting parts; and

(iii) mixtures thereof.

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

The preferred superstructure of this application not only improves the rigidity of the parent macrocycle, but also facilitates the folding of the macrocycle, allowing it to coordinate with the metal in the gap. A suitable superstructure can be very simple, such as a joint section, as either of the sections shown in Figures 1 and 2 below can be used.

Fig. 1 wherein n is an integer, such as 2-8, preferably less than 6, generally 2-4, or

In Fig. 2, m and n are integers of about 1-8, more preferably 1-3; Z is N or CH; T is a compatible substituent, such as H, alkyl, trialkylammonium, halogen, nitro , Sulfonate, etc. The aromatic ring in 1.10 can be replaced by a saturated ring, where the atoms in Z attached to the ring can include N, O, S or C.

Suitable MRLs are further illustrated, but not limited, by the following compounds:

Figure 3. This is a highly preferred MRL of the invention which is a cross-linked, methyl substituted (all nitrogen atoms are tertiary nitrogen atoms) cyclam derivative. This ligand is formally named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the extended Von Baeyer system. See "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 having macrocyclic rigid ligands suitable for use in the compositions of the present invention generally include known compounds meeting the definitions herein and more preferably any of a number of novel compounds designed specifically for existing detergent or cleaning applications. , which is non-limitingly exemplified with any of the following compounds: dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) Dihydrate-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane hexafluoromanganese(II) hydrate-hydroxy-5,12-dimethyl- 1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese hexafluorophosphate (III) dihydrate-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] Manganese(II) hexadecanetetrafluoroborate (III) Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese (II) Dichloro-5,1 2-dibenzyl -1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza Bicyclo[6.6.2]hexadecanemanganese(II) dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II ) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II)

f. Other Bleach Catalysts - The compositions of the present invention 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)propanesulfonate). Other bleach catalysts include cationic bleach catalysts described in US Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256 and WO 95/13351, WO 95/13352 and WO 95/13353.

As a practical example, and not intended to be limiting, the compositions and cleaning methods of the present application can be adjusted to provide active bleach catalyzing species on the order of at least one part per million in the aqueous wash medium, preferably from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, most preferably from about 0.1 ppm to about 5 ppm bleach catalyst species. To obtain such concentrations in wash liquors of automatic washing processes, typical compositions of the present invention comprise 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 a bleach catalyst, especially manganese or cobalt catalyst.

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 this bleaching system is to attenuate the undesired decomposition of the organic catalyst and to allow the peracid to bleach the fabric to be cleaned, such as soiled fabric, in the wash solution before the organic catalyst has acted.

The time period between activation of the peracid in the wash solution and activation of the organic catalyst compound is from about 1 second to about 24 hours. Additionally, since the organocatalyst compound is relatively stable in the wash solution, the peracid can be activated in the wash solution after the organocatalyst compound is activated or effective.

The purpose of the delayed addition bleach system (which may or may not be used in conjunction with the present invention) is to maximize the bleaching effect of the peracid on fabrics to be cleaned, such as soiled fabrics, in the wash solution prior to the introduction of the organic catalyst compound. In other words, the organic catalyst compound contained in the bleaching system is activated in the wash solution after the fabric to be cleaned is added to the wash solution. Alternatively, due to the increased stability of the organocatalyst compound, bleaching systems may be used in which the organocatalyst compound is activated in the wash solution before the fabric to be cleaned is added to the wash solution.

A preferred bleaching system according to the invention is a bleaching system comprising:

(a) a source of peroxygen; and

(b) zwitterionic organic catalyst compounds;

Wherein the zwitterionic organic catalyst compound is activated in the wash solution containing the bleach system some time after activation of the peroxygen source. As mentioned above, the source of peroxygen is preferably selected from:

(i) prefabricated peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acid and salts, perimidic acid and salts, peroxymonosulfuric acid and salts and mixtures thereof, and

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

In addition to the organic catalyst(s) previously described in this application, the bleach systems of the present invention preferably comprise one or more cleaning aid materials which are preferably compatible with the organic catalyst(s) and/or any enzymes present in the bleaching system. compatible. As used herein, the term "compatible" means that the substances of the bleaching system do not impair the bleaching activity of the organic catalyst and/or any enzymatic activity of any enzyme present in the bleaching system to such an extent that the organic catalyst and/or enzyme Not as effective as would be required under normal use conditions. The term "cleaning aid material" as used herein means: for obtaining the particular type of bleaching system and product form (e.g. liquid; granule; powder; bar; paste; spray; tablet; gel; foam composition) ) any liquid, solid or gaseous substance selected, which is also preferably compatible with the protease and bleach used in the composition. Granular compositions may also be in "compact" form and liquid compositions may be in "concentrated" form.

The specific selection of cleaning aid materials is readily made by consideration of the surface, item or fabric to be cleaned and the desired composition form for the wash conditions in use (eg, by use of a laundering cleaner). Examples of suitable cleaning aid materials include, but are not limited to, the surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes described in U.S. Pat. , enzyme stabilization system, chelating agent, brightener, soil release polymer, dye transfer agent, dispersant, foam suppressor, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescer, fabric conditioner agent, hydrolyzable surfactant, preservative, antioxidant, anti-shrinkage agent, anti-wrinkle agent, bactericide, fungicide, colored spot decoration, silver care agent (silvercare), rust and/or anti-corrosion agent, alkali Sexual source, solubilizer, carrier, processing aid, pigment and PH control agent. Specific bleaching system materials will be exemplified and detailed later in this application.

If the cleaning aid material is not compatible with the various protease variants in the bleach system, then a suitable method can be used to separate the cleaning aid material and the various protease variants (out of contact with each other) until the two components are mixed . A suitable method may be any method known in the art, such as gelcaps, capsules, tablets, physical separation, and the like.

Such bleaching systems include detergent compositions for cleaning hard surfaces, in any form (e.g. liquid, granule, paste, foam, spray, etc.); detergent compositions for cleaning fabrics, in any form (e.g. granule, liquid , bar formulations, etc.); dishwashing compositions (in any form, including granular and liquid autodishwashers); oral bleaching systems, in any form (such as dentifrice, toothpaste, and mouthwash); and denture bleaching systems , in any form (eg liquid, tablet).

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

Bleaching systems can comprise from about 1% to about 99.9% by weight of the composition of cleaning adjunct materials.

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

When the bleaching systems of the present invention are formulated into compositions suitable for use in washing machine washing methods, the compositions of the present invention preferably comprise surfactant and builder compounds and additionally one or more detergency adjunct materials, the detergency aid The material is 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 may also be used as detergent additive products in solid or liquid form. Such additive products are used to supplement or enhance the performance of conventional detergent compositions and can be added at any stage of the cleaning process.

When formulated as compositions for use in manual dishwashing methods, the compositions of the present invention preferably comprise a surfactant and preferably other cleaning aid materials selected from the group consisting of organic polymers, suds boosters, Group II Metal ions, solvents, hydrotropes and additional enzymes.

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

In terms of composition, the "compact" form of the bleaching system of the present invention is best reflected by the density and the amount of inorganic filler salt; inorganic filler salt is a traditional ingredient in detergent compositions in powder form; In the composition, the filler salt exists in a large amount, generally 17-35% of the total weight of the composition. In compact compositions, the filler salt is present in an amount not exceeding 15% by weight of the total composition, preferably not exceeding 10% by weight of the composition, most preferably not exceeding 5% by weight of the composition. Inorganic filler salts such as those referred to in the present compositions are selected from alkali and alkaline earth metal sulfates and chlorides. A preferred filler salt is sodium sulfate.

The liquid bleaching systems of the present invention may also be in "concentrated form", in which case the liquid bleaching systems of the present invention contain lower amounts of water compared to conventional liquid detergents. The water content of the concentrated liquid bleaching system is generally preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the bleaching system. cleaning aid material

Although not necessary for the purpose of the present invention, several traditional auxiliaries enumerated later are suitable for the bleaching system of the present invention, and can be added in preferred embodiments of the present invention as required, such as assisting or improving cleaning performance, for Treatment of substrates to be cleaned, or to improve the aesthetic properties of bleaching systems, such as the use of fragrances, colorants, dyes, etc. The exact nature of these additional components and the level at which they are added will depend upon the physical form of the composition and the nature of the cleaning operation being performed. Unless otherwise specified, the bleaching systems of the present invention can be formulated, for example, as all-purpose or "heavy-duty" cleaners, in particular laundry detergents, in granular or powder form; all-purpose detergents in liquid, gel or paste form, especially So-called heavy-duty liquid types; liquid delicate fabric detergents; hand dishwashing detergents or light-duty dishwashing detergents, especially those that are rich in suds; machine-washing dishwashing detergents, including various tablets for domestic and institutional use , granular, liquid and rinse aids; liquid cleaners and disinfectants, including antibacterial hand washes, laundry soap bars, mouthwashes, denture cleaners, car or carpet shampoos, bathroom cleaners; hair shampoos and shampoos ; shower gels and foam bath and metal cleaners; and cleaning aids such as bleach additives and "stain stick" or pre-treatment types.

Surfactants - The compositions of the present invention preferably comprise a detersive surfactant. Detersive surfactants are generally selected from anionic, nonionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof. By selection of the type and amount of detersive surfactant and other adjunct ingredients disclosed herein, the detergent compositions of the present invention can be formulated for laundry washing or other various cleaning applications including dishwashing, among others. Thus, the particular surfactant used may vary widely depending on the particular end use envisioned. Suitable surfactants are described below. Examples of suitable nonionic, anionic, cationic, amphoteric and zwitterionic surfactants are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). Various types of such surfactants are also generally disclosed at Column 23, line 58 through Column 29, line 23 of US Patent 3,929,678, issued December 30, 1975 to Laughlin et al.

Surfactants are generally present in an amount from about 0.1%, preferably from about 1%, more preferably from about 5% to about 99.9%, preferably to about 80%, more preferably to about 35% by weight of the bleach system , most preferably to about 30%.

Anionic Surfactants - The anionic surfactants used in the present invention are preferably selected from linear alkylbenzene sulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates Salt, Alkyl Alkoxy Sulfate, Alkyl Sulfonate, Alkyl Alkoxy Carboxylate, Alkyl Alkoxylated Sulfate, Sarcosinate, Taurate and mixtures thereof. Anionic detersive surfactants can be used herein in an effective amount generally from about 0.5 wt% to about 90 wt%, preferably from about 5 wt% to about 60 wt%, more preferably from about 10 wt% to about 30 wt%.

Alkyl sulfate surfactants are another class of important anionic surfactants for use in the present invention. When used in combination with polyhydroxy fatty acid amides (see below), these overall cleaning properties include excellent grease/oil cleaning over a wide range of temperatures, wash concentrations and wash times, in addition to being able to produce excellent overall cleansing properties, It also dissolves the alkyl sulfates and improves formulatability in liquid detergent formulations. These surfactants are water soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbon group, preferably an alkyl or hydroxyalkyl group with a C ₁₀ -C ₂₀ alkyl moiety, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation such as an alkali metal (Group IA) cation (e.g. sodium, potassium, lithium), a substituted or unsubstituted ammonium cation such as methyl-, dimethyl- and Trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like. In general, _C12-16 alkyl chains are preferred at lower wash temperatures (eg, below about 50°C) and _C16-18 alkyl chains are preferred at higher wash temperatures (eg, above about 50°C).

Alkyl alkoxylated sulfate surfactants are another class of useful anionic surfactants. These surfactants are generally water-soluble salts or acids of the formula RO(A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl having a C ₁₀ -C ₂₄ alkyl moiety , preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than 0, generally between about 0.5 and about 6 Between, more preferably between about 0.5 and about 3, M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are contemplated for use in the present invention. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and those derived from alkanolamines such as monoethanolamine, di Cation of ethanolamine, triethanolamine and mixtures thereof. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylated (1.0) sulfates, C ₁₂ -C ₁₈ alkyl polyethoxylated (2.25) sulfates, C ₁₂ -C ₁₈ alkyl Polyethoxylated (3.0) sulfates, _C12 - _C18 alkyl polyethoxylated (4.0) sulfates, wherein M is conveniently selected from sodium and potassium. The surfactants useful in the present invention are prepared from natural or synthetic alcohol starting materials. Chain lengths indicate average hydrocarbon distribution, including branching.

Additionally and preferably, the surfactant may be a medium chain branched alkyl sulfate, a medium chain branched alkyl alkoxylate or a medium chain branched alkyl alkoxylate sulfate. These surfactants are further described in the following patents: 60/061,971, 1997.10.14, 6881P; 60/061,975, 1997.10.14, 6882P; 60/062,086, 1997.10.14, 6883P; 1997.10.14 patent 60/061,916 with proxy number 6884P, 1997.10.14 patent 60/061,970 with proxy number 6885P, 1997.10.14 patent 60/062,407 with proxy number 6886P. Other suitable mid-chain branched surfactants are found in U.S. Patent Application 60/032,035 (Attorney No. 6401P), 60/031,845 (Attorney No. 6402P), 60/031,916 (Attorney No. No.6403P), 60/031,917 (the agent number is No.6404P), 60/031,761 (the agent number is No.6405P), 60/031,762 (the agent number is No.6406P) and 60/031,844 (the agent number is No. 6409P). Mixtures of these branched chain surfactants and conventional linear surfactants are also suitable for use in the compositions of the present invention.

Further preferred anionic surfactants are the so-called modified alkylbenzene sulfonate surfactants or MLAS. Some suitable MLAS surfactants, their methods of preparation and exemplary compositions are further described in co-pending U.S. Patent Application 60/053,319 (Attorney No. 6766P), 60/053,318 (Attorney No. 6767P) , 60/053,321 (the agent number is No.6768P), 60/053,209 (the agent number is No.6769P), 60/053,328 (the agent number is No.6770P), 60/053,186 (the agent number is No.6771P), 60 /055,437 (Agent No. 6796P), 60/105,017 (Agent No. 7303P) and 60/104,962 (Agent No. 7304P).

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

Nonionic Detergent Surfactants - Suitable nonionic surfactants are generally described in column 13, line 14 to column 16, line 6 of U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin et al., incorporated herein as refer to. Exemplary, 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 which include water soluble amine oxides comprising an alkyl moiety of about 10 to about 18 carbon atoms and two alkyl moieties selected from the group consisting of from about 1 to about 3 carbon atoms and hydroxyalkyl moieties; water-soluble phosphine oxides comprising an alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms; and water-soluble sulfoxides comprising an alkyl moiety of about 10 to about 18 carbon atoms and an alkyl and hydroxyalkyl moiety selected from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include those having the molecular formula Amine oxide surfactants, wherein ^R3 is an alkyl, hydroxyalkyl or alkylphenyl group containing about 8 to about 22 carbon atoms or a mixture thereof; ^R4 is an alkylene group containing about 2 to 3 carbon atoms or a hydroxyalkylene group or a mixture thereof; x is from 0 to about 3; each ^R is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or contains from about 1 to about 3 rings Polyethylene oxide groups of oxyethylene groups. The R ⁵ groups 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. The amine oxide is preferably present in the composition in an effective amount, more preferably in an amount from about 0.1 wt% to about 20 wt%, even more preferably from about 0.1 wt% to about 15 wt%, even more preferably from about 0.5 wt% to about 10 wt% .

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols. Polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkylphenols and alkylene oxides having an alkyl group having from about 6 to about 12 carbon atoms in a linear or branched chain configuration. In a preferred embodiment, ethylene oxide is present in an amount from 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 the GAF Company; and ^Triton® X-45, X-114, X-100, and X-102, all sold by the Rohm & Haas Company sell. These compounds are generally referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Condensates of fatty alcohols and from about 1 to about 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 condensation products of alcohols having alkyl groups containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^® 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear secondary alcohols and 9 moles of ethylene oxide), Tergitol ^® 24-L-6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohol and 6 moles of ethylene oxide, and has a narrow molecular weight distribution), both sold by Union Carbide Corporation; ^Neodol® 45-9 (C ₁₄ -C ₁₅ linear alcohol and 9 moles Condensation product 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 and 7 moles of Condensation product of ethylene oxide), Neodol ^® 45-4 (condensation product of C ₁₄ -C ₁₅ linear alcohol and 4 moles of ethylene oxide), sold by Shell Chemical Company, and Kyrot ^® EOB (C ₁₃ -C ₁₅ Alcohol and 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".

Preferred alkyl polyglycosides have the formula

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group comprises from about 10 to about 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first made and then reacted with glucose or a source of glucose to form a glycoside (attached at the 1-position) to which another glycosyl unit can then be attached at its 1-position to the previous Between the 2-, 3-, 4- and/or 6-positions of the glycosyl units, preferably predominantly in the 2-position.

Fatty acid amide surfactants have the following molecular formula: wherein ^R is an alkyl group containing from about 7 to about 21 (preferably about ⁹ to about 17) carbon atoms, each R is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkane and -( _C2H4O ) _xH , where x varies from about 1 to _about 3.

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

When present in the compositions of the present invention, the nonionic surfactant is preferably present in an effective amount, more preferably in an amount from about 0.1 wt% to about 20 wt%, even more preferably from about 0.1 wt% to about 15 wt%, even further More preferably from about 0.5 wt% to about 10 wt%.

Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions herein may also comprise an effective amount of a polyhydroxy fatty acid amide surfactant. "Effective amount" means that the formulator of the composition can select an amount of polyhydroxy fatty acid amide to be added to the composition to improve the cleaning performance of the detergent composition. Overall, the addition of about 1 wt% of polyhydroxy fatty acid amides for conventional levels improved cleaning performance.

The detergent compositions herein generally comprise about 1% by weight of the polyhydroxy fatty acid amide surfactant, preferably from about 3% to about 30% by weight of the polyhydroxy fatty acid amide. This polyhydroxy fatty acid amide surfactant component comprises the following compound of structural formula: Wherein: R ¹ is H, C ₁ -C ₄ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ² is C ₅ -C ₃₁ hydrocarbon group, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most Preference is given to linear C ₁₁ -C ₁₅ alkyl or alkenyl groups, or mixtures thereof; Z is a polyhydroxyl hydrocarbon radical having a linear hydrocarbon radical chain directly attached to at least 3 hydroxyl groups, or an alkoxylated (preferably ethoxylated) or propoxylated) derivatives. Z is preferably derived 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 and high maltose corn syrup can be used, as well as the simple sugars listed above. These corn syrups can yield a mixture of sugar components for Z. It should be understood that the present invention by no means excludes other suitable starting materials. Z is preferably selected from -CH2-(CHOH) _n - _CH2OH , -CH( _CH2OH )-(CHOH) _{n-1 -CH2OH} , -CH2-( _CHOH ) ₂ (CHOR')(CHOH) _-CH2OH and its alkoxylated derivatives, wherein n is an integer from 3 to 5 inclusive, R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially _-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, stearamide, oleamide, laurylamide, myristamide, capricamide, palmitamide, tallowamide and the like.

Z may be 1-deoxyglucosyl, 2-deoxyfructosyl, 1-deoxymaltosyl, 1-deoxylactosyl, 1-deoxygalactosyl, 1-deoxymannosyl, 1-deoxymaltotriosyl, etc.

Methods of making polyhydroxy fatty acid amides are known in the art. Generally speaking, it can generate corresponding N-alkyl polyhydroxyl amine in the reductive amination reaction of alkylamine and reducing sugar, and then make N-alkyl polyhydroxyl amine and fatty acid aliphatic ester or triglyceride in N-alkyl, N-polyhydroxy fatty acid amide products are produced in the condensation/amide reaction. Methods for preparing compositions comprising polyhydroxy fatty acid amides are disclosed, for example, in the following patents: British Patent Specification 809,060, Thomas Hedley & Co., Ltd., published February 18, 1959, U.S. Patent 2,965,576, issued December 20, 1960 to E.R. Wilson , and US Patent 2,703,798 issued to Anthony M. Schwartz on March 8, 1955, and US Patent 1,985,424 to Piggott on December 25, 1934, which are incorporated herein by reference.

Diamines - preferred liquid detergent compositions for use 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 anionic surfactants present are active The ratio of agent to diamine is from about 40:1 to about 2:1. Said diamine can also increase the detergency to oily or greasy food while maintaining moderate foam.

其中每个R²⁰都独立选自H，C₁-C₄直链或支链烷基，具有如下结构式的亚烷氧基：Diamines suitable for use in the compositions of the present invention have the following structural formula:

Wherein each R ²⁰ is independently selected from H, C ₁ -C ₄ straight chain or branched chain alkyl, and an alkyleneoxy group having the following structural formula:

-(R ²¹ O) _y R ²² wherein R ²¹ is C ₂ -C ₄ linear or branched chain alkylene and mixtures thereof; R ²² is H, C ₁ -C ₄ alkyl and mixtures thereof; y is from 1 to about 10; X is selected from the following units:

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, having the following molecular formula Alkyleneoxyalkylene:

-(R ²¹ O) _y R ²¹ -wherein R ²¹ and y are the same as defined above;

ii) C ₃ -C ₁₀ straight chain, C ₃ -C ₁₀ branched chain, C ₃ -C ₁₀ ring, C ₃ -C ₁₀ branched chain cycloalkylene group, C ₆ -C ₁₀ arylene group, wherein the The unit comprises one or more electron donating or electron withdrawing moieties that impart a pKa of said diamine of greater than about 8; and

iii) A mixture of i) and ii), provided that the pKa of the diamine is at least about 8.

The pK ₁ and pK ₂ of the preferred diamines of this invention are both from about 8 to about 11.5, preferably from about 8.4 to about 11, more preferably from about 8.6 to about 10.75. For the purposes of the present invention, the term "pKa" is equivalent to the terms " _pK1 " and " _pK2 " or to both, respectively. Throughout the present specification, the term pKa is used in this application in the same manner as those of ordinary skill in the art. Pka values are readily obtained from standard literature sources such as "Critical Stability Constants: Volume 2, Amines", Smith and Martel, Plenum Press, NY and London, (1975).

For the purposes of the definition used herein, the pKa value of a diamine is defined as measured in an aqueous solution having an ionic strength of from about 0.1 to about 0.5 M at 25°C. As used herein, pKa is an equilibrium constant that depends on temperature and ionic strength and, therefore, is not determined in the manner described above and values reported in references do not fully correspond to the values and ranges encompassed by the present invention. For the avoidance of ambiguity, the relevant conditions and/or parameters for pKa values used in the present invention are as defined here, or see "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is potentiometric titration of sodium hydroxide against acid and determination of pKa according to an appropriate method as described and referenced in "The Chemist's Ready Reference Handbook", Shugar and Dean, McGrawHill, NY, 1990.

In view of performance and availability, preferred diamines are 1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane (pK ₁ =10.5; pK ₂ =8.8), 1,6-diamino Hexane (pK ₁ =11; pK ₂ =10), 1,3-diaminopentane (Dytek EP) (pK ₁ =10.5; pK ₂ =8.9), 2-methyl-1,5-diaminopentane Alkane (Dytek A) (pK ₁ =11.2; pK ₂ =10.0). Other preferred substances are primary/primary diamines with _C4 - _C8 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, its molecular formula:

1,6-diaminohexane, its molecular formula is:

1,3-diaminopropane, its molecular formula is:

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

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

1,3-diaminobutane, its molecular formula is:

Jeffamine EDR 148, which is a diamine with an alkyleneoxy skeleton, its molecular formula is: 3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine), its molecular formula is:

1,3-bis(methylamino)cyclohexane, its molecular formula is: additional detergent components

The following are non-limiting examples of additional detergent ingredients (adjunct ingredients) suitable for use in bleaching systems, particularly laundry detergent compositions, of the present invention, said adjunct ingredients including builders, brighteners, soil release polymers , dye transfer agents, dispersants, enzymes, foam suppressors, dyes, fragrances, colorants, filler salts, hydrotropes, photoactivators, fluorescent agents, fabric conditioners, hydrolyzable surfactants, preservatives, anti Oxidizing agents, chelating agents, stabilizers, anti-shrinkage agents, anti-wrinkle agents, bactericides, fungicides, anti-corrosion agents and mixtures thereof.

Builders - The bleach systems of the present invention preferably comprise one or more detergent builders or builder systems. When present, the composition generally comprises at least about 1 wt % builder, preferably from about 5 wt %, more preferably from about 10 wt % to about 80 wt %, preferably to about 50 wt %, more preferably to about 30 wt % detergent builders.

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

Inorganic or phosphorus-containing detergent builders including, but not limited to, alkali metal, ammonium and alkanolammonium polyphosphates (such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphonates, Phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, in some instances non-phosphate builders are desired. Importantly, the compositions of the present invention are so-called "under-built" even with so-called "weak" builders (compared to phosphates) such as citrates or with zeolite or layered silicate builders. Its performance is still surprisingly good.

Examples of silicate builders are alkali metal silicates, especially those having a SiO2: _Na2O ratio of _1.6 :1 to 3.2:1 and layered silicates, as described in Layered sodium silicate in US Patent 4,664,839 issued to Rieck on May 12, 1987. NaSKS-6 is the trademark for a crystalline layered silicate sold by Hoechs t (often abbreviated in this application as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has _the delta- _Na2SiO5 morphology of layered silicates. 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 suitable for use in the present invention, however, other such phyllosilicates may also be used, such as those having the general formula _{NaMSixO2x +1} · _yH2O , wherein M is sodium or H, x is 1.9-4, preferably 2, and y is 0-20, preferably 0. Various other layered silicates available from Hoechst include the alpha, beta, gamma forms NaSKS-5, NaSKS-7 and NaSKS-11. As noted above, delta- _Na2SiO5 (Na SKS-6 form) is most preferred for use in _this application. Other silicates may also be used, such as manganese silicates, which are useful as edge strengtheners in granular formulations, as stabilizers in oxygen bleaches and as components of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates disclosed in German Patent Application 2,321,001 published November 15, 1973.

Aluminosilicate builders are suitable for use herein. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions and can also be a very important builder ingredient in liquid detergent formulations. Aluminosilicate builders include those materials having the following empirical formula:

[M _z (zAlO ₂ ) _y ]·xH ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetic derivatives. A method of preparing aluminosilicate ion exchange materials is disclosed in US Patent 3,985,669, issued October 12, 1976 to Krummel et al. Synthetically preferred synthetic crystalline aluminosilicate ion exchange materials for use herein 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:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O wherein x is about 20 to about 30, especially about 27. This material is called zeolite A. Dehydrated zeolites (x=0-10) may also be used in the present invention. Preferably the aluminosilicate has a particle size of 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 carboxyl groups, preferably at least 3 carboxyl groups. Polycarboxylate builders are generally added to the compositions in acid form, but may also be added in neutral salt form. When used in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Polycarboxylate builders include a wide variety of useful materials. An important class of polycarboxylate builders includes the ether polycarboxylates, including oxydisuccinates, disclosed in U.S. Patent 3,128,287 issued to Berg on April 7, 1964, and Lamberti et al on January 18, 1972. US Patent 3,635,830, issued on February 3, 1976 to Lamberti in US Patent 3,936,448. See also "TMS/TDS" builders in US Patent 4,663,071, Bush et al., issued May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds, such as those described in the following patents: U.S. Patent 3,923,679 to Rapko on December 2, 1975; U.S. Patent 3,923,679 to Crutchfield et al. Patent 4,158,635; US Patent 4,120,874, issued October 17, 1978 to Crutchfield et al; and US Patent 4,120,903, issued July 25, 1978 to Crutchfield et al.

Other useful detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, various alkali metal, ammonium and substituted ammonium polyacetates such as ethylenediaminetetraacetate and nitrilotriacetate, and polycarboxylates such as maleic acid, succinate acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

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 origin 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 mixtures.

Also suitable for use in the bleaching systems of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates, related compounds being disclosed in US Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecene base succinate etc. Among them lauryl succinate is preferred, which is described in European patent application 86200690.5/0,200,263 published on November 5, 1986.

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

Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids may also be added to the composition alone or with the above-mentioned builders, especially citrate and/or succinate builders, to provide additional builder activity . Such use of fatty acids will generally result in reduced foam and should be taken into account by the formulator.

In the case of phosphorus-based builders, particularly in bar formulations for handwashing operations, the various alkali metal phosphates such as the well known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can also be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, eg, US Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

Chelating Agents - The bleaching systems of the present invention may also optionally contain one or more iron and/or manganese chelating agents. The chelating agent may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof as defined below. Without wishing to be bound by theory, it is believed that the advantages of these materials are due in part to their unique ability to remove iron and manganese from wash solutions 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 suitable for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly the [S,S] isomer.

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or as an auxiliary builder together with, for example, insoluble builders such as zeolites, layered silicates, etc. agent.

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

Dye Transfer Inhibitors - The bleaching systems of the present invention may also contain one or more dye transfer inhibiting compounds for inhibiting the transfer of dissolved and suspended dyes from one fabric to another, in the case of fabrics involving colored fabrics This dye transfer phenomenon is encountered during washing and conditioning operations.

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 polyvinylimidazole or mixtures thereof. Examples of such dye transfer inhibitors are described in US Patent 5,707,950 and US Patent 5,707,951.

Other suitable dye transfer inhibiting agents include, but are not limited to, crosslinked polymers. Cross-linked polymers are polymers whose backbone has a certain degree of cross-linking; these cross-links can be chemical or physical connections, and can be connected by active groups on the backbone or branch chains. Crosslinked polymers are described in the Journal of Polymer Science, Vol. 22, pp. 1035-1039.

In one embodiment, the cross-linked polymer is made in such a way as to form a three-dimensional rigid structure, the cross-linked polymer traps the dye in the pores formed by 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.

Addition of the polymer can also enhance the performance of the enzymes in the bleaching system of the present invention.

These dye transfer inhibitors are capable of complexing or adsorbing fade-sensitive dyes eluted from colored fabrics before they can bind to other articles in the wash liquor.

When present in the bleaching system of the present invention, the dye transfer inhibiting agent is present in an amount of from about 0.0001%, more preferably from about 0.01%, most preferably from about 0.05% to about 10%, more preferably from about 0.05% by weight of the bleaching system. Preferably to about 2%, most preferably to about 1%.

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

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

Especially copolymers of acrylate and methacrylate such as 480N having a molecular weight of 4000 can be incorporated into the detergent compositions of the present invention in an amount of 0.5-20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptizer compound having a lime soap dispersibility value (LSDP) of no greater than 8, preferably no greater than 7, most preferably no greater than 6, as defined below. The calcium soap peptizer compound is preferably present in an amount of 0 to 20% by weight.

The effectiveness of lime soap peptizers is quantified by the lime soap dispersing power (LSDP), which is determined using the lime soap dispersant test described in HC Borghetty and CA Bergman in J.Am.Oil.Chem.Soc., pp. 27 Vol. 88-90 (1950) in the article. Calcium soap dispersion tests are commonly used by those skilled in the art, see for example the following review articles: WN Linfield, Surfactant science Series, Vol. 7, p. 3; WN Linfield, Tenside surf.det., Vol. 27, 159-163 (1990); and MK Nagarajan, WF Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989). LSDP is the required dispersant and the weight percentage of sodium oleate for dispersing calcium soap deposits, said calcium soap deposits are 333ppm CaCO ₃ (Ca: Mg=3: 2) equivalent by 0.025g sodium oleate in 30ml Formed in hard water.

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

Examples of surfactants suitable for use herein with a LSDP of not greater than 8 include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C ₁₈ alkyl ethoxy sulfates having an average degree of ethoxylation of 1-5 , in particular C ₁₂ -C ₁₅ alkyl ethoxy sulfate surfactants with a degree of ethoxylation of 3 (LSDP=4), and average ethoxylated sulfate surfactants sold by BASF GmbH under the trademarks Lutensol A012 and Lutensol A030, respectively. C ₁₄ -C ₁₅ ethoxylated alcohols with a degree of hydration of 12 (LSDP=6) or 30.

Polymeric calcium soap peptizers suitable for use in the present invention are described in the article by M.K. Nagarajan, W.F. Masler in Cosmetics and Toiletries, 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 in combination with hydrophilic/hydrophobic bleach formulations are also useful as lime soap peptizing compounds.

Enzymes - In addition to the amylases of the present invention, the bleaching system may contain one or more detergent enzymes for cleaning and/or fabric care. Such enzymes may include proteases, amylases, cellulases and lipases. They may be added to the non-aqueous liquid bleaching systems of the present invention in the form of suspensions, "pellets" or "granules". Another suitable enzyme includes enzymes in slurry form in non-ionic surfactants, such as those sold by Novo Nordisk under the trademark "SL" or microencapsulated enzymes sold by Novo Nordisk under the trademark "LDP." Suitable enzymes and their amounts are described in US Patent 5,576,282.

Enzymes in the form of traditional enzyme granules added to the compositions of the present invention are particularly preferred for use in the present invention. Such particles typically range in size from about 100-1,000 microns, more preferably from about 200-800 microns, and are suspended throughout the non-aqueous aqueous liquid phase of the composition. It has been found that the enzyme granules in the compositions of the invention have a particularly desirable enzyme stability compared to other forms of enzymes in terms of maintaining enzyme activity for extended periods of time. Thus, compositions using enzyme granules need not contain conventional enzyme stabilizers, such as are typically necessary when enzymes are added to aqueous liquid detergents.

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratinases, Reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tanninase, pentosanase, malanase, β-glucanase, arabinoside Enzymes, hyaluronidases, chondroitinases, laccases, known amylases, mannanases, xyloglucanases and mixtures thereof. A preferred combination is a bleaching system comprising a mixture of conventionally used enzymes such as proteases, lipases, cutinases, and/or cellulases in combination with the amylases of the invention.

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

A suitable protease is subtilisin, which is obtained from special strains of Bacillus subtilis and Bacillus licheniformis (subtilisin BPN and BPN'). A suitable protease is the protease obtained from a Bacillus strain having maximal activity throughout the pH range 8-12 developed by Novo Industries A/S of Denmark, hereinafter referred to as "Novo" and marketed as ESPERASE( ^R) . The preparation of this and analogous enzymes is described in British Patent 1,243,784 to Novo. Other suitable proteases include ^ALCALASE® , ^DURAZYM® and ^SAVINASE® sold by Novo and ^MAXATASE® , ^MAXACAL® , ^PROPERASE® and ^MAXAPEM® (Maxacal for Designer Proteins) sold by Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in European Patent Application Serial No. 87 303 761.8 filed on April 28, 1987 (see in particular pages 17, 24 and 98) referred to herein as "Protease B" and those proteases referred to as modified bacterial serine proteases in European Patent Application 199,404 of the Venegas application published on October 29, 1986, referred to herein as "Protease A". More preferred is the protease referred to in the present application as "Protease C", which is a variant of alkaline serine protease obtained from Bacillus, wherein lysine is substituted for arginine at position 27 and tyrosine is substituted for 104 valine, serine replaces asparagine at position 123, and alanine replaces threonine at position 274. Protease C is described in EP90915958:4 corresponding to WO91/06637 published on May 16, 1991. Genetically modified variants, particularly of Protease C, are also included. See also the high pH protease produced by 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 WO92/03529A to Novo. When desired, proteases with reduced adsorption and increased hydrolysis can be obtained as described in WO 95/07791 to Procter & Gamble. Recombinant trypsin-like proteases suitable for use in the detergents of the present invention are described in WO 94/25583 to Novo.

In more detail, the protease known as "Protease D" is a carbonyl hydrolase variant with an amino acid sequence not found in nature, which is derived by substituting different amino acids for many amino acid residues in the precursor carbonyl hydrolase Yes, the substituted position is the +76 position of the carbonyl hydrolase, and it is also preferably combined with one or more amino acid residue positions selected from the positions corresponding to: +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. The numbered positions here correspond to the positions of Bacillus amyloliquefaciens subtilisin, which is described in WO 95/10615, published April 20, 1995, filed by Genencor International. Also suitable for use in the present invention are the proteases described in patent applications EP251446 and WO91/06637 and the protease BLAP ^(R) described in WO91/02792. The amount of protease added to the bleaching system 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 the following published PCT applications: WO95/30010, published Nov. 9, 1995, filed by Procter & Gamble Company; WO95/30011, published Nov. 9, 1995, filed by Procter & Gamble Company; published Nov. 9, 1995, filed by Procter & Gamble Company WO95/29979.

Other particularly useful proteases are protease variants with multiple substitutions comprising substitution of an amino acid residue corresponding to position 103 of Bacillus amyloliquefaciens subtilisin with another naturally occurring amino acid residue, simultaneously with another naturally occurring The resulting amino acid residues are substituted at one or more of the amino acid residues corresponding to the following positions of Bacillus amyloliquefaciens subtilisin: 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 ,246,247,248,249,251,252,253,254,255,256,257,258,259,260,261,262,263,265,268,269,270,271,272,274 and 275 ; wherein, when the protease variant comprises substitutions at amino acid residues corresponding to positions 103 and 76, there are also amino acid residues corresponding to positions 27, 99, 101, 104, 107, 109, 123 of Bacillus amyloliquefaciens subtilase , 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 amino acid residue positions at one or more amino acid residue positions, and/or multiple substitutions Protease variants comprising amino acid residues at positions corresponding to one or more of amino acid residue positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliquefaciens subtilisin with another naturally occurring amino acid residue Substitution with radicals is described in PCT Published Applications WO99/20727, WO99/20726 and WO99/20723 belonging to the Procter & Gamble Company.

More preferred protease variants include combinations of substitutions selected from the group consisting of:

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 preferred protease variants comprise combinations of substitutions selected from the group consisting of:

    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/23E/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/245A/248D/252K;

68A/103A/104I/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/104I/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 preferred protease variants comprise combinations of substitutions selected from the group consisting of: 101/103/104/159/232/236/245/248/252, preferably 101G/103A/104I/159D/232V/236H/245R/ 248D/252K.

Cellulases suitable for use in the present invention include bacterial or fungal cellulases. The optimum pH range for these cellulases is preferably 5-9.5. Suitable cellulases are disclosed in US Patent 4,435,307 to Barbesgoard et al., which discloses fungal cellulases produced by Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by Humicola grisea var. thermoidea strains, in particular Humicola grisea strain DSM1800.

Other suitable cellulases are cellulases produced by Humicola insolens having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids; Endoglucanase of ~ 43kD of Sulfase activity; The preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO91/17243. Suitable cellulases are also the EGIII cellulases obtained from Trichoderma longibrachiatum, which are described in WO 94/21801, Genencor, published September 29, 1994. Particularly suitable cellulases are cellulases with a color-preserving effect. Examples of such cellulases are those described in European Patent Application 91202879.2 (Novo) filed on November 6, 1991. Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitable. See also WO91/17243.

Peroxidases are well known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Bleaching systems containing peroxidases are disclosed in patents such as US Patents 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO89/099813, WO89/09813 and European Patent Application EP91202882.6 filed on November 6, 1991 and February 20, 1996 Application EP96870013.8. Also suitable are laccases.

Preferred synergists are substituted phenothiazines and phenoxazines, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO94/12621) and substituted syringyl esters (C3-C5 substituted alkyl syringyl esters) and phenol. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.

Said peroxidase levels added to the bleaching system are typically 0.0001% to 2% active enzyme by weight of the bleaching system.

Other preferred enzymes that may be included in the bleaching system of the present invention include lipases. Lipases suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154 disclosed in British Patent 1,372,034. Suitable lipases include those for which antibodies to lipases produced by the microorganism Pseudomonas fluorescens IAM1057 show a positive immunological cross-reactivity. This lipase is commercially available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan under the trademark Lipase P "Amano" (hereinafter referred to as "Amano P"). Other suitable commercially available lipases include Amano-CES, a lipase obtained from Chromobacter viscosum, such as Chromobacter viscosum variant lipolyticum NRRLB 3673 obtained from Toyo Jozo Co., Takata-gun, Japan; And Chromobacterium viscous lipase from USBiochemical Corp. of the United States and Disoynth Co. of the Netherlands and lipase from Pseudomonas gladioli. Particularly suitable lipases are lipases such as 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.

Suitable enzymes are also cutinases [EC 3.1.1.50], which are considered a special class of lipases, ie lipases that do not require interfacial activation. The addition of cutinases to bleaching systems has been described eg in WO 88/09367 (Genencor).

Lipase and/or cutinase are generally added in the bleaching system in an amount of 0.0001%-2% active enzyme by weight of the bleaching system.

Known amylases may be included (alpha and/or beta) for removal of carbohydrate based stains. Cleaning compositions incorporating mutant amylases are described in WO 94/02597, Novo Nordisk A/S, published 3 February 1994. See also WO 94/18314 to Genencor published 18 August 1994 and WO 95/10603 to Novo Nordisk A/S published 20 April 1995. Other known amylases for use in bleaching systems include alpha- and beta-amylases. Alpha-amylases are well known in the art and include those disclosed in US Patent 5,003,257; EP 252,666; WO91/00353; FR 2,676,456; EP 285,123; Amylase in. Other suitable amylases are stability-enhanced amylases including PURAFACT OX ^AM® as described in WO94/18314 published on August 18, 1994 and WO96/05295 of Genencor published on February 22, 1996, and WO95 published on April 1995. Amylase variants disclosed in /10603 commercially available from Novo Nordisk A/S.

Examples of commercially available alpha-amylase products are ^TERMAMYL® , ^BAN® , ^FUNGAMYL® and ^DURAMYL® all commercially available from Novo Nordisk A/S Denmark. Other suitable amylases are described in WO95/26397: α-amylases ^{characterized} by having a ratio of The activity is at least 25% higher than the specific activity of TERMAMYL ^(R) . Other amylases with improved properties with respect to activity levels and thermostability combined with higher activity levels are described in WO95/35382.

Compositions of the invention may also comprise a mannanase. The mannanase is preferably selected from the following three mannanolytic enzymes: EC 3.2.1.25: β-mannosidase, hereinafter referred to as "mannanase" EC 3.2.1.78: endo-1,4-β - Mannosidases and EC 3.2.1.100: 1,4-β-mannobiotic glycosidases and mixtures thereof (IUPAC Classification - Enzyme Nomenclature, 1992 ISBN 0-12-227165-3 Academic Press).

When a mannanase is present in the treatment composition of the invention, it more preferably comprises a beta-1,4-mannosidase (E.C. 3.2.1.78) known as mannanase. The term "mannanase" or "galactomannanase" denotes a mannanase according to the official definition in the prior art, which is known as endomannan-1,4-β-mannosidase, also May be referred to as β-mannanase and endo-1,4-mannanase, and catalyze 1,4- Random hydrolysis of β-D-mannosidic linkages.

Specifically, mannanases (EC 3.2.1.78) consist of a group of polysaccharases that degrade mannan and represent enzymes capable of cleaving polysaccharide chains containing Enzyme of glycosidic bonds in lactomannan, glucomannan and galactoglucomannan. Mannans are polysaccharides with a backbone consisting of β-1,4-linked mannose; glucomannans are polysaccharides with a backbone of more or less isotactic β-1,4-linked mannose and glucose ; Galactomannans and galactoglucomannans are mannans and galactomannans with alpha-1,6 linked galactose side chains. These compounds can be acetylated.

Degradation of galactomannan and galactoglucomannan can be facilitated by complete or partial removal of galactose side chains. In addition, the degradation of acetylated mannan, glucomannan, galactomannan, and galactoglucomannan can be facilitated by complete or partial deacetylation. Acetyl groups can be removed with alkali or mannan acetylesterase. The oligomers released by mannanase or by a mixture of mannanase and α-galactosidase and/or mannan acetylesterase can be further degraded to remove from β-mannosidase and/or β- Free maltose is released in glucosidase.

Mannanases have been identified in several Bacillus species. For example, Talbot et al., Appl. Environ. Microbiol., Vol. 56, No. 11, pp. 3505-3510 (1990) describe a dimeric form of β-mannanase from Bacillus stearothermophilus , which has a molecular weight of 162 kDa and an optimal pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) describe a molecular weight of 38 kDa obtained from Bacillus subtilis with optimal activity at pH 5.0 and 55°C and a β-mannanase with a pI of 4.8. JP-03047076 discloses a β-mannanase obtained from the genus Bacillus having 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 preparation of alkaline, thermostable β-mannanases which hydrolyze β-1,4-D-mannopyranosidic linkages such as mannans to produce mannooligosaccharides. JP-63036774 relates to Bacillus microorganism FERM P-8856, which produces β-mannanase and β-mannosidase at alkaline pH. Alkaline β-mannanase obtained from alkaliphilic Bacillus sp. AM001 is disclosed in JP-08051975. A pure mannanase from Bacillus amyloliquefaciens for bleaching pulp and paper and its preparation is disclosed in WO97/11164. WO 91/18974 describes a hemicellulase, such as a dextranase, xylanase or mannanase, which is active at extreme pH and temperature. Enzymes having mannanase activity obtained from Aspergillus aculeatus, CBS 101.43, are disclosed in WO 94/25576 and are useful for degrading or modifying plant or algal cell wall materials. Mannanase isolated from Trichoderma reseei for bleaching lignocellulosic pulp is disclosed in WO93/24622. Hemicellulases capable of degrading mannan-containing hemicelluloses are described in WO 91/18974 and pure mannanases obtained from Bacillus amyloliquefaciens are described in WO 97/11164.

The mannanase is preferably an alkaline mannanase as defined below, more preferably a mannanase obtained from bacterial origin. The laundry detergent compositions of the present invention particularly comprise an alkaline mannanase selected from the group consisting of mannanases obtained from strain Bacillus agaradhaerens NICMB 40482; those obtained from Bacillus subtilis strain 168, gene yght Mannanase; a mannanase obtained from Bacillus sp. 1633 and/or a mannanase obtained from Bacillus sp. AAI12. The most preferred mannanase for inclusion in the detergent compositions of the present invention is the mannanase produced by Bacillus sp. 1633, which is described in co-pending Danish patent application with application number 1998 01340.

The term "alkaline mannanase" refers to an enzyme comprising at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity in a given pH range of 7-12, preferably 7.5-10.5 .

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

i) a polypeptide prepared by Bacillus agaradhaerens, NCIMB 40482; 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 has at least 70% similarity to said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or to Polyclonal antibodies raised against the polypeptide in purified form are immunoreactive.

The invention also includes a corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide having mannanase activity, said polypeptide comprising nucleotide 97-nucleotide in SEQ ID NO: 1 as shown in U.S. Patent Application Serial No. 09/111,256 the nucleotide sequence shown at 1029;

(b) a homologue of (a);

(c) a polynucleotide molecule encoding an amino acid having mannanase activity identical to amino acid residue 32 to amino acid residue 343 of SEQ ID NO: 2 as shown in U.S. Patent Application Serial No. 09/111,256 Polypeptides with at least 70% identical sequence;

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

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

The plasmid pSJ1678 containing the polynucleotide molecule (DNA sequence) encoding the mannanase was transformed into an Escherichia coli strain, which was deposited by the inventors of the present invention on May 18, 1998 for the purpose of patent procedure according to the Budapest International Convention on the Deposit of Microorganisms. It was deposited at Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, under the accession number DSM 12180.

A second more preferred enzyme is the mannanase derived from Bacillus sp. strain 168 described in co-pending US Patent Application Serial No. 09/095,163. More specifically, the mannanase is:

i) encoded by the coding portion of a DNA sequence as shown in SED ID No. 5 or an analog of said sequence given in U.S. Patent Application Serial No. 09/095,163; and/or

ii) a polypeptide comprising the amino acid sequence shown in SEQ ID No. 6 as given in U.S. Patent Application Serial No. 09/095,163; or

iii) analogues of the polypeptides defined in ii), which have at least 70% similarity to said polypeptides, or are derived from said polypeptides by substitution, deletion or addition of one or more amino acids, or in relatively purified form Polyclonal antibodies raised against the polypeptides are immunoreactive.

The invention also includes a corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide having mannanase activity, said polypeptide containing the nucleotide sequence shown in SEQ ID NO: 5 as given in U.S. Patent Application Serial No. 09/095,163 ;

(b) a homologue of (a);

(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 as set forth in U.S. Patent Application Serial No. 09/095,163;

(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 Danish patent application with application number 1998 01340. More specifically, the mannanase is:

i) a polypeptide produced by Bacillus sp. I633;

ii) a polypeptide comprising an amino acid sequence as shown in positions 33-340 of SEQ ID NO: 2 as given in Danish Patent Application No. 1998 01340; or

iii) an analogue of the polypeptide defined in i) or ii), which has at least 65% similarity to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or to Polyclonal antibodies raised against the polypeptide in purified form are immunoreactive.

The invention also includes corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide having mannanase activity, said polypeptide comprising nucleotide 317-nucleotide 1243 in SEQ ID NO: 1 as given in Danish patent application with application number 1998 01340 the nucleotide sequence shown;

(b) a homologue of (a);

(c) a polynucleotide molecule encoding the amino acid sequence from amino acid residue 33 to amino acid residue 340 in SEQ ID NO: 2, having mannanase activity, as given in Danish Patent Application No. 1998 01340 at least 65% identical polypeptides;

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

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

The plasmid pBXM3 containing the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention was transformed into an Escherichia coli strain, which was deposited in May 1998 for the purpose of patent procedure by the inventors of the present invention according to the Budapest International Convention on the Deposit of Microorganisms. Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany was deposited on 29th April under the accession number DSM 12197.

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

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

ii) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of SEQ ID NO: 2 as given in Danish Patent Application No. 1998 01341; or

iii) an analogue of the polypeptide defined in i) or ii), which has at least 65% similarity to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or to Polyclonal antibodies raised against the polypeptide in purified form are immunoreactive.

The invention also includes corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide with mannanase activity, the following polypeptide contains nucleotides 225-1236 in SEQ ID NO: 1 as provided in Danish patent application with application number 1998 01341 the nucleotide sequence shown;

(b) a homologue of (a);

(c) a polynucleotide molecule encoding the amino acid sequence from amino acid residue 25 to amino acid residue 362 of SEQ ID NO: 2, having mannanase activity, as given in Danish Patent Application No. 1998 01341 at least 65% identical polypeptides;

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

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

The plasmid pBXM containing the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention was transformed into an Escherichia coli strain, which was deposited on October 1998 for the purpose of patent procedure by the inventors of the present invention according to the Budapest International Convention on the Deposit of Microorganisms. Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, deposited on 7th July, the accession number is DSM 12433.

Mannanase, if present, is preferably added to the treatment compositions of the invention at a level of 0.0001% to 2%, more preferably 0.0005% to 0.1%, most preferably 0.001% to 0.02% pure enzyme by weight of the composition .

The compositions of the invention may also comprise xyloglucanase. The xyloglucanase suitable for use in the present invention is an enzyme that exhibits endoglucanase activity specific to xyloglucan, and its amount is preferably about 0.001% to about 1% by weight of the composition, more preferably about 0.01% to about 0.5%. The term "endoglucanase activity" as used in this application means that the enzyme hydrolyzes the enzyme present in any cellulosic material such as cellulose, cellulose derivatives, lichenan, β-D-glucan or xyloglucan The ability of 1,4-β-D-glycosidic linkages in Endoglucanase activity can be determined according to methods known in the art, some examples of which are described in WO94/14953 et seq. One unit of endoglucanase activity (such as CMCU, AVIU, XGU or BGU) is defined as the production of 1 μmol reducing sugar/min from a dextran matrix such as CMC (CMCU), acid-swellable Crystalline cellulose (AVIU), xyloglucan (XGU) or grain beta-glucan (BGU). Reducing sugars were determined as described in WO94/14953 and hereinafter. The specific activity of the endoglucanase on the substrate is defined as units/mg protein.

A suitable enzyme exhibits at its maximal activity an XGU endoglucanase activity (hereinafter referred to as "specific to xyloglucan") which:

i) is encoded by a DNA sequence comprised or included 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) TTAACATCTT TTCACCATGA (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) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15 )(p)CAACATCCCC GGTGTTCTGG G(SEQ ID NO：16)(q)AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCCAGCCGACCGATTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTTTCCGTTCTCTCCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTGCGGTCAGTGGGATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGAGACGGCCGGCACCGGCTCCC AGTGCACTGG AGTCGACTCC TACACCGGCG ACACCATCGCTTGTCACACCAGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG(SEQ IDNO：17)or( r)CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTGCGTGGCGGAGGCTGCCGGGA  GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCGTGTTTCAGTCCCTAGGCAGG  ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCAGGAGACGCTGTATAGGGGAT  AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGTCCTGTACATACAATGCATAT  ACCAATTATA CCTACCAAAA AAAAAAAAAAA AAAAAAAAAA AAAA(SEQ ID NO：18)或编码对木葡聚糖有特异的内切葡聚糖酶活性的多肽homologous sequence,

ii) The antibodies produced by the highly purified endoglucanase encoded by the DNA sequence defined in i) and obtained from Aspergillus aculeatus, CBS 101.43 are immunoreactive and specific for xyloglucan.

More specifically, the term "specific to xyloglucan" used in this application means that the endoglucanase exhibits its maximum endoglucanase activity on xyloglucan matrix, while on other Cellulose-containing matrices such as carboxymethylcellulose, cellulose or other dextrans exhibit preferably less than 75% activity, more preferably less than 50% activity, most preferably less than about 25% activity.

The specificity of the endoglucanase to xyloglucan is preferably further defined as the relative activity, which is measured as the amount of reducing sugar released by incubating the enzyme under optimal conditions with xyloglucan and the other substrate tested, respectively. For example, specificity can be defined as the activity of xyloglucan relative to β-glucan (XGU/BGU), the activity of xyloglucan relative to carboxymethylcellulose (XGU/CMCU), or the activity of xyloglucan The value is preferably greater than about 50, such as 75, 90 or 100 relative to the activity of acid-swellable microcrystalline cellulose (XGU/AVIU).

The term "obtained from" used in the application not only refers to the endoglucanase produced by bacterial strain CBS 101.43, but also refers to the DNA sequence coding isolated from bacterial strain CBS 101.43 and is translated with said DNA sequence endoglucanases produced in host organisms. The term "homologue" as used in this application refers to a polypeptide encoded by DNA that hybridizes to the same probe under certain specified conditions (such as pre-soaked in 5xSSC, and 5xSSC at -40°C, 5x Denhardt's solution and 50 μg of denatured sonicated bovine thymus DNA were prehybridized for 1 hour, then hybridized at -40°C for 18 hours in the same solution supplemented with 50 μCi 32-P-dCTP-labeled probe and incubated at 40°C, 2xSSC, 0.2% SDS, washed three times for 30 minutes) as the DNA code for endoglucanase specific to xyloglucan. More specifically, the term means a DNA sequence that is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific to xyloglucan, including any sequence shown above. The sequences are at least 75%, at least 80%, at least 85%, at least 90% or even at least 95% homologous. The term is intended to include modifications to 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 correspond to the introduction of a DNA structure comprising any of the aforementioned DNA sequences. Codon usage by the host organism, or nucleotide substitutions that result in a different amino acid sequence and thus possibly a different amino acid sequence and thus possibly a different protein structure, which may produce an endonuclease with different properties from the original enzyme Glucanase mutants. Other examples of possible modifications are insertion of one or more nucleotides into the sequence, addition of one or more nucleotides at one end of the sequence, or deletion of one or more nucleotides at one end of the sequence or within the sequence.

The endoglucanase specific for xyloglucan suitable for use in the present invention preferably has an XGU/BGU, XGU/CMU and/or XGU/AVIU ratio (as defined above) greater than 50, such as 75, 90 or 100 An endoglucanase.

In addition, when the endoglucanase specific to xyloglucan is 100% active on xyloglucan, it is preferably substantially inactive on β-glucan and/or on carboxymethylcellulose and/or Or the microcrystalline cellulose exhibits up to 25%, such as up to 10% or about 5%, of the activity. Furthermore, the endoglucanase specific for xyloglucan of the present invention is preferably substantially free of the transferase activity which has been observed for most endoglucanases specific for xyloglucan of plant origin .

Endoglucanases specific for xyloglucans can be obtained from the mold species Aspergillus aculeatus as described in WO 94/14953. A microbial endoglucanase specific for xyloglucan is also described in 94/14953. Endoglucanases specific to plant-derived xyloglucans have also been described, but these enzymes have transferase activity and are therefore considered secondary to xyloglucan whenever complete degradation of xyloglucan is required. Dextran-specific microbial endoglucanase. Another advantage of microbial enzymes is that they are generally produced in higher amounts in microbial hosts than enzymes from other sources.

If present, xyloglucanase is preferably added to the treatment composition of the invention in an amount of 0.0001% to 2%, more preferably 0.0005% to 0.1%, most preferably 0.001% to 0.02% pure by weight of the composition. enzyme.

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

The enzyme is generally added in the bleaching system in an amount of 0.0001%-2% active enzyme by weight of the bleaching system. The enzyme can be added as a separate single ingredient (pellet, granule, stabilized liquid, etc. containing one enzyme) or as a mixture of two or more enzymes (eg composite granules).

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

A class of enzymatic substances and their incorporation into synthetic bleaching systems are also disclosed in WO 93/07263 and WO 93/07260 issued to Genencor International; WO 89/08694 issued to Novo; and McCarty issued January 5, 1971. US Patent 3,553,139 to et al. Some enzymes are also disclosed in US Patent 4,101,457, Place et al., issued July 18, 1978, and US Patent 4,507,219, Hughes, issued March 26, 1985. Enzyme materials suitable for use in liquid detergent formulations and methods for their incorporation into such formulations are disclosed in US Patent 4,261,868, issued 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 Patent 3,600,319, issued August 17, 1971 to Gedge et al., EP 199,405, and EP 200,586, issued October 29, 1986, to Venegas. Enzyme stabilization systems are also described, eg, in US Patent No. 3,519,570. Useful Bacillus sp. AC13 producing proteases, xylanases and cellulases is described in WO9401532 to Novo. The enzymes used in this application can be stabilized by the presence in the finished composition of a water-soluble source of calcium and/or magnesium ions capable of providing calcium and/or magnesium ions to the enzyme. Suitable enzyme stabilizers and their amounts are described in US Patent 5,576,282.

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

Laundry Methods - In addition to the laundering of fabrics, dishes and other hard surfaces and personal cleansing body parts described herein, the present invention also includes methods of laundry pretreatment of soiled fabrics which involve washing with conventional aqueous wash solutions Highly concentrated forms of the above bleaching systems are used prior to fabric contact with the stain and/or soiled spot directly. Preferably, the bleach system is left in contact with the stain/spot for about 30 seconds to 24 hours before washing the pretreated soiled substrate in a conventional manner. More preferably, the pretreatment time ranges from about 1 to 180 minutes.

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

Some abbreviations known to those skilled in the art are used in the following embodiments, which are consistent with the disclosure content of the present application.

Example I

Bleaching detergent compositions in the form of granular laundry detergents are exemplified by the following formulations.

A B C D E Organic Catalyst* 0.034 0.06 0.03 0.10 0.05 Traditional activation agent (NOBS) 2.00 2.80 2.00 1.80 5.30 Traditional activation agent (TAED) 0.00 0.00 0.60 0.00 Sodium of sodium carbonate 5.30 0.00.00 0.00 sodium 0.00.00 5.30 3.60 4.30 Linear Alkyl Benzene Sulfonate 12.00 0.00 12.00 0.00 21.00C45AE0.6S 0.00 15.00 0.00 15.00 0.00C2 N-Dimethylamine Oxide 0.00 2.00 0.00 2.00 0.00C12 Cocamidopropyl Alkaline Palm 1.50 0.00 0.00 0 1 -Netic opium 1.70 2.00 1.70 2.00 0.00---C12 diodes hydroxyl chloride 1.50 0.00 1.50 0.00 0.00 ammonium AE23-6.5T 2.50 3.50 3.50 1.00C25E3S 4.00 0.00 0.00 0.00 Sodium 25.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.005.00 25.00 Acrylic/maleic acid copolymer 0.00 0.00 0.00 0.00 1.00 Polyacrylic acid, partially neutralized 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 0.00 0.00 2.00酸钠3.00 3.00 3.00 3.00 6.00碳酸氢钠5.00 5.00 5.00 5.00 5.00Savinase(4T) 1.00 1.00 1.00 1.00 0.60Termamyl(60T) 0.40 0.40 0.40 0.40 0.40Lipolase(100T) 0.12 0.12 0.12 0.12 0.12Carezyme(5T) 0.15 0.15 0.15 0.15 0.15 diethylenetriaminepenta 1.60 1.60 1.60 1.60 0.40 (methylene phosphonic acid) brightener 0.20 0.20 0.20 0.05 0.20 sulfonated zinc phthalocyanine photosensitized bleaching 0.50 0.00 0.25 0.00 0.00 agent MgSO ₄ 2.20 2.20 42Na0 2.20 2.6 _2SO4 balance balance balance balance *organic _catalyst can be any zwitterionic organic catalyst described in this application, preferably iminium based organic catalyst, more preferably dihydroisoquinolinium based organic catalyst catalyst.

Any of the above compositions can be used to wash fabrics. When washing, its concentration in water at 25° C. is 3500 ppm, and the water:clothes ratio is 15:1. The pH is generally about 9.5, however, the pH can be adjusted by changing the ratio of the acid and the alkylbenzene sulfonate in the sodium salt form.

Example II

Bleaching detergent compositions in the form of granular laundry detergents are exemplified by the following formulations.

A B C D E Organic Catalyst* 0.009 0.04 0.14 0.14 0.002 Traditional activated agent (NOBS) 1.80 0.00 0.00 1.00 1.00 Traditional activation agent (TAED) 0.00 1.00 2.50 0.00 sodium carbonate 5.30 0.00 0.00 0.00 sodium sodium 0.00 9.00 17.60 9.60 9.09.60 9.00 Linear Alkylbenzene Sulfonate 21.00 12.00 0.00 12.00 12.00C45AE0.6S 0.00 0.00 15.00 0.00 0.00C2 N-Dimethylamine Oxide 0.00 0.00 2.00 0.00 0.00C12 Cocamidopropyl Alkaline 50.00 1.50 1.50 1 N-Methyldextran 0.00 1.70 2.00 1.70 1.70 Amide C12 Dimethyl Hydroxyethyl Chloride 1.00 1.50 0.00 1.50 1.50 Ammonium AE23-6.5T 0.00 2.50 3.50 2.50 2.50C25E3S 0.00 4.00 0.004 5.00 Sodium Triphosphate 5.00 25.00 15.00 15.00 polyacryonic acid, partially and 0.00 3.00 3.00 3.00 3.00 3.00 0.50 0.0 0.50 0.50 0.00.40 0.40 0.40 0.40 sodium carbonate 0.00 2.00 2.00 Sodium siliconate 6.00 3.00 3.00 3.00 sodium hydrogenate sodium hydrogen. 2.00 5.00 5.00 5.00 5.00Savinase(4T) 0.60 1.00 1.00 1.00 1.00Termamyl(60T) 0.40 0.40 0.40 0.40 0.40Lipolase(100T) 0.12 0.12 0.12 0.12 0.12Carezyme(5T) 0.15 0.15 0.15 0.15 0.15二亚乙基三胺五0.40 0.00 1.60 0.00 0.00 (methylene phosphonic acid) brightener 0.20 0.30 0.20 0.30 0.30 sulfonated zinc phthalocyanine photosensitized bleaching 0.25 0.00 0.00 0.00 0.00 MgSO ₄ 0.64 0.00 2.20 0.00 0.00Na ₂ SO ₄ balance balance balance balance Quantitative balance * The organic catalyst can be any zwitterionic organic catalyst described in this application, preferably an iminium-based organic catalyst, more preferably a dihydroisoquinolinium-based organic catalyst.

Any of the above compositions can be used to wash fabrics. When washing, its concentration in water at 25° C. is 3500 ppm, and the water:clothes ratio is 15:1. The pH is generally about 9.5, however, the pH can be adjusted by changing the ratio of the acid and the alkylbenzene sulfonate in the sodium salt form.

Example III

A bleaching detergent powder of the present invention contains the following ingredients: ingredient WT % organic catalyst*0.01Nobs 2.0 Teta -water sodium borate 10c12 linear alkyl sulfonate 8 phosphate (sodium trimer phosphate) 9 sodium carbonate 20 20 Yunmu 15 whitening agent, spice 0.3 sodium chloride 25 water and secondary substances to 100 %*Organic catalyst can be an arbitrarily dual -sex ion organic catalyst described in this application. It is a dihydroisoquinolinium-based organic catalyst.

Example IV

A laundry bar suitable for hand-washing soiled fabrics was prepared by standard extrusion and comprised the following ingredients: Component Wt % Organic Catalyst* 0.02 NOBS 1.7 TAED 0.2 Sodium Perborate Tetrahydrate 12C12 Linear Alkyl Benzene Sulfonate 30 Phosphate (sodium tripolyphosphate) 10 sodium carbonate 5 sodium pyrophosphate 7 coconut oil monoethanolamide 2 zeolite A (0.1-10 micron) 5 carboxymethyl cellulose 0.2 polyacrylate (molecular weight: 1400) 0.2 brightener , fragrance 0.2 protease 0.3CaSO ₄ 1MgSO ₄ 1 water 4 filler ² balance to 100% *The organic catalyst can be any zwitterionic organic catalyst described in this application, preferably an iminium-based organic catalyst, more preferably a dihydroiso Quinolinium-based organic catalysts. ² can be selected from readily available materials such as CaCO ₃ , mica, clay, silicates and the like. Acidic fillers can be used to lower the pH.

Example V

Use standard legal system to prepare a laundry and washing agent composition for machine washing. This composition includes the following components: ingredient WT % Organic Catalyst*0.3TAed 10.0 Sodium Sodium Borate 9.2 Sodium Carbonate 23.74 Activant Surface activity 14.80 aluminum silicate salt 21.30 Silicate 1.85 Tysteroid Trone Trone Trone 0.43 Polyacrylate 2.72 Plague 0.23 Polyetal Disterol Solid 1.05 Sulfate 8.21 Spice 0.10 Mixture 0.10 mixed object 0.43 Water measurement*Organic catalyst can be this application The arbitrary zwitterionic organic catalyst is preferably an iminium-based organic catalyst, more preferably a dihydroisoquinolinium-based organic catalyst.

The composition can be used to wash fabrics. When washing, its concentration in a solution at 20-40° C. is about 1000 ppm, and the ratio of water to fabric is about 20:1.

Example VI ingredients WT % Organic Catalyst*0.082Nobs 7.20 Teta -water Sodium Borate 8.0 sodium carbonate 21.0 Activation Activant 12.0 Aluminum Silicate 18.0 Trone Trone Aitate 0.3 Non -ionic Surface activity 0.5 Polyacryonic acid 2.0 increase increase White agent 0.3 sulfate 17.0 spice 0.25 mixed objects 2.95 water measurement*organic catalyst can be an arbitrarily bipolar ion organic catalyst described in this application. organic catalyst.

The composition can be used as an assistant for washing fabrics. When used, its concentration in a solution at 5-50° C. is about 850 ppm, and the ratio of water and fabrics is about 20:1.

Example VII

There is a formula for bleaching combinations suitable for high foam phosphate -like: ingredients A (WT %) B (WT %) organic catalyst*0.02 0.018nobs 1.90 2.00 Sodium boron sodium 2.25 3.00 carbonate 13.00 13.00 Octobic surface activity surface activity Agent 19.00 19.00 Odor surfactant 0.60 0.60 non-ionic surfactant-0.40 sodium trimer 22.50 22.50 Trinamine triaine 0.90 0.90 acrylic/macar acid cluster 0.90 0.90 carboxyl cellulose 0.40 protease 0.70 0.70 amylase 0.36 0.36 cellulose enzyme 0.35 0.35 white whitening agent 0.16 0.18 magnesium sulfate 0.70 0.70 water 3.0 1.0 sodium sulfate measurement and measurement*Organic catalyst can be an arbitrarily double -sex organic catalyst described in this application. based organic catalysts, more preferably dihydroisoquinolinium based organic catalysts.

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 can be made therein without departing from the spirit and scope of the invention. These modifications are within the scope of the invention protected by the appended claims.

The formulator can choose any suitable method for preparing the compositions of the present invention, 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;

In addition to the above examples, the bleaching systems of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are described in US Patent Nos. 5,679,630; 5,565,145; 5,478,489; 5,470,507;

Although the present invention has been described 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 to the present invention without departing from the scope of the present invention. The present invention should not be limited to what is described in the specification.

Sequence Listing <110> Procter & Gamble Company (The Procter & Gamble Company)

R.R. Dykstra (Dykstra, Robert)

P.J. Kellett (Kellett, Patti) <120> Color-protecting washing method using zwitterionic formulation components <130>7758M<150>60/151,174<151>1999-08-27<160>18<170>PatentIn version 3.0 <210> 1 <211> 21 <212> DNA <213> Aspergillus Aculeatus <400> 1ATTCATTTGT GGACAGGA C 21 <210> 211> 20 <212> DNA <213> Aspergillus Aculeatus) <400> 2GTTGATCGCA CATTGACCA 20 <210> 3 <211> 20 <212> DNA <213> Aspergillus Aculeatus <400> 3acccccccccgattc 20 <211> 20 <212> DNA <213> DNA <213> > Aspergillus Aculeatus <400> 4CTTCCCCCCCCCATCAT 20 <210> 5 <211> 20 <212> DNA <213> Aspergillus Aculeatus <400> 5TTACACACACACACACACACATGA 20 <211> 62111111111111111111111110> 6211110> 621111111110> 62111111110> 621111111110> 6 <210> 621111110> 62111110> 6211111> 62111 <212>DNA<213>棘孢曲霉(Aspergillus aculeatus)<400>6agctttccct tctctccctt                                                        20<210>7<211>28<212>DNA<213>棘孢曲霉(Aspergillus aculeatus)<400>7gccaccctgg cttccgctgc cagcctcc                                               28< 210> 8 <211> 20 <212> DNA <213> Aspergillus Aculeatus <400> 8GACAGTAGCA ATCCAGCATT 20 <210> 9 <211> 20 <212> DNA <213> Aspergillus Aculeatus <) 400> 9AGCATCAGCC GCTTTTGTACA 20 <210> 10 <211> 20 <212> DNA <213> Aspergillus Aculeatus <400> 10ccatgaagtttttg 20 <210> 11 <212> 20 <213> spiny spine spine spine spine spine spine spine spiny spiny spine曲霉(Aspergillus aculeatus)<400>11gcactgcttc tctcccaggt                                                        20<210>12<211>20<212>DNA<213>棘孢曲霉(Aspergillus aculeatus)<400>12gtgggcggcc cctcaggcaa                                                        20<210>13<211>20<212> DNA <213> Aspergillus Aculeatus <400> 13ACGCTCCCC AATTTTTCTCT 20 <210> 14 <211> 19 <212> DNA <213> Aspergillus Aculeatus) 211> 20 <212> DNA <213> Aspergillus Aculeatus <400> 15GGCGCAGGT TTGGCCAGC 20 <210> 16 <211> 21 <212> DNA <213> Aspergillus Aculeatus <400> 16CACCACCACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACCACACACACACACACACACACACCACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACACCA g                                                       21<210>17<211>347<212>DNA<213>棘孢曲霉(Aspergillus aculeatus)<400>17aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga    60ttgtccttcc ttacctcacc atcatttaac atcttttcac catgaagctt tcccttctct    120cccttgccac cctggcttcc gctgccagcc tccagcgccg cacacttctg cggtcagtgg    180gataccgcca ccgccggtga cttcaccctg tacaacgacc tttggggcga gacggccggc    240accggctccc agtgcactgg agtcgactcc tacagcggcg acaccatcgc ttgtcacacc    300agcaggtcct ggtcggagta gcagcagcgt caagagctat gccaacg                  347<210>18<211>294<212>DNA<213>棘孢曲霉(Aspergillus aculeatus)<400>18cagcatctcc attgagtaat cacgttggtg ttcggtggcc cgccgtgttg cgtggcggag    60gctgccggga gacgggtggg ggtggtggtg ggagagaatg tagggcgccg tgtttcagtc 120cctaggcagg ataccggaaa accgtgtggt aggaggttta taggtttcca ggagacgctg    180tataggggat aaatgagatt gaatggtggc cacactcaaa ccaaccaggt cctgtacata    240caatgcatat accaattata cctaccaaaa aaaaaaaaaa aaaaaaaaaa aaaa          294

Claims (25)

1. A bleaching system for laundering fabrics in need of cleaning comprising from about 0.001 ppm to about 5 ppm of a zwitterionic organic catalyst compound selected from the group consisting of: a) An aryliminium zwitterion having a net charge of about +3 to about -3, the aryliminium zwitterion is represented by the following formula [II]:

Wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, Nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula:

Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; b) An oxaziridinium zwitterion having a net charge of about +3 to about -3 is represented by the following formula [IV]:

wherein R ^5' -R ^7' are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silane radical, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula: Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1,2 or 3; T' _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; and c) mixtures thereof. 2. The bleaching system according to claim 1, wherein said bleaching system further comprises from about 2.0 ppm to about 1200 ppm of one or more peroxygen sources. 3. The bleaching system according to claim 1, wherein said bleaching system further comprises from about 0.5 ppm to about 300 ppm of one or more peracids. 4. The bleaching system according to claim 1, wherein said bleaching system further comprises from about 1.0 ppm to about 600 ppm of one or more peroxygen compounds. 5. The bleaching system according to claim 2, wherein said source of peroxygen is selected from the group consisting of: (a) prefabricated peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof; (b) a source of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof; and bleach activators. 6. The bleaching system according to claim 1, wherein said zwitterionic organic catalyst compound is present in a concentration of from about 0.01 ppm to about 3 ppm. 7. A bleaching system according to Claim 6 wherein said zwitterionic organic catalyst compound is present in a concentration of from about 0.1 ppm to about 2 ppm. 8. A bleaching system according to Claim 7 wherein said zwitterionic organic catalyst compound is present in a concentration of from about 0.2 ppm to about 1 ppm. 9. The bleaching system according to claim 1, wherein said zwitterionic organic catalyst compound is selected from the group consisting of: a) Aryliminium zwitterions having an electrostatic charge of from about +3 to about -3, represented by the formula [XII]: Wherein, when G exists, m is 1-3, when G does not exist, m is 1-4; n is an integer of 0-4; ^each R is independently selected from substituted or unsubstituted groups, these groups The group is selected from H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and alkoxy Carbonyl, and any two adjacent ^R26 substituents can be combined to form a fused aryl, fused carbocycle or fused heterocycle; ^R25 can be a substituted or unsubstituted group selected from H, Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; in There is also a group represented by the following formula in this formula:

Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from the following groups: Wherein q is an integer of 1-8; R ²⁹ are independently selected from substituted or unsubstituted groups selected from linear or branched H, alkyl, cycloalkyl, alkaryl, aryl, aryl Alkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido; G is selected from: (1)-O-; (2)-N(R ³⁰ )-; and (3) -N(R ³⁰ R ³¹ )-; R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ are substituted or unsubstituted groups independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl radical, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido; any of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ One can be combined with any other of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ to form a part of an ordinary ring; any twin R ²⁷ -R ²⁸ can be combined to form a carbonyl; any phase The adjacent R ²⁷ -R ³¹ can be combined to form an unsaturated part; and any one of the substituents R ²⁷ -R ³¹ can be combined to form a substituted or unsubstituted fused unsaturated part; b) Oxaziridinium zwitterions having a net charge of about +3 to about -3, represented by the following formula [XIV]:

Wherein, when G exists, m is 1-3, and when G does not exist, m is 1-4; n is an integer of 0-4; each R ^26' is independently selected from substituted or unsubstituted groups, these Groups selected from H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and alkane Oxycarbonyl, and any two adjacent R ^26' substituents can combine to form a fused aryl, fused carbocycle or fused heterocycle; R ^25' can be a substituted or unsubstituted group selected from From H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and alkoxy Carbonyl; a group represented by the formula: Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1 or 2 ; T' _o is selected from the following groups: Wherein q is an integer of 1-8; R ^29' are independently selected from substituted or unsubstituted groups, these groups are selected from linear or branched H, alkyl, cycloalkyl, alkaryl, aryl , aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido; G is selected from: (1)-O-; (2)-N(R ^30' )-; and (3) -N(R ^30' R ^31' )-; R ^27' , R ^28' , R ^30' and R ^31' are substituted or unsubstituted groups independently selected from H, oxygen, Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbonyl, carboxyalkyl and amido; R ^25' , R ^26' , R ^27' , any one of R ^28' , R30' and R ^31' can be combined with any other one of R ^25' , R ^26' , R ^27' , R ^28' , R ³⁰ ' and R ^31' to form a common A part of the ring; any twin R ^27' -R ^28' can be combined to form a carbonyl; any adjacent R ^27' -R ^31' can be combined to form an unsaturated part; and wherein the substituents R ^27' -R ^31' Any of the groups of may combine to form a substituted or unsubstituted fused unsaturated moiety; and c) mixtures thereof. 10. The bleaching system according to claim 9, wherein said zwitterionic organic catalyst compound is an aryliminium zwitterion represented by formula [XII], wherein R ²⁵ is H or methyl, and R ²⁶ is independently selected from H, alkyl and alkoxy, and groups represented by the formula: Z _p ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- , and p is 1 or 2. 11. A bleaching system according to claim 10, wherein said zwitterionic organic catalyst compound is an aryliminium zwitterion represented by the formula [XII], wherein, for a group represented by the formula:

Z _p ^- is -CO ₂ ^- , -SO ₃ ^- or -OSO ₃ ^- , p is 1, and T _o is selected from the following groups:

Wherein q is an integer of 2-4; R ²⁹ are each independently selected from H, linear or branched C ₁ -C ₁₈ substituted or unsubstituted alkyl and aryl. 12. The bleaching system according to claim 1, wherein said bleaching system further comprises a surfactant. 13. The bleaching system according to claim 1, wherein said bleaching system further comprises an enzyme. 14. The bleaching system according to claim 1, wherein said bleaching system further comprises a chelating agent. 15. A bleaching system according to claim 2, wherein said bleaching system is present in said bleaching system in a molar ratio of said peroxygen source to said zwitterionic organic catalyst compound greater than 1:1. 16. A process for preparing the bleaching system of claim 1, comprising: a) providing a wash solution; and b) adding to said wash solution a bleaching composition comprising an amount of a zwitterionic organic catalyst compound selected from the group consisting of: i) Aryliminium zwitterions having a net charge of about +3 to about -3, represented by the following formula [II]: Wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, Nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula: Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; ii) an oxaziridinium zwitterion having a net charge of about +3 to about -3 represented by the following formula [IV]:

Wherein R ^5' -R ^7' are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silane radical, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula:

Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1,2 or 3; T' _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; and c) mixtures thereof; The resulting concentration of the zwitterionic organic catalyst compound in the wash solution is from about 0.001 ppm to about 5 ppm. 17. A method of laundering fabrics in need of cleaning, the method comprising contacting said fabrics with a laundry solution comprising the bleaching system of claim 1. 18. The method according to claim 17, wherein said fabric is a colored fabric. 19. The method according to claim 17, wherein said method is carried out in an automatic washing machine. 20. A bleaching system for washing fabrics in need of cleaning, comprising: a) a source of peroxygen; and b) Zwitterionic organic catalyst compounds selected from: i) Aryliminium zwitterions having a net charge of about +3 to about -3, represented by the following formula [II]:

Wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, Nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula:

Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; ii) an oxaziridinium zwitterion having a net charge of about +3 to about -3 represented by the following formula [IV]:

wherein R ^5' -R ^7' are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silane radical, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula: Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1,2 or 3; T' _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; and c) mixtures thereof; wherein said bleaching system is present in a molar ratio of said peroxygen source to said zwitterionic organic catalyst compound greater than 1:1. 21. A bleaching system according to Claim 20, wherein said bleaching system is present in said bleaching system in a molar ratio of said peroxygen source to said zwitterionic organic catalyst compound of from about 30,000:1 to about 10:1. 22. A bleaching system according to Claim 21 wherein said bleaching system is present in said bleaching system in a molar ratio of said peroxygen source to said zwitterionic organic catalyst compound of from about 10,000:1 to about 50:1. 23. A bleaching system according to Claim 22 wherein said peroxygen source is present in said bleaching system to said zwitterionic organic catalyst compound in a molar ratio of from about 5,000:1 to about 100:1. 24. A bleaching system according to Claim 23 wherein said bleaching system is present in said bleaching system in a molar ratio of said peroxygen source to said zwitterionic organic catalyst compound of from about 3,500:1 to about 150:1. 25. A bleaching system for laundering fabrics in need of cleaning, comprising: a) overacid; and b) Zwitterionic organic catalyst compounds selected from: i) Aryliminium zwitterions having a net charge of about +3 to about -3, represented by the following formula [II]: Wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, Nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula:

Wherein Z _p ^- forms a covalent bond with T _o , Z _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1, 2 or 3; T _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; ii) an oxaziridinium zwitterion having a net charge of about +3 to about -3 represented by the following formula [IV]: wherein R ^5' -R ^7' are independently selected from substituted or unsubstituted groups selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silane radical, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxyl and alkoxycarbonyl; groups represented by the formula are also present in this formula: Where Z′ _p ^- forms a covalent bond with T′ _o , Z′ _p ^- is selected from -CO ₂ ^- , -SO ₃ ^- , -OSO ₃ ^- , -SO ₂ ^- and -OSO ₂ ^- , p is 1,2 or 3; T' _o is selected from substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle; and c) mixtures thereof; wherein said bleaching system is present in said bleaching system in a molar ratio of said peracid to said zwitterionic organic catalyst compound greater than 1:1.