JP2003508581A - Controlled activation of prescription ingredients, compositions using the same and methods of washing - Google Patents

Abstract

  (57) [Summary] The present invention relates to a method for the controlled activation of formulation components, such as organic catalysts, in a cleaning solution. More particularly, the present invention relates to products and bleaching compositions containing such ingredients, and to methods of laundering using such ingredients.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a controlled method of activation of formulation ingredients, such as organocatalysts, in cleaning solutions.
thod for the controlled availability). More particularly, the present invention relates to products and bleaching compositions containing such ingredients, and laundry methods using such ingredients.

[0002] In recent years, oxygen bleaching agents are more and more being used in household and personal care products for facilitating the removal of stains and dirt. Bleach removes stains on those products,
It is particularly desirable for cleaning, whitening and bactericidal properties of lightly soiled fabrics and for dye transfer prevention. Oxygen bleaches are especially prevalent in laundry products such as detergents, automatic dishwashing products, and hard surface cleaners. However, oxygen bleaches are somewhat limited in their effectiveness. Common defects include fabric color damage and washer damage. Furthermore, oxygen bleaches tend to be very sensitive to temperature changes. For example, the lower the temperature of the solution using the oxygen bleach, the lower the bleaching effect. Efficient oxygen bleaching in solution typically requires temperatures above 60 ° C.

To solve the above temperature dependence, a group of compounds called “bleach activators” has been developed. Bleach activators, typically perhydrolyzable acyl compounds having a leaving-group such as oxybenzene sulfonate, react with reactive oxygen groups, typically hydrogen peroxide, or its anions. To form a more effective peroxyacid oxidant. The peroxyacid compound then oxidizes the stained or soiled substrate. However, bleach activators are also somewhat temperature dependent. Bleach activators are more effective at warm water temperatures of about 40 ° C to about 60 ° C. At water temperatures below about 40 ° C, peroxyacid compounds lose some of their bleaching efficacy.

US Pat. Nos. 5,360,568, 5,360,569 and 5,370,826 (all Madison
Attempts have been made to develop effective bleaching systems under low temperature water conditions, as described in et al.). However, the dihydroisoquinolinium bleach enhancers disclosed in these references, when combined with peroxygen compounds, cause undesired decomposition, especially in the presence of wash solution components.

US Pat. Nos. 5,576,282 and 5,817,614 (both Miracle et al.)
It further describes attempts to develop bleach systems comprising organic catalysts that are effective under cold water conditions and are color safe.

However, the prior art does not suggest or describe the delayed (controlled) addition of formulation ingredients according to the invention, such as organic catalysts.

From the above, researchers are seeking ways to suppress (or control) the degradation of the organocatalyst, especially prior to contact with oxidizing stains.

Therefore, organic catalysts and compositions containing organic catalysts that provide effective bleaching even at low water temperatures, improve stability against undesired organic catalyst decomposition, and provide maximum peracid performance early in the wash cycle. There is a need for an effective way to populate.

[0009]

[Outline of the Invention]

The present invention provides a method of introducing an organic catalyst, in particular a bleach-enhancing compound, a bleaching substance, a modified amine, a modified amine oxide, a sulfone imine, a phosphonimine, an N-acyl imine and / or a thiodiazole dioxide. To meet the demands of.

Examples of the advantages afforded by the organocatalyst loading method of the present invention include excellent bleaching effect even at low water temperatures, typically a pre-mixing step prior to adding the fabric to be washed (ie, the spotted fabric). In order to avoid decomposition of the organic catalyst that occurs during cleaning, and to maximize the concentration of peracid against stains on the fabric, peracid may be added to the stained fabrics that should be washed before adding the organic catalyst. Include, but are not limited to, allowing bleaching, and reducing the peracid concentration by bleaching, thereby reducing the rate of organocatalytic decomposition by excess peracid present in the wash solution. is not.

In one aspect of the invention, the organocatalyst, with or without a peroxygen source, is controlled by the controlled activation method defined by Test Methods I, II and / or III described below. And a method of laundering a fabric to be washed, which method comprises dosing a washing solution containing the fabric, preferably with a source of peroxygen.

In another aspect of the invention, the test methods I, II described below, when introduced into the wash solution with or without a peroxygen source, preferably with a peroxygen source. And / or a bleaching composition comprising an organic catalyst that is effective (chemically effective to interact with other compounds) by a controlled activation method defined by III and is capable of bleaching. I will provide a.

In yet another aspect of the present invention, Test Method I, described below, when dosed to the wash solution with or without a peroxygen source, preferably with a peroxygen source. Organocatalysts enabled by controlled activation methods defined by II and / or III (chemically effective to interact with other compounds) to effect bleaching in the form of dye transfer inhibition To provide a product comprising.

In yet another aspect of the present invention, Test Method I, described below, when dosed to the wash solution with or without a peroxygen source, preferably with a peroxygen source. A product comprising an organocatalyst that can be bleached by being activated (chemically effective to interact with other compounds) by a controlled activation method defined by II and / or III And further comprising instructions for washing the fabric to be washed with the organic catalyst, the instructions for use in which at least most of the organic catalyst is washed by the dosing means after adding the fabric to the washing solution. A certain amount of organic catalyst (with or without a peroxygen source) so that it is added to the solution
Provided is a product comprising the step of introducing the product comprising into a cleaning solution containing fabric.

Surprisingly, in a cleaning solution containing a source of peroxygen and a fabric to be cleaned, the controlled activation method defined by test methods I, II and / or III described below is effective The presence of an organic catalyst (which is chemically effective so that it interacts with other compounds) causes the organic catalyst which becomes effective (chemically effective so that it interacts with other compounds) to be washed instantaneously. It was found that the bleaching performance was enhanced compared to when in solution.

Controlling the effectiveness of the organocatalysts of the present invention in a wash solution containing a source of peroxygen and a fabric by a controlled activation method defined by Test Methods I, II and / or III described below. This allows the peroxygen source / peracid to be bleached early in the wash cycle, while its concentration is highest, while at the same time exposing the organocatalyst to the highest peroxygen source / peracid concentration. Can be avoided, thereby reducing the decomposition of the organic catalyst. Then, test methods I and II described below
The controlled activation method defined by and / or III can render the organic catalyst effective (chemically effective to interact with other compounds). When activated in the wash solution, the organocatalyst can react with the remaining available peracid to form an oxygen transfer agent (bleach) that can oxidize the stain. This allows the peroxygen source / peracid and the organic catalyst to be further advantageously utilized. Without being bound by theory, organocatalysts, especially bleach-enhancing compounds, react with peroxygen sources, preferably peracids, to form oxygen transfer agents (bleaches). Various degradation pathways can cause the degradation of bleach enhancing compounds or oxygen transfer agents to form degradation products that can also react with peroxygen sources / peracids.

Therefore, by controlling the effectiveness of the organocatalyst, and thereby the contact timing between the organocatalyst and the peroxygen source / peracid in the wash solution, the presence of such catalysts in the wash solution is controlled. A maximum peroxygen source / peracid can provide maximum bleaching for a particular stain on the fabric before it is contacted with the organic catalyst.

Under typical wash conditions, peracid reacts more slowly with the stain than the oxygen transfer agent, so that available oxygen is often present in the peracid form at the end of the wash cycle. At the end of the wash cycle, the available oxygen is low, which reduces the bleaching rate, wasting residual peracid after the wash is complete. In fact, as the wash cycle progresses, the concentration (after perhydrolysis is complete) begins to drop due to the peracid bleaching stains and stains. Bleaching with peracid is relatively slow (especially at low wash temperatures from a kinetic point of view) and requires long wash times and high peracid concentrations to increase stain removal efficiency. It is important and necessary to have a high peracid concentration for a particular oxidizable stain to allow the organic catalyst to act on all oxidizable stains. Peracids have been found to react rapidly with organic catalysts to form bleaching materials, which then react rapidly with oxidizable stains.

Therefore, an object of the present invention is to provide a test method that exhibits excellent performance even in a low temperature solution, reduces (suppresses) undesired decomposition, and maximizes the performance of peracid early in the cleaning cycle. By the controlled activation method defined by I, II and / or III,
A method of loading an organic catalyst, a controlled activation method defined by Test Methods I, II and / or III described below, to load a fabric containing washing solution with an organic catalyst to wash the fabric to be washed. Laundering method, test methods I and II described below
And / or a bleaching composition comprising an organocatalyst that can be activated by a controlled activation method defined by III, and a test method described below, which is added to a wash solution containing the fabric to be washed. It is to provide a product comprising an organic catalyst which can be activated by a controlled activation method defined by I, II and / or III. These and other objects, features and advantages of the invention will be apparent to those skilled in the art from the following description and claims.

All percentages, ratios and proportions are expressed by weight unless otherwise indicated. All references cited are included here for reference.

[0021]

[Detailed Description of the Invention]

The present invention provides a cleaning solution containing a fabric to be cleaned (ie, a fabric with stains / soils), by a controlled activation method defined by Test Methods I, II and / or III described below. Organic catalyst compounds, also called catalysts (“bleach enhancer compounds”, “bleaching substances”, “modified amines”, “modified amine oxides”, sulfonimines, phosphinimines, thiodiazole dioxides and mixtures thereof),
Discloses a new and very useful method for inputting

The controlled activation method for loading the organocatalyst of the present invention can enhance the bleaching effect and reduce (or suppress) undesired decomposition even in low temperature applications. As a result, the organocatalysts of the present invention and the method of using them very effectively reduce undesired decomposition, increase catalyst efficiency, improve bleaching effect and thus improve performance. Further, the organocatalysts of the present invention and methods of use thereof maximize peracid performance early in the wash cycle and improve overall performance. The controlled activation method defined by Test Methods I, II, and / or III, described below, allows the organic catalysts to be controlled in a controlled manner rather than all at once (the entire amount of organic catalyst is effective at one time). , Which can be chemically effective in interacting with other compounds in the wash solution.

Definitions "Effective" as used herein means chemically effective in interacting with another compound.

As used herein, “peroxygen source” means a material that produces peroxygen compounds,
The peroxygen compound itself can be included. Examples include, but are not limited to, bleach activators, peracids, percarbonates, perborates, hydrogen peroxide, bleach-enhancing compounds, and / or bleaching substances (eg oxaziridinium). Not a thing.

As used herein, “peroxygen compound” includes peracids and peroxides (eg hydrogen peroxide, alkyl hydroperoxides, etc.).

As used herein, “peracid” means a peroxyacid, such as peroxycarboxylic acid and / or peroxymonosulfate (trade name OXONE) and salts thereof.

The method of introducing the organic catalyst of the present invention acts in cooperation with or without an ordinary peroxygen bleaching source, preferably in cooperation with each other, to enhance the above-mentioned bleaching effect and to effect undesired decomposition. To reduce.

The organic catalyst compounds organic catalysts compounds such as bleach enhancing and bleaching agents, examples of U.S. Patent No. 5,04
1,232, 5,045,223, 5,047,163, 5,310,925, 5,413,733, 5
, 360,568, 5,482,515, 5,550,256, 5,360,569, 5,478,357,
No. 5,370,826, No. 5,442,066, No. 5,576,282, No. 5,760,222, No. 5,753,599
Nos. 5,652,207 and 5,817,614, published PCT patent application WO98 / 23602, WO
95/13352, WO95 / 13353, WO95 / 13351, WO97 / 06147 and WO98 / 23717,
And European Patent No. 728182, but is not limited thereto.

The organocatalyst compounds of the present invention and bleaching compositions (products) containing such organocatalyst compounds which are particularly useful in the method of the present invention are described in Test Methods I, II and / or III described below. It is an organic catalyst compound satisfying the conditions and a composition containing the compound.

Preferably, the organocatalytic compound of the present invention, more preferably the iminium-based organocatalytic compound of the present invention, comprises a bleach enhancer compound, a modified amine, a modified amine oxide, a sulfone imine, a phosphinimine, a thiodiazole dioxide. And mixtures thereof, but are not limited thereto.

I. Bleach-enhancing compound The bleach-enhancing compound of the present invention, preferably an iminium-based bleach-enhancing compound,
Examples include, but are not limited to, aryliminium cations having a net charge of about +3 to about -3, aryliminium polyions, and aryliminium zwitterions having a net charge of about +3 to about -3. Absent.

A preferred organocatalyst in the present invention and for the bleaching composition of the present invention is a bleach enhancer compound selected from the aryliminium zwitterionic system or its oxaziridinium bleaching material, which comprises This is because, unlike aryliminium cations and / or oxaziridinium cations, zwitterions effectively bleach without excessive damage to the fabric color.

A. Aryliminium Cations and Polyions Aryliminium cations and aryliminium polyions with a net charge of about +3 to about -3 are represented by Formula [I] below.

[Chemical 75] Wherein R ² and R ³ are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy. Selected from a group, substituted or unsubstituted, saturated or unsaturated group, R ¹ and R ⁴ are H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl A nitro, halo, cyano, alkoxy, keto and carboalkoxy group, substituted or unsubstituted, saturated or unsaturated group, X ⁻ is a suitable charge balance, preferably bleaching It is a counterion compatible with the agent, and v is an integer of 1 to 3.

Preferably, the aryliminium cations and aryliminium polyions having a net charge of about +3 to about −3 are represented by formula [XI] below.

[Chemical 76] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
And n is an integer of 0 to 4 and each R²⁰Are independently H, alkyl,
Low alkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo, cyclo
Ano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy
A group selected from the group consisting of substituted, unsubstituted, and substituted groups.
Selected, all two vic-R²⁰Substituents may be combined to form fused aryl, condensed
R carbocycles or fused heterocycles can be formed and R¹⁸Is H, alkyl,
Chloroalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro
, Halo, cyano, sulfonate, alkoxy, keto, carboxyl, and cal
Selected from the group consisting of dialkoxy groups, substituted or unsubstituted
R is good¹⁹Is substituted or unsubstituted, saturated or tired
Japanese, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl
And a group selected from the group consisting of heterocycles, G is (1) -O-, (2)-
N (R²³)-, And (3) -N (R²³R²⁴)-Selected from the group consisting of
, R²¹~ R²⁴Are independently H, oxygen, linear or branched C₁~ C_{1 Two} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
Cycloalkyl, and selected from the group consisting of heterocycles, substituted, or
An unsubstituted group, with the proviso that R is¹⁸, R¹⁹, R²⁰, R²¹~ R²⁴ Is all R¹⁸, R¹⁹, R²⁰, R²¹~ R²⁴Common by combining with any of
Can form part of a ring, all gem-R²¹~ R²²Are combined
Can form a carbonyl and all vic-R²¹~ R²⁴Are united
Unsaturation can be formed and the substituent R²¹~ R²⁴Throat groups are also combined
Substituted or unsubstituted fused unsaturated moieties can be formed and X ⁻ Is a suitable charge-balancing counterion, preferably a counterion that is compatible with the bleach.
It is on and v is an integer from 1 to 3.

More preferably, the aryliminium cations and aryliminium polyions having a net charge of about +3 to about -3 represented by formula [XI] have the formula [XI]:
R ¹⁸ is H or methyl and R ¹⁹ is H or a substituted or unsubstituted saturated or unsaturated C ₁ -C ₁₄ alkyl.

B. Aryliminium Zwitterion The aryliminium zwitterion having a net charge of about +3 to about -3 has the formula:
Represented by [II].

[Chemical 77] Wherein R ^{5 to} R ⁷ are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy. There is also a group selected from the group consisting of, selected from a substituted or unsubstituted group, which is represented by the formula:

[Chemical 78] Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is ^{_{-CO 2 -, -SO 3 -,}} -OS
Selected from the group consisting of O ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3 and T ₀ is a substituted or unsubstituted saturated or unsaturated alkyl. , Cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle.

Preferably, the aryliminium zwitterion with a net charge of about +3 to about −3 is represented by formula [XII] below.

[Chemical 79] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
And n is an integer of 0 to 4, each R ²⁶ is independently H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, alkoxy. , A keto, a carboxyl, and a carboalkoxy group, selected from a substituted or unsubstituted group, all two vic-R ²⁶ substituents are combined to form a fused aryl, fused Carbocycles or fused heterocycles can be formed and R ²⁵ is H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, And a carboalkoxy group, which may be a substituted or unsubstituted group, Also exists a group represented by the following formula,

[Chemical 80] Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is ^{_{-CO 2 -, -SO 3 -,}} -OS
Selected from the group consisting of O ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3, and T ₀ is

[Chemical 81] Is selected from the group consisting of: wherein q is an integer from 1 to 8;²⁹Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R^Thirty)-, And (3) -N (R^ThirtyR³¹) -Selected from the group consisting of ²⁷ , R²⁸, R^ThirtyAnd R³¹Are independently H, oxygen, alkyl, cyclo
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alco
Group consisting of xy, arylcarbonyl group, carboxyalkyl group and amido group
R is a substituted or unsubstituted group selected from R²⁵, R^{Two 6} , R²⁷, R²⁸, R^ThirtyAnd R³¹Is all R²⁵, R²⁶, R²⁷,
R²⁸, R^ThirtyAnd R³¹To form part of a common ring with any of
And all gem-R²⁷~ R²⁸Combine to form carbonyl
Can and all vic-R²⁷~ R³¹Can combine to form unsaturation
Yes, substituent R²⁷~ R³¹Substituted or combined with any group of
Uncondensed fused unsaturated moieties can be formed.

More preferably, the aryliminium zwitterion having a net charge of about +3 to about -3 represented by formula [XII] is a substance of formula [XII] wherein R ²⁵ is H or methyl, And expression

[Chemical formula 82] For the groups represented by, _{Z p} ^- is _-CO ² _-, ^-SO 3 -, -OSO ₃ ^- and is, p is 1 or 2, more preferably _{Z p} ^- is -SO ₃ ^- or -
It includes a substance that is OSO ₃ ⁻ and p is 1.

II. Modified Amines / Amine Oxide Compounds Modified amines and / or amine oxide compounds of the present invention include, but are not limited to, modified amines and amine oxides having a net charge of from about +3 to about -3.

A. Modified amine The modified amine is represented by the following formulas [V] and [VI].

[Chemical 83] In the formula, R ^{9 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl,
Selected from alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups and groups having anionic and / or cationic charges, substituted, or Selected from unsubstituted groups, R ⁸ and R ¹¹ , when present, are substituted or unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, A group selected from the group consisting of heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy groups and groups having anionic and / or cationic charges, R ¹² being a leaving group, protonated form pK _a value _{(H 2} O basis) 37> p
Within the range of K _a > −2, provided that all R ^{8 to} R ¹² , when present, can be combined to form a fused aryl, fused carbocycle or fused heterocycle, wherein: There are also groups represented by the formulas below.

[Chemical 84] Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is ^{_{-CO 2 -, -SO 3 -,}} -OS
Selected from the group consisting of O ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3 and T ₀ is a substituted or unsubstituted saturated or unsaturated alkyl. , Cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle.

[0041]   Preferably, the modified amine is represented by the following formulas [XV] and [XVI].

[Chemical 85] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
And n is an integer from 0 to 4, R ³⁴ is a substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl, percarboxyl, sulfonate, peroxy, A group selected from the group consisting of sulfonate groups, wherein each R ³⁵ is independently H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Selected from the group consisting of cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups, substituted or unsubstituted, all two vic-R ³⁵ substituents being combined. Condensed aryl,
Fused carbocycles or fused heterocycles may be formed, R ³² is H, alkyl,
Selected, substituted or unsubstituted, from the group consisting of cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups. R ³³ may be a group, R ³³ may be a substituted or unsubstituted, saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle. , In this formula, there is a group represented by the following formula,

[Chemical 86] Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is ^{_{-CO 2 -, -SO 3 -,}} -OS
Selected from the group consisting of O ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3, and T ₀ is

[Chemical 87] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R³⁹)-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of ³⁶ , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloalkyl
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
A group consisting of cis, arylcarbonyl group, carboxyalkyl group and amido group
R is a group selected from, substituted or unsubstituted, R³², R³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R ³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with either
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a group
Can be combined to form a carbonyl, all vic-R³⁶, R³⁷,
R³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R ³⁷ , R³⁹And R⁴⁰All of the groups are substituted or substituted.
Unfused fused unsaturated moieties can be formed.

Examples of such modified amines are those wherein R ³⁴ is substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl, percarboxyl, sulfonate and peroxy. Examples include, but are not limited to, modified amines selected from the group consisting of sulfonate groups.

Preferably, the R ³⁴ group is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups. The following examples illustrate such modified amines of the invention, but do not necessarily limit the scope of the invention.

[Chemical 88]

[0044]   More preferably, with respect to the modified amine represented by the formulas [XV] and [XVI], R
³⁴Is a leaving group and its protonated form is pK_aValue (H_TwoO standard) is 3
0> pK_a> 0, more preferably 23> pK_a> 3, more preferably 21> p
K_a> 9, most preferably 17> pK_aIt falls within the range of> 11.

Preferably, with respect to the modified amine represented by the formulas [XV] and [XVI], R ¹²
Is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups.
More preferably, with respect to the modified amine represented by the formulas [XV] and [XVI], R ^1
2 is selected from the group consisting of hydroxy or perhydroxy.

Further preferred modified amines represented by formulas [XV] and [XVI] have a net charge of about +1 to about -1, R ³² is H or Me, and R ³⁴ is hydroxy and peroxy. A group selected from the group consisting of hydroxy groups, wherein R ³⁵ is independently selected from the group consisting of H, alkyl, nitro, halo, sulfonate, alkoxy, carboxyl and carboalkoxy groups, and / or Z _p ^- is -C
O ₂ ^-, -SO ₃ ^- or -OSO ₃ ^- modified amines is.

With respect to the modified amine, R ¹² is a leaving group (LG) and its protonated form has a pKa value (H ₂ O basis) of 37> pK _a > -2, preferably 30> pK _a > 0. , More preferably 23> pK _a > 3, and even more preferably 17> pK _a > 11.
Most preferably R ¹² is a leaving group consisting of a substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy group, R ^{8 to} R ^{8 12} can be combined to form a fused aryl, fused carbocycle or fused heterocycle.

B. Modified amine oxide The modified amine oxide of the present invention is represented by the following formulas [VII] to [X].

[Chemical 89] In the formula, R ^{8 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl,
Selected from alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups and groups having anionic and / or cationic charges, substituted, or Selected from unsubstituted groups, R ¹¹ is a substituted or unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, A group selected from halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups and groups having anionic and / or cationic charges, R ¹² is a leaving group and its protonated form the pK _a value _{(H 2} O basis) 37> in the range of _pK a> -2 Where R ^{8 to} R ¹² , when present, can be combined to form a fused aryl, fused carbocycle or fused heterocycle, which also includes groups represented by the formulas Exists.

[Chemical 90] Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is ^{_{-CO 2 -, -SO 3 -,}} -OS
Selected from the group consisting of O ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3 and T ₀ is a substituted or unsubstituted saturated or unsaturated alkyl. , Cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle.

[0049]   Preferably, for the modified amine oxide represented by the formulas [VII] to [X], R^{1 Two} Is a leaving group and its protonated form is pK_aValue (H_TwoO standard) is 30
> PK_a> 0, more preferably 23> pK_a> 3, more preferably 21> pK _a > 9, most preferably 17> pK_aIt falls within the range of> 11.

[0050] Preferably, for the modified amine oxides represented by the formula [VII] ~ [X], R 1 2 is, has been or unsubstituted, substituted, saturated or unsaturated hydroxy,
It is selected from the group consisting of perhydroxy, alkoxy and peralkoxy groups. More preferably, with respect to the modified amine oxide represented by the formulas [VII] to [X],
R ¹² is selected from the group consisting of hydroxy or perhydroxy.

Further, preferably, the modified amine oxide is also represented by the following formulas [XVII] to [XX].

[0052]

[Chemical Formula 91]

[Chemical Formula 92] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
And n is an integer from 0 to 4, R ³⁴ is a substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl, percarboxyl, sulfonate, peroxy, A group selected from the group consisting of sulfonate groups, wherein each R ³⁵ is independently H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Selected from the group consisting of cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups, substituted or unsubstituted, all two vic-R ³⁵ substituents being combined. Condensed aryl,
Fused carbocycles or fused heterocycles may be formed, R ³² is H, alkyl,
Selected, substituted or unsubstituted, from the group consisting of cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups. R ³³ may be a group, R ³³ may be a substituted or unsubstituted, saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle. , In this formula, there is a group represented by the following formula,

[Chemical formula 93] Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is ^{_{-CO 2 -, -SO 3 -,}} -OS
Selected from the group consisting of O ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3, and T ₀ is

[Chemical 94] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R³⁹)-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of ³⁶ , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloalkyl
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
A group consisting of cis, arylcarbonyl group, carboxyalkyl group and amido group
R is a group selected from, substituted or unsubstituted, R³², R³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R ³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with either
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a group
Can be combined to form a carbonyl, all vic-R³⁶, R³⁷,
R³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R ³⁷ , R³⁹And R⁴⁰All of the groups are substituted or substituted.
Unfused fused unsaturated moieties can be formed.

Examples of such modified amine oxides are those where R ³⁴ is substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl, percarboxyl, sulfonate and Examples include, but are not limited to, modified amine oxides selected from the group consisting of persulphonate groups.

Preferably, the R ³⁴ group is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups.

[Chemical 95]

[0055] More preferably, with respect to modified amine oxides represented by the formula [XVII] and [XX], R ³⁴ is a leaving group, the protonated form pK _a value (H 2 _O basis) 30 > PK _a > 0, more preferably 23> pK _a > 3, even more preferably 21> pK _a > 9, and most preferably 17> pK _a > 11.

Preferably, for the modified amines represented by formulas [XVII]-[XX], R ³⁴ is
It is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups. More preferably, with respect to modified amine oxides represented by the formula [XVII] ~ [XX], R 3 4 is selected from the group consisting of hydroxy or perhydroxy.

[0057]   More preferred modified amine oxides represented by the formulas [XVII] and [XX] are
, The net charge is about +1 to about -1, and R³²Is H or Me, and R³⁴But hi
A group selected from the group consisting of droxy and perhydroxy groups, R³⁵But
, Independently, H, alkyl, nitro, halo, sulfonate, alkoxy, carboxy
Selected from the group consisting of sil and carboalkoxy groups, and / or Z_p ⁻ Is -CO_Two ⁻, -SO_Three ⁻Or -OSO_Three ⁻The modified amine oxide which is
You can

[0058]   With regard to modified amine oxides, R¹²Is a leaving group (LG) and its proton
The modified form is pK_aValue (H_TwoO standard) is 37> pK_a> -2, preferably 30
> PK_a> 0, more preferably 23> pK_a> 3, more preferably 17> pK _a > 11, most preferably R¹²Is or has been replaced
Unsaturated, saturated or unsaturated hydroxy, perhydroxy, alkoxy or
And a leaving group consisting of a peralkoxy group, R⁸~ R¹²Are combined and curtailed
Combined aryls, fused carbocycles or fused heterocycles can be formed.

[0059] Examples of suitable modified amine compounds of the present invention (modified amine and / or modified amine oxides) (and protonated form of the pK _a values of ^{R 12} _{(H 2} O reference)) is

[Chemical 96]

[Chemical 97] However, the present invention is not limited to these.

The modified amine compounds of the present invention work in conjunction with a peroxygen source to provide a more effective bleaching system. Sources of peroxygen are well known in the art and sources of peroxygen for use in the present invention include peroxygen compounds as well as compounds that form an effective amount of peroxygen in situ under the conditions used by the consumer. Can comprise any of these well known sources, including: The peroxygen source includes a hydrogen peroxide source, an in situ formation of a peroxy acid anion resulting from the reaction of the hydrogen peroxide source with a bleach activator,
Preformed peracid compounds or suitable mixtures of peroxygen sources are mentioned. Of course, as will be appreciated by those skilled in the art, other sources of peroxygen may be used without departing from the scope of the present invention. Preferred are peroxygen source organic and / or inorganic peracids.

IV. Sulfonimine, Phosphonimine, N-Acylimine, Thiodiazoledimine
Oxide The sulfonimine, phosphonimine, N-acylimine and thiodiazole dioxide of the present invention are represented by the following formulas [XXIa], [XXIb], [XXII] and [XXIII], respectively.
Represented by

[Chemical 98] Wherein R ^{41 to} R ⁴⁴ , when present, are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, And a substituted or unsubstituted, saturated or unsaturated group selected from the group consisting of and carboalkoxy groups, with the proviso that R ^{41 to} R ⁴⁴ are all other R ^{41 to} R ^44. Can form a part of a common ring including a fused aryl, fused carbocycle or fused heterocycle.

II. Bleaching substances Bleaching substances (oxaziridinium, oxaziridine) can also be used directly according to the invention. The bleaching material of the present invention includes an oxaziridinium cation having a net charge of about +3 to about -3, an oxaziridinium polyion, and a net charge of about +3 to about -3.
An oxaziridinium zwitterion that is about -3, oxaziridine sulfonimine,
Examples include, but are not limited to, oxaziridine phosphonimine, oxaziridine thiodiazole dioxide, and mixtures thereof.

The organocatalysts, especially the aryliminium cations, aryliminium polyions, aryliminium zwitterions, sulfonimines, phosphinimines, thiodiazole dioxides of the present invention, act as a source of peroxygen (if present). It works together to enhance the bleaching effect. Without being bound by theory, the organocatalyst reacts with a source of peroxygen to give a more active bleaching agent, a quaternary oxaziridinium and / or oxaziridine compound, for example as represented by the following reaction: Form.

[Chemical 99] Oxaziridinium and / or oxaziridine compounds have higher or more favorable activity at lower temperatures as compared to peroxygen compounds.

A. Oxaziridinium cations and polyions Oxaziridinium cations and polyions with a net charge of about +3 to about -3 are represented by formula [III] below.

[Chemical 100] In the formula, R ^{2 ′ to} R ^{3 ′} are independently H, alkyl, cycloalkyl, aryl,
Selected from the group consisting of alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl and carboalkoxy groups, substituted or unsubstituted, R ^{1 ′} and R ^{4 ′} are substituted or unsubstituted, saturated or unsaturated,
Is a group selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy groups, and X ⁻ is a suitable charge balance. Is a counter ion compatible with the bleaching agent, and v is an integer of 1 to 3.

Preferably, the oxaziridinium cation and polyion having a net charge of about +3 to about −3 are represented by the following formula [XIII]:

[Chemical 101] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
And n is an integer of 0 to 4 and each R^{20 '}Are independently H, alkyl,
Chloroalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
From a substituted or unsubstituted group selected from the group consisting of xy groups
All 2 vic-Rs selected^{20 '}Substituents are combined and fused aryl
, Fused carbocycles or fused heterocycles can be formed, R^{18 '}Is H, Archi
Group, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl,
Nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
And carboalkoxy groups selected from the group consisting of, substituted or substituted
Not a group, R^{19 '}Is saturated, either substituted or unsubstituted.
Or unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, ara
Is a group selected from the group consisting of a rualkyl and a heterocycle, G is (1) -O-,
(2) -N (R^{23 '})-, And (3) -N (R^{23 '}R^{24 '})-Consists of
Selected from the group R^{21 '}~ R^{24 '}Are independently H, oxygen, linear or
Chain-shaped C₁~ C₁₂Alkyl, alkylene, alkoxy, aryl, alkali
Selected from the group consisting of aryl, aralkyl, cycloalkyl, and heterocycle,
A substituted or unsubstituted group, provided that R is^{18 '}, R^{19 '},
R^{21 '}~ R^{24 '}Is all R^{18 '}, R^{19 '}, R^{21 '}~ R^{24 '}Nozu
Can bind to it to form part of a common ring, and all gem-R^{21 '}~
R^{22 '}Can combine to form a carbonyl, and all vic-R
^{21 '}~ R^{24 '}Can combine to form unsaturation, the substituent R^{21 '}~ R ^{24 '} Any of the groups of the above may be combined and substituted or unsubstituted
Can form a summation moiety and have a substituent R^{21 '}~ R^{24 '}Any group of
To form fused unsaturated moieties that can be substituted or unsubstituted.
, X⁻Is compatible with a suitable charge-balancing counterion, preferably bleach
It is a counterion and v is an integer of 1 to 3.

More preferably, the oxaziridinium cation and the oxaziridinium polyion represented by formula [XIII] having a net charge of about +3 to about -3 are represented by formula [XIII]
, R ^{18 ′} is H or methyl, and R ^{19 ′} is H or a substituted or unsubstituted, saturated or unsaturated C ₁ -C ₁₄ alkyl and cycloalkyl.

B. Oxaziridinium Zwitterion The oxaziridinium zwitterion, which has a net charge of about +3 to about -3, has the formula:
Represented by [IV].

[Chemical 102] Wherein R ^{5 ′ to} R ^{7 ′} are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and There is also a group selected from the group consisting of carboalkoxy groups, selected from substituted or unsubstituted groups, of the formula:

[Chemical 103] In the formula, Z ′ _p ⁻ is covalently bonded to T ′ ₀ , Z ′ _p ⁻ is —CO ₂ ⁻ , —SO ₃ ⁻ ,
-OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, p is 1
2 or 3 and T ′ ₀ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle.

Preferably, the oxaziridinium zwitterion with a net charge of about +3 to about -3 is represented by formula [XIV] below.

[Chemical 104] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
And n is an integer from 0 to 4, and each R ^{26 ′} is independently H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Selected from the group consisting of a cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy group, substituted or unsubstituted, wherein all two vic-R ^{26 '} substituents are combined. To form a fused aryl, fused carbocycle or fused heterocycle, R ^{25 ′} is H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl,
It may be a substituted or unsubstituted group selected from the group consisting of nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl and carboalkoxy groups, the formula being represented by the formula: There is also a group,

[Chemical 105] In the formula, Z ′ _p ⁻ is covalently bonded to T ′ ₀ , Z ′ _p ⁻ is —CO ₂ ⁻ , —SO ₃ ⁻ ,
Selected from the group consisting of —OSO ₃ ^— , —SO ₂ ^— and —OSO ₂ ^— , and a is 1
Or 2 and T ′ ₀ is

[Chemical formula 106] Is selected from the group consisting of: wherein q is an integer from 1 to 8;^{29 '}Is independent
, Linear or branched, H, alkyl, cycloalkyl, alkali-
Ru, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbo
A substituted, selected from the group consisting of nyl, carboxyalkyl and amido groups.
Or a group not substituted, G is (1) -O-, (2) -N
(R^{30 '})-, And (3) -N (R^{30 '}R^{31 '})-Selected from the group consisting of
And R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Are independently H, oxygen,
Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene
, Heterocycles, alkoxy, arylcarbonyl groups, carboxyalkyl groups and
A substituted or unsubstituted group selected from the group consisting of
R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}All
And R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Nozu
Can bind to it to form part of a common ring, and all gem-R^{27 '}~
R^{28 '}Can combine to form a carbonyl, and all vic-R
^{27 '}~ R^{31 '}Can combine to form unsaturation, the substituent R^{27 '}~ R ^{31 '} Any of the groups of the above may be combined and substituted or unsubstituted
A sum part can be formed.

More preferably, the aryliminium zwitterion represented by formula [XIV] having a net charge of about +3 to about −3 is a substance of formula [XIV] wherein R ^{25 ′} is H or methyl. , And expressions

[Chemical formula 107] Of, Z _'p ^- is ^{_{-CO 2 -, -SO 3 -,}} -OSO 3 - and is, p is 1 or 2
Including substances that are

[0070] c) oxaziridine sulfonimines, Hosuhon'imin, N- Ashiruimin, Ji methiodide azole dioxide oxaziridine sulfonimines [XXIVa], Hosuhon'imin [XXIVb], N- Ashiruimin [XXV] and thio oxadiazole dioxide [XXVI] and [XXVII] are represented as follows.

[Chemical 108] Wherein R ^{41 ′ to} R ^{44 ′} , when present, are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, Selected from a substituted or unsubstituted group selected from the group consisting of carboxyl and carboalkoxy groups, provided that R ^{41 ′ to} R ^{44 ′} are all other R ^{41 ′ to} R ^{44 ′} Can form a part of a common ring including a fused aryl, fused carbocycle or fused heterocycle.

Suitable examples of X ⁻ , an anionic counterion include BF ₄ ⁻ , OTS ⁻ and other international patents WO97 / 06147, WO95 / 13352, WO95 / 13353, WO95 / 13351. , WO98
/ 23717, U.S. Pat.Nos. 5,360,568, 5,360,569, 5,482,515, 5,550,2
56, 5,478,357, 5,370,826, 5,442,066, European Patent 72818
2B1 and British Patent No. 1215656 include, but are not limited to, anionic counterions. The anionic counterion is preferably compatible with the bleaching agent.

[0072]   In all structures where there is no net charge, the compound has no counterion.

Suitable examples of X ⁺ , a cationic counterion for all structures with a negative net charge include, but are not limited to, Na ⁺ , K ⁺ , H ⁺ .

Suitable examples of anionic and cationic counterions for all structures with multiple net charges include, but are not limited to, those mentioned above.

Other Organocatalyst Compounds In addition to the bleach enhancer compounds, bleaching agents and modified amines and amine oxides disclosed above, the organocatalyst compounds react with peracids to form oxygen transfer agents (bleaches). It can be any compound known in the art that is capable of

Organocatalyst Compound Concentration The organocatalyst compound of the present invention is present in the wash solution at about 0.00001% by weight of the composition (
0.0001 ppm) to about 10% by weight (100 ppm), preferably about 0.0% of the composition.
001 wt% (0.001 ppm) to about 2 wt% (20 ppm), more preferably about 0
． 005 wt.% (0.05 ppm) to about 0.5 wt.% (5 ppm), more preferably about 0.01 wt.% (0.1 ppm) to about 0.2 wt.% (2 ppm), most preferably about 0. It can be added in an amount of from 02 wt% (0.2 ppm) to about 0.1 wt% (1 ppm).

Preferably, the bleaching composition of the present invention comprises an organocatalyst compound in an amount such that the concentration of bleach enhancer compound in the wash solution is from about 0.001 ppm to about 5 ppm. More preferably, the bleach composition of the present invention has a molar ratio of peroxygen compound to organocatalyst compound in the wash solution of greater than 1: 1, more preferably greater than 10: 1, even more preferably greater than 50: 1. It comprises in excess of the peroxygen compound (if present) and the organocatalyst compound. The preferred molar ratio range of peroxygen compound to organocatalyst compound is about 30,000: 1 to about 10: 1, more preferably about 10,000: 1 to about 50: 1, and more preferably about 5,000: 1. To about 100: 1, more preferably about 3,500: 1 to about 150: 1.

The converted value (ppm) is based on a product concentration of 1000 ppm when used for the purpose of illustration. A 1000 ppm wash solution of a product containing 0.2% by weight of an organocatalytic compound is
The organic catalyst compound concentration becomes 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2 wt% of an organocatalyst compound will give an organocatalyst compound concentration of 6.5 ppm.

The methods of introducing the organocatalyst compound of the invention and of the bleaching composition (product) containing such an organocatalyst compound, which are particularly effective in the method of the invention, define the structure here. Organocatalyst compounds and compositions containing the same satisfying a preferred method for bleaching a stained substrate in an aqueous medium using a peroxygen source and an organocatalyst compound, the medium comprising: Compound to about 0 per liter of medium
． 05-about 250 ppm active oxygen derived from peroxygen compounds, and 0.01 ppm
To about 5 ppm, preferably about 0.01 ppm to about 3 ppm, more preferably about 0.1 ppm to
Includes about 2 ppm, most preferably about 0.2 ppm to about 1 ppm of the organocatalytic compound.

Such a preferred method for bleaching a stained substrate in an aqueous medium using a source of peroxygen and an organocatalytic compound is a method of bleaching a stained substrate that needs to be washed. It is especially useful in applications where color safety is important. In such applications, the preferred embodiment (eg, 0.01 ppm to about 3 ppm) is particularly important in achieving reasonable color safety. In applications where the color safety of the stained substrate that needs to be cleaned is less important, higher concentrations at the time of use are preferred.

Degradation of Organocatalysts Organocatalysts, particularly the bleach-enhancing compounds of the present invention, are sensitive to degradation by a variety of degradation routes, including but not limited to aromatization routes. The aromatization (decomposition) reaction of 6-membered ring bleach-enhancing compounds is described in Hanquet et al., Tetrahedron 1993, 49.
, pp. 423-438 and described below, it is not bound by theory, but is well known in the art.

[Chemical 109]

Other means of decomposition include hydroxide anions, perhydroxides (per hydroxides) present under washing conditions.
hydroxide) against bleach-enhancing compounds and / or bleaches by nucleophiles, including but not limited to attack by anions, carboxylate anions, percarboxylate anions, and other nucleophiles Includes (but not limited to) attacks. For example, without being bound by theory, the decomposition reaction of a 6-membered ring oxaziridinium (the whole process of which may lead to a decrease in the bleaching effect) is represented as follows.

[Chemical 110]

Controlled Activation Method for Organocatalysts Surprisingly, in a wash solution containing a fabric, the controlled activation method defined by Test Methods I, II and / or III described below was used. It has been found that the organocatalysts provided have enhanced bleaching performance as compared to organocatalysts not provided by the controlled activation method defined by Test Methods I, II and / or III described below. .

By means of the controlled activation method defined by Test Methods I, II and / or III described below, all means and / or methods suitable for loading the organocatalysts of the present invention are provided by the present invention. Can be used by

Examples of input means and / or methods falling within the scope of the present invention are shown below, but are not limited thereto.

Dosing Means The dosing means of the present invention comprises a controlled activation method defined by Test Methods I, II and / or III described below so that the organic catalyst is effective in the wash solution, Any means that can control the effectiveness of the organocatalyst of the present invention can be used.

To a suitable dosing means is added a sustained release material comprising the organic catalyst of the present invention, for example capsule encapsulation or agglomerates or other sustained release materials, with test method I described below. The controlled release method defined by II and / or III comprises the controlled release material controlling the effectiveness of the organic catalyst such that the organic catalyst is effective in the wash solution, It is not limited to this. Preferably, the sustained release material is organocatalytic until the peroxygen source (if present) is released, preferably after the bleaching time has elapsed, and / or the fabric has been added to the wash solution. Control effectiveness.

Addition of Encapsulated Organic Catalyst As noted above, another suitable dosing means of the present invention is to provide the encapsulated organic catalyst with or without the detergent composition as a source of peroxygen (presence). ) Is added to the wash solution before or after it is added to the wash solution and / or before or after the fabric that needs to be washed is added to the wash solution. The encapsulated organocatalyst can include, but is not limited to, a bleaching composition comprising the organocatalyst of the present invention, wherein the peroxygen source (if present) is released, preferably The bleaching composition resists release of most of the amount of organic catalyst until after the bleaching time has elapsed and / or the fabric that needs to be washed has been added to the wash solution. For example, if the encapsulated organic catalyst is added to the wash solution before adding the fabric that needs to be washed to the wash solution, the encapsulated organic catalyst will not release the organic catalyst until after the fabric is added to the wash solution. resist. Typically, this time is from about 2 minutes, more preferably from 1 minute, more preferably from 1 second to about 10 minutes, preferably up to 7 minutes, more preferably up to 5 minutes. However, in rare cases this time can be up to 24 hours or more.

On the other hand, when the encapsulated organic catalyst is added to a wash solution that contains the fabric that needs to be washed, the encapsulated organic catalyst causes any peracid present in the wash solution to bleach the fabric. It is preferable to resist the release of the organic catalyst until after. Typically, this time is from about 2 minutes, more preferably from 1 minute, more preferably from 1 second to about 10 minutes, preferably up to 7 minutes, more preferably up to 5 minutes.

All suitable encapsulating materials known to those skilled in the art can be used. Examples of such suitable encapsulation materials for encapsulating the organic catalysts of the present invention include plastics such as thermoplastics, acrylonitrile, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and mixtures thereof, and And / or siliceous materials such as, but not limited to, glass. Commercially available microspheres are EXPANCEL from Expancel (Akzo Nobel) of Sweden.
PQ Corp. under the trade name of PM 6545, PM 6550, PM 7220, PM 7228, EXTENDOSPHER
Available under ES, LUXSIL, Q-CEL, SPHERICEL tradenames and from Malinckrodt under ALBUMEX tradenames.

Other suitable encapsulating materials include biopolymers such as starch, and polyethylene glycol and paraffin waxes described in US Patent No. 5,703,034, Offshack et al., Owned by The Procter & Gamble Company. To be

The encapsulated organic catalyst comprises one or more organic catalysts of the invention,
Optionally one or more of the following detergent ingredients: filler salts, surfactants, other bleaching agents, enzymes, preferably enzymes stable to bleaching agents, chelating agents, builders, dye transfer inhibitors. , Perfumes, fabric softening agents, soil release agents, and brighteners.

The preferred form of the encapsulated organic catalyst is a gel cap, but is not limited thereto.

Agglomerates Containing Organic Catalysts As mentioned above, still another preferred means of feeding the present invention is to use the agglomerates containing organic catalysts of the present invention in a washing solution with a peroxygen source (if present). Adding to the wash solution before, after, and / or after adding the fabric that needs to be washed to the wash solution. Agglomerated organocatalysts can include, but are not limited to, bleaching compositions that include the organocatalysts of the present invention, where the peroxygen source (if present) is released and preferably bleached. The bleaching composition resists release of most of the amount of organic catalyst until after a period of time has elapsed and / or after the fabric that needs to be washed has been added to the wash solution.

For example, if the agglomerates containing a certain amount of organic catalyst are added to the wash solution before the fabric that needs to be washed is added to the wash solution, the agglomerates will not be added until after the fabric is added to the wash solution. Resist the release of. Typically, this time is from about 2 minutes, more preferably from 1 minute, more preferably from 1 second to about 10 minutes, preferably 7 minutes.
Up to a minute, more preferably up to 5 minutes. However, in rare cases, this time is 2
It may take up to 4 hours or more.

On the other hand, if the agglomerates containing a certain amount of organic catalyst are added to the fabric solution that needs to be washed after adding the fabric that needs to be washed, the agglomerates are present in the wash solution. It is preferred that all the peracids that do resist the release of the organic catalyst until after all the stains on the fabric have been bleached. Typically, this time is from about 2 minutes, more preferably from 1 minute, more preferably from 1 second to about 10 minutes, preferably 7 minutes.
Up to a minute, more preferably up to 5 minutes.

All suitable agglomerate materials known to those skilled in the art can be used. Examples of suitable coalescing materials for agglomerating the organocatalysts of the present invention include solid, water-soluble, ionizable materials such as organic acids, salts of organic and inorganic acids, and mixtures thereof. However, the present invention is not limited to these. Examples of such agglomerates are both The Pr
It is described in U.S. Patent Nos. 5,540,855, Bailley et al. and 5,482,642, Agar et al., owned by Octer & Gamble Company.

The agglomerates containing organic catalysts comprise one or more organic catalysts of the invention and optionally one or more of the following detergent components: filler salts, surfactants, other bleaching agents,
Enzymes, preferably enzymes that are stable to bleach, chelating agents, builders,
Dye transfer inhibitors, fragrances, fabric softeners, soil release agents, and brighteners,
Can comprise.

Bleaching Compositions Comprising Organic Catalysts In addition to the encapsulation and agglomerates described above, the organic catalysts of the present invention, regardless of their form, can be used in other bleaching compositions with a peroxygen source. can do.
For example, organic catalysts can be used in laundry additive products.

The bleach-enhancing compounds of the present invention can be used in bleaching compositions with or without a peroxygen source, preferably with a peroxygen source. In the bleaching composition of the present invention, the peroxygen source is from about 0.1 (1 ppm) to about 60% by weight (600 ppm) of the composition.
), Preferably about 1 (10 ppm) to about 40% by weight (400 ppm) of the composition, the organocatalytic compound being about 0.00001 (0.0001) of the composition.
ppm) to about 10% by weight (100 ppm), preferably about 0.0001 (0.
001 ppm) to about 2% by weight (20 ppm), more preferably about 0.005 (0.05
ppm) to about 0.5% by weight (5 ppm), more preferably about 0.01 (0.1 ppm)
To about 0.2 wt% (2 ppm), most preferably about 0.02 (0.2 ppm) to about 0.02.
It can be present in an amount of 1% by weight (1 ppm).

The converted value (ppm) is based on a product concentration of 1000 ppm when used for the purpose of illustration. A 1000 ppm wash solution of a product containing 0.2% by weight of an organocatalytic compound is
The organic catalyst compound concentration becomes 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2 wt% of an organocatalyst compound will give an organocatalyst compound concentration of 6.5 ppm.

A preferred bleach-enhancing compound concentration is about 300 grams of bleach-enhancing compound molecular weight /
On a molar basis, preferably the bleach-enhancing compound has a molecular weight of about 150-10.
It may be 00 grams / mole and may be higher for oligomeric or polymeric bleach-enhancing compounds. For example, in the bleaching composition of the present invention, more preferably when the bleach enhancer compound is present from about 0.005 (0.05 ppm) to about 0.5% (5 ppm),
The molar (M) concentration of the bleach enhancer compound is 1.7 × 10 ⁻⁸ M to 1.7 × 10 ⁻⁵ M.
Is. When a high molecular weight organic catalyst compound is used in the bleaching composition of the present invention,
The preferred molarity does not change, but the preferred weight concentration (ppm) increases accordingly. For example, a bleach-enhancing compound having a molecular weight of about 600 grams / mole is about 0.0
More preferably from 1 (0.1 ppm) to about 1.0% (10 ppm). For oligomeric or polymeric bleach-enhancing compounds, the more preferred molarity is based on the monomeric units associated with the iminium or oxaziridinium active site.

Particularly effective in the method of the present invention, the method of introducing the organic catalyst compound of the present invention and the method of introducing the bleaching composition (product) containing such an organic catalyst compound have a structure defined herein. Organocatalyst compounds and compositions containing the same satisfying a preferred method for bleaching a stained substrate in an aqueous medium using a peroxygen source and an organocatalyst compound, the medium comprising: Compound to about 0 per liter of medium
． 05-about 250 ppm active oxygen derived from peroxygen compounds, and 0.01 ppm
To about 5 ppm, preferably about 0.01 ppm to about 3 ppm, more preferably about 0.1 ppm to
Includes about 2 ppm, most preferably about 0.2 ppm to about 1 ppm of the organocatalytic compound.

Such a preferred method for bleaching a stained substrate in an aqueous medium using a peroxygen source and an organocatalyst compound is a method of staining a substrate that needs to be washed. It is especially useful in applications where color safety is important. In such applications, the preferred embodiment (eg, 0.01 ppm to about 3 ppm) is particularly important in achieving reasonable color safety. In applications where the color safety of the stained substrate that needs to be cleaned is less important, higher concentrations at the time of use are preferred.

The organocatalysts of the present invention which are particularly useful in the bleaching compositions of the present invention are preferably organocatalysts by the controlled activation method defined by Test Methods I, II and / or III described below. Can be effective in a wash solution comprising a bleaching composition comprising.
The organocatalyst can be activated alone in the wash solution containing the organocatalyst by the controlled activation method defined by Test Methods I, II and / or III described below. Alternatively, a bleaching composition containing an organic catalyst can be effectively treated in a wash solution containing a bleaching composition by a controlled activation method as defined by Test Methods I, II and / or III described below. It can be manufactured as possible.

The bleaching compositions of the invention are advantageously used in laundry applications, hard surface cleaning, automatic dishwashing applications, whitening and / or bleaching applications related to wood pulp and / or textiles, fungicides and / or Disinfectant applications, as well as cosmetic applications, such as dentures, teeth,
Can be used on hair and skin. However, because of the unique advantages of both high potency in low temperature solutions and the ability to very effectively reduce undesired organocatalytic degradation, the organocatalysts of the present invention find use in laundry applications, such as detergents. It is ideally suited for the bleaching of fabrics and / or the bleaching of dyes (e.g. dye transfer inhibition) by the use of bleaching agents or laundry bleach additives. Furthermore, the organocatalysts of the present invention can be used in granular, powder, bar, paste, foam, gel and liquid compositions.

Accordingly, the bleaching compositions of the present invention include various other detergent ingredients that are desirable for laundry applications. Such ingredients include cleaning surfactants, other bleaching agents including other bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other detergent ingredients. However, the present invention is not limited to these. Compositions including any of these various additional detergent ingredients preferably have a pH in a 1% solution of the bleaching composition of about 6 to about 12, more preferably about 8 to about 10.5.

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

The bleaching composition preferably further comprises a source of peroxygen, as described in detail below. The bleaching composition can also include a powder or liquid composition containing a hydrogen peroxide source or a peroxygen source, as described in detail below.

When the bleaching composition comprises a hydrogen peroxide source, the laundry additive product preferably further comprises a bleach activator as described in detail below.

Another embodiment of the invention provides a method for laundering a fabric to be laundered. A preferred method comprises contacting the fabric with a laundry solution. The fabric can include most of all fabrics that can be laundered under conditions normally used by consumers. The laundry solution comprises the bleaching composition described in detail herein. The water temperature is preferably about 0 ° C to about 50 ° C, or higher. The water to fabric ratio is preferably about 1
: 1 to about 15: 1.

The laundry solution may further comprise at least one additional detergent ingredient selected from the group consisting of detergent surfactants, other bleaches, chelating agents, detergent enzymes and mixtures thereof. . Preferably, the laundry solution has a pH in a 1% solution of the bleaching composition of about 8 to about 10.5.

Another aspect of the invention provides a laundry additive product. Laundry additive products are
It comprises an organic catalyst as described in detail above. Such laundry additive products are very suitable for inclusion in the washing process if further bleaching effect is desired. Such cases include, but are not limited to, cold solution laundry applications.

The organocatalysts of the present invention, which are particularly useful in the laundry additive product of the present invention, are prepared by the controlled activation method defined by Test Methods I, II and / or III described below. It can be effective in a wash solution comprising a laundry additive product comprising. The organocatalyst can be activated alone in the wash solution containing the organocatalyst by the controlled activation method defined by Test Methods I, II and / or III described below. Alternatively, a laundry additive product containing an organic catalyst is treated with an organic solvent in a wash solution containing a laundry additive product by a controlled activation method as defined by Test Methods I, II and / or III described below. It can be manufactured so that the catalyst can be effective.

The laundry additive product preferably further comprises a source of peroxygen, as described in detail below. The laundry additive product can also include a powder or liquid composition containing a hydrogen peroxide source or a peroxygen source, as described in detail below.

Further, when the laundry additive product comprises a hydrogen peroxide source, it is desirable that the laundry additive product further comprises a bleach activator as described in detail below.

Preferably, the laundry additive product is packaged in a dosage form and uses a peroxygen source,
Add it to the washing process where you want to enhance the bleaching effect. Such single dose forms include pills, tablets,
A gel cap or other single dosage unit may be included, for example a pre-measured powder or liquid. Fillers or carrier materials can optionally be included to increase the volume of the composition. Suitable fillers or carrier materials can be selected from, but not limited to, various sulfates, carbonates and silicates, talcs, clays, and the like. Fillers or carrier materials for liquid compositions may be water or low molecular weight primary and secondary alcohols including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Monohydric alcohols can also be used. The composition is about 5
˜90% by weight of such materials can be included. PH using acidic filler
Can also be lowered.

A preferred bleaching composition comprises (a) a bleaching system comprising a source of peroxygen, and (b) an organic catalyst, as defined by Test Methods I, II and / or III as described below. A bleaching composition in which the organocatalyst becomes effective in the wash solution by a controlled activation method.

Bleaching System The bleaching composition of the present invention preferably comprises a bleaching system in addition to the organic catalyst of the present invention. Bleaching systems typically comprise a source of peroxygen. Sources of peroxygen are well known in the art and sources of peroxygen for use in the present invention include peroxygen compounds as well as compounds which provide an effective amount of peroxygen in situ under the conditions of use of the consumer. ,
Any of these well known sources can be included. Peroxygen sources include hydrogen peroxide sources, in situ formation of peroxy acid anions by reaction of hydrogen peroxide sources with bleach activators, preformed peracid compounds or mixtures of suitable peroxygen sources. Is mentioned. Of course, as will be appreciated by those skilled in the art, other sources of peroxygen can be used without departing from the scope of the present invention. Preferably, the peroxygen source is selected from the group consisting of (i) percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. A preformed peracid compound, and (ii) a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and a bleach activator Is selected from the group consisting of

When present, the source of peroxygen (source of peracid and / or hydrogen peroxide) is typically from about 1% by weight of the composition, preferably from about 5% to about 30% by weight, Preferably levels are up to about 20% by weight. The amount of bleach activator, if present, is
Typically about 0.1% by weight of the bleaching composition comprising a bleach activator in addition to the bleaching agent.
From about 0.5% to about 60% by weight, preferably from about 40% by weight.

A. Preformed Peracids The preformed peracid compounds used herein are all convenient compounds that are stable and give an effective amount of peracid anion under the conditions of use of the consumer. The organic catalyst of the present invention is, of course, percarboxylic acid and salt, percarbonic acid and salt, perimidic acid and salt,
Peroxymonosulfates and salts, and mixtures thereof (examples of which are Miracle et
al., US Pat. No. 5,576,282) and can be used in conjunction with a preformed peracid compound selected from the group consisting of:

[0122]   One group of suitable organic peroxycarboxylic acids has the general formula:

[Chemical 111] Wherein R is an alkylene or substituted alkylene group containing 1 to about 22 carbon atoms, or phenylene or a substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C (O) OH. Alternatively, it is -C (O) OOH.

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

[Chemical 112] In the formula, Y is, for example, H, CH ₃ , CH ₂ Cl, —C (O) OH or —C (O) OO.
H and n is an integer of 0-20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[Chemical 113] In the formula, Y is, for example, hydrogen, alkyl, alkylhalogen, halogen, or -C (O) O.
H or -C (O) OOH.

Typical monoperoxy acids useful herein include alkyl and aryl peroxy acids such as (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids such as peroxy-a-naphthoic acid, monoperoxyphthalic acid. (Magnesium salt hexahydrate),
And o-carboxybenzamide peroxyhexanoic acid (sodium salt), (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA). ), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA) and N, N-phthaloylaminoperoxycaproic acid (PAP), (iii) amidoperoxy acids such as monononyl peroxysuccinic acid Amide (N
APSA) or the monononylamide of peroxyadipic acid (NAPAA).

Among the typical peroxy acids useful herein are alkyl diperoxy acids and aryl diperoxy acids such as (iv) 1,12-diperoxide decanedioic acid, (v) 1,9-diperoxy acid. Azelaic acid, (vi) diperoxybrassic acid, diperoxysebacic acid and diperoxyisophthalic acid, (vii) 2-decyldiperoxybutane-1,4-dioic acid, (viii) 4,4′-sulfonylbisperoxybenzoic acid Acid, and the like.

Such bleaching agents are described in US Pat. No. 4,483,781, Hartman, published November 20, 1984,
U.S. Pat.No. 4,634,551, Burns et al., European Patent Application 0,133,354, Ba
nks et al., published February 20, 1985, and U.S. Pat.No. 4,412,934, Chung et al.
, Published November 1, 1983. The source is U.S. Patent No. 4,634,551,
6-nonylamino-described in detail in Burns et al., January 6, 1987.
Also included is 6-oxoperoxycaproic acid. Persulfate compounds such as OXONE,
Also manufactured and sold by EI DuPont de Nemours of Wilmington, DE, can be used as a suitable source of peroxymonosulfate.

B. Hydrogen Peroxide Source The hydrogen peroxide source may be any suitable source of hydrogen peroxide, such as US Pat.
It can be present at levels as detailed in 5,576,282. For example, the hydrogen peroxide source can be selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof.

The hydrogen peroxide supply source is Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 “Bleacher (Study)”.
And various forms of sodium perborate and sodium percarbonate, including various coatings and modified forms.

The preferred source of hydrogen peroxide used herein may be any convenient source, including hydrogen peroxide itself. For example, perborates such as sodium perborate (
All hydrates, but preferably mono- or tetrahydrates), sodium carbonate hydride or equivalent percarbonate, sodium pyrophosphate hydride, urea hydride, or sodium peroxide Can be used here. Source of available oxygen, eg persulfate bleach (eg OXONE (trade name) monopersulfate, manufactured by DuPont)
Is also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of all convenient hydrogen peroxide sources can also be used.

Preferred percarbonate bleaches have an average particle size of about 500 micrometers to about 1,
000 micrometers, less than about 10% by weight of particles smaller than about 200 micrometers, and about 10 particles larger than about 1,250 micrometers.
It is less than or equal to weight%. If desired, the percarbonate can be coated with silicates, borates or water-soluble surfactants. Percarbonates are used in various commercial sources such as FM
C, Solvay and Tokai Denka.

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

B. Bleach Activator Preferably, the source of peroxygen in the composition is formulated with an activator (peracid precursor compound). The active agent is from about 0.01% by weight of the composition, preferably from about 0.5% by weight, more preferably from about 1% to about 15% by weight, preferably about 10%.
It is present at levels up to wt%, more preferably up to about 8 wt%. Bleach activators, as used herein, are all compounds which, when used in conjunction with a hydrogen peroxide source, form in situ the peracid corresponding to the bleach activator. Examples of various active agents are described in detail in US Pat. Nos. 5,576,282, 4,915,854, 4,412,934, but are not limited thereto. See also US Pat. No. 4,634,551 for other exemplary bleaches and activators useful herein.

Preferred activators are tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BO).
BS), nonanoyloxybenzene sulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzene sulfonate (C ₁₀ -OBS),
Benzoyl valerolactam (BZVL), octanoyl oxybenzenesulfonate (C ₈ -OBS), it is selected from the group consisting of over-hydrolyzable (perhydrolyzable) esters, and mixtures thereof, benzoyl caprolactam and benzoyl valerolactam is most preferred. Particularly preferred bleach activators in the pH range of about 8 to about 9.5 are those with OBS or VL leaving groups.

Preferred hydrophobic bleach activators include nonanoyloxybenzene sulfonate (N
OBS), 4- [N- (nonanoyl) aminohexanoyloxy] -benzenesulfonate sodium salt (NACA-OBS) (examples thereof are US Pat. No. 5,523).
, 434), lauroyloxybenzene sulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzene sulfonate (UDOBS or C ₁₁ -OBS containing unsaturation at the 10 position), and Examples include, but are not limited to, decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are all US Pat. No. 5,698,504, incorporated herein by reference.
Issue, Christie et al., December 6, 1997, Issue 5,695,679, Christie et al.,
December 9, 1997, No. 5,686,401, Willey et al., November 11, 1997, No. 5,
, 686,014, Hartshorn et al., Promulgated November 11, 1997, No. 5,405,412, Willey
et al., promulgated April 11, 1995, 5,405,413, Willey et al., promulgated April 11, 1995, 5,130,045, Mitchell et al., promulgated 14 July 1992, and 4,412,934.
Issue, Chung et al., Promulgated November 1, 1983, and pending U.S. patent application Ser. No. 08/709,
It is an activator described in each specification of 072 and 08 / 064,564.

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

Quaternary substituted bleach activators can also be included. The bleaching composition is preferably a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (
QSP), more preferably the former. Preferred QSBA structures are all incorporated herein by reference, US Pat. No. 5,686,015, Willey et al., November 1997.
Promulgated on 11th, No. 5,654,421, Taylor et al., Promulgated on August 5, 1997, No. 5,460,747, Gosselink et al., Promulgated on October 24, 1995, No. 5,584,888, Miracle et al., 1
Further publications are published in Dec. 17, 996 and in No. 5,578,136, Taylor et al., Published Nov. 26, 1996.

Highly preferred bleach activators useful herein are each of the above-identified US Pat.
Amide-substituted materials as disclosed in 5,698,504, 5,695,679, and 5,686,014. Preferred examples of such bleach activators include (
6-octanamidocaproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate, and mixtures thereof.

[0139]   US Pat.Nos. 5,698,504, 5,695,679, and 5,68, respectively, described above.
6,014 and 4,966,723, Hodge et al., Promulgated October 30, 1990
Other useful activators disclosed in the publication are benzoxazine type activators, such as C ₆ H_Four--C (O) OC (R¹) = N-condensed material,
Include.

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

US Pat. Nos. 5,698,504, 5,695,679, and 5,68, respectively, described above.
Acyl lactam activators, such as those disclosed in US Pat. No. 6,014, particularly acyl caprolactam (see, eg, WO 94-28102A) and acyl valerolactam (US Pat. No. 5,503,639, incorporated herein by reference). , Willey et a
l., promulgated August 2, 1996) is very useful here.

D. Organic Peroxides, Especially Diacyl Peroxide In addition to the bleaching agents described above, the bleaching compositions of the present invention can optionally include an organic peroxide. All organic peroxides are included here by reference Kirk Oth
mer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley & Sons, 19
82 See pages 27-90, especially pages 63-72. If diacyl peroxide is used, it preferably has little adverse effect on stain formation / film formation.

E. Metal-containing bleach catalyst bleaching compositions can optionally use metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a transition metal cation with a specific bleach catalyst activity, such as a cation of copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese, which has most of the bleach catalyst activity. , Or no auxiliary metal cations, such as zinc or aluminum cations, and sequestering agents with limited stability constants for catalysts and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphone). Acid acids) and their water-soluble salts. Such a catalyst is described in U.S. Pat.
0,243, Bragg, promulgated February 2, 1982.

[0145]   i.Manganese metal complex-If desired, the composition may be catalyzed by a manganese compound.
Can be used. Such compounds and amounts used are well known in the art.
, U.S. Pat.No. 5,576,282, Miracle et al., Promulgated November 19, 1996,
No. 5,246,621, Favre et al., Promulgated September 21, 1993, No. 5,244,594, Favre et
al., published September 14, 1993, No. 5,194,416, Jureller et al., published March 16, 1993.
Cloth, No. 5,114,606, van Vliet et al., Promulgated May 19, 1992, and published Europe.
No. 549,271A1, No. 549,272A1, No. 544,440A2, and No. 544,490.
The manganese-based catalysts disclosed in the respective specifications of A1 are listed. These catalysts
A preferred example of^IV _Two(u-O)_Three(1,4,7-trimethyl-1,4,
7-triazacyclononane)_Two-(PF₆)_Two, Mn^III _Two(u-O)₁(u-OA
c)_Two(1,4,7-trimethyl-1,4,7-triazacyclononane)_Two-(Cl
O_Four)_Two, Mn^IV _Four(u-O)₆(1,4,7-triazacyclononane)_Four-(Cl
O_Four)_Four, Mn^IIIMn^IV _Four(u-O)₁(u-OAc)_Two (1,4,7-tri
Methyl-1,4,7-triazacyclononane)_Two-(ClO_Four)_Three, Mn^IV(1,
4,7-Trimethyl-1,4,7-triazacyclononane (OCH_Three)_Three-(PF
₆) And mixtures thereof. Other metal-based bleach catalysts are referenced above
U.S. Pat. Nos. 4,430,243 and 5,114,611, van Kraling.
En, promulgated May 19, 1992, inclusive. Manganese and various complexes
A method for enhancing bleaching using bodily ligands is disclosed in US Pat. No. 4,728,455, Rerek, 19
Issued March 1, 1988, No. 5,284,944, Madison, Issued February 8, 1994, No. 5,246,612
, Dijik et al., Promulgated 21 September 1993, No. 5,256,779, Kerschner et al., 1993.
Promulgated on October 26, No. 5,280,117, Kerschner et al., Proposed January 18, 1994, No. 5,
274,147, Kerschner et al., Promulgated 28 December 1993, 5,153,161, Kerschne.
r et al., promulgated October 6, 1992, and 5,227,084, Martens et al., 1993.
Promulgated on July 13, listed.

Ii. Cobalt Metal Complexes— Cobalt bleach catalysts useful herein are known and are described, for example, in US Pat. No. 5,597,936, Perkins et al., Issued Jan. 28, 1997, 5,595,96.
No. 7, Miracle et al., Promulgated January 21, 1997, No. 5,703,030, Perkins et al., 1
Promulgated December 30, 997, and ML Tobe, "Base Hydrolysis of Transition-Meta
l Complexes ", Adv. Inorg. Bioinorg. Mech ., (1983), 2, pp. 1-94. The most preferred cobalt catalyst herein has the formula [Co (NH ₃ ) ₅ OAc] T _y , where “OAc” represents the acetate moiety and “T _y ” is the anion. Salt, especially cobalt chloride pentaamine acetate [Co (NH ₃ ) ₅ O
Ac] Cl ₂ , as well as [Co (NH ₃ ) ₅ OAc] (OAc) ₂ and [Co (NH ₃ ) ₅ O
_{Ac] (PF 6) 2,} [Co (NH 3) 5 OAc] (SO 4), [Co (NH 3) 5 OAc] (
BF ₄ ) ₂ and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (here “PAC”)
Is.

These cobalt catalysts are described in the above-mentioned US Pat. Nos. 5,597,936, 5,595,967, and 5,597,936.
Nos. 703,030, Tobe and related references therein, and U.S. Pat. No. 4,810,410 to Diakun et al., Promulgated March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45, The Synthesis and Characteriza
tion of Inorganic Compounds, WL Jolly (Prentice Hall; 1970), pp. 461-3
, Inorg. Chem. , 18 , 1497-1502 (1979), Inorg. Chem. , 21 , 2881-2885 (1982)
, Inorg. Chem. , 18 , 2023-2025 (1979), Inorg. Synthesis, 173-176 (1960),
And the known procedure as disclosed in Journal of Physical Chemistry , 56 , 22-25 (1952).

Iii. Transition Metal Complexes of Large Polycyclic Rigid Ligands-The present compositions preferably include transition metal complexes of large polycyclic rigid ligands as bleach catalysts. The term "macropolycyclic rigid ligand" is used in the following description as "MRL.
May be abbreviated. The amount used is a catalytically effective amount of about 1 ppb.
The above are preferred, eg up to about 99.9%, more typically about 0.001 ppm
Or more, preferably about 0.05 ppm to about 500 ppm (where "ppb" is one billionth
It means "part by weight", and "ppm represents one part by million."

Suitable transition metals, for example Mn, are exemplified below. "Great multi-cycle" means MRL
Is both macrocyclic and polycyclic. "Polycyclic" means at least bicyclic. The term "rigid" as used herein includes "having superstructure" and "cross-bridged". "Stiffness" is defined as the opposite condition with reduced flexibility. See DH Busch., Chemical Review s., (1993), 93 , 847-860, which is included here for reference. More specifically, "rigidity" as used herein means that the MRLs are equivalent (ring size and type and number of atoms in the main ring are equal), but the superstructure found in the MRL (especially the bonding moieties). Alternatively, it means that it should be significantly stiffer than the macrocycle (parent macrocycle), preferably without the cross-bridge portion). In determining the relative stiffness of macrocycles with or without superstructure, experts use the free form (rather than the metal-bound form) of the macrocycle. Rigidity is well known to be useful in comparing macrocycles and suitable means for determining, measuring or comparing stiffness include computational methods (e.g. Zimmer, Chemical Reviews., (1995), 95 (38), 2629-2648 or Ha
See ncock et al., Inorganica Chimica Acta , (1989), 164, 73-84.

The preferred MRLs herein are a special type of cross-bridged, ultra-rigid ligand. “Cross-bridge” is illustrated in 1.11 below, but is not limited thereto. 1.11, the cross - bridge _-CH 2 CH ₂ - is a moiety.
This moiety bridges N ¹ and N ⁸ in the illustrated structure. Comparison result, "the same side" bridge, for example, when introducing the bridge so as across the N ¹ and N ¹² in 1.11 "cross - bridge" not sufficient to constitute a not preferable.

Suitable metals for the rigid ligand complex 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 R
There is u (IV). Preferred transition metals for the present transition metal bleach catalysts include manganese, iron and chromium.

More generally, the MRLs (and corresponding transition metal catalysts) of the invention will comprise (a) at least one macrocyclic main ring comprising 4 or more heteroatoms, and (b) preferably Selected from (i) a bridging superstructure, such as a binding moiety, (ii) a cross-bridged superstructure, such as a cross-bridged binding moiety, and (iii) a combination thereof, Suitably, it comprises a covalently bonded non-metallic superstructure that can increase the rigidity of the macrocycle.

The term “superstructure” is used herein as defined by Busch et al. In the literature (see, eg, Busch's article in “Chemical Review”).

The preferred superstructures here not only enhance the rigidity of the parent macrocycle, but also facilitate the folding of the macrocycle so that the macrocycle coordinates with the metal in the cleft. . A suitable superstructure may be remarkably simple, for example, a bond such as any of the bond illustrated in FIGS. 1 and 2 below may be used.

[Chemical 114] In the formula, n is an integer, for example 2 to 8, preferably less than 6, typically 2 to 4.
Or

[Chemical 115] Wherein m and n are integers from about 1 to 8, more preferably 1 to 3, Z is N or CH, and T is a compatible substituent such as H, alkyl, trialkylammonium. , Halogen, nitro, sulfonate, and the like. The aromatic ring in 1.10 can be replaced by a saturated ring, where the atoms connected to the ring in Z can include N, O, S or C.

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

[0156]

[Chemical formula 116] This is the MRL of the present invention, a highly preferred, cross-bridged, methyl substituted (all nitrogen atoms are tertiary) derivatives of cyclam.
Formally, this ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane using the extended von Baeyer scheme. `` A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations
1993 '', R. Panico, WH Powell and JC Richer (Eds.), Blackwell Scientif
See ic Publications, Boston, 1993, especially Section R-2.4.2.1.

Suitable transition metal bleach catalysts for use in the compositions of the present invention are generally known compounds according to the definition of the present invention, and more preferably especially designed for the laundry and cleaning applications. In addition, a large number of novel compounds exemplified below are included, but not limited thereto.

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2]
] Hexadecanemanganese (II) diaco-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2]
Hexadecane manganese (II) hexafluorophosphate aco-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate diako-5 12-Dimethyl-1,5,8,12-tetraazabicyclo [6.6.2]
Hexadecane manganese (II) tetrafluoroborate dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2
] Hexadecane manganese (III) hexafluorophosphate dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo
[6.6.2] Hexadecanemanganese (II) dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.
.2] Hexadecane manganese (II) dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (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) As a practical matter, but not limited to, the composition and washing method
On the order of at least one hundred millionth, preferably about 0.01 ppm to about 25 ppm, more preferably about 0.05 ppm to about 10 ppm, most preferably about 0.1 ppm to about 5 ppm.
Of the active bleach catalyst can be adjusted to provide an aqueous wash medium. To obtain such levels in the wash liquor of an automated wash process, a typical composition of the present invention comprises from about 0.0005 to about 0.2% by weight of the wash composition, more preferably about 0.004%. ~
It comprises about 0.08% by weight of a bleach catalyst, especially a manganese or cobalt catalyst.

Preferably, the peroxygen source is selected from a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof and bleach activators. To be done. Preferably, the bleach activator is selected from the group consisting of the hydrophobic bleach activators disclosed herein.

The purpose of such a bleaching composition is for fabrics that reduce undesired decomposition of the organic catalyst in the wash solution and need to be washed before the organic catalyst becomes effective, such as spotted fabrics. To achieve the peracid bleaching performance.

Detergent Ingredients Although not essential for the purposes of the present invention, some conventional adjunct ingredients, exemplified below, are suitable for use in the present bleaching compositions and are incorporated into the preferred embodiments of the present invention. , To enhance or enhance cleaning performance, to treat substrates to be cleaned, or to improve the aesthetics of bleaching compositions, such as in the case of perfumes, colorants, dyes, etc. The exact nature and level of incorporation of these additional ingredients will depend on the physical form of the composition and the nature of the washing operation using it. Unless otherwise indicated, the bleaching compositions according to the invention are, for example, general-purpose or "heavy duty" detergents, for example in granular or powder form, in particular laundry detergents, liquids, gels or pastes, in particular the so-called heavy duty liquid types. Includes all-purpose cleaners, liquid luxury fabric detergents, hand dishwashers or light duty dishwashers, especially highly foamed cleaners, household and industrial tablets, granules, liquids and rinse aid types Machine dishwashing, hand sanitizer, laundry bar, mouthwash, denture cleaner, car or carpet shampoo, liquid cleaners and disinfectants including bathroom cleaners, hair shampoo and hair rinse, shower gel and foam bath and metal Cleaning agents, as well as cleaning aids, such as bleaching additives and "stain remover" or pretreatment types It can be formulated Te.

Surfactant Preferably, the bleaching composition of the present invention comprises a surfactant or a surfactant system, wherein the surfactant is nonionic and / or anionic and / or cationic. Based surfactants and / or amphoteric and / or zwitterionic systems and / or
Alternatively, it can be selected from semipolar nonionic surfactants.

Surfactants are typically from about 0.1% by weight of the bleaching composition, preferably about 1%.
% By weight, more preferably from about 5% by weight to about 99.9% by weight of the bleaching composition, preferably up to about 80% by weight, more preferably up to about 35% by weight and most preferably up to about 30% by weight. Present in an amount of.

Surfactants may be nonionic, anionic, amphoteric, zwitterionic, or cationic. Mixtures of these surfactants can also be used. A preferred bleaching composition is
It comprises an anionic surfactant or a mixture of an anionic surfactant and other surfactants, especially nonionic surfactants.

Surfactants are preferably formulated to be compatible with the enzyme components present in the composition. Most preferably, in liquid or gel compositions, the surfactants are formulated to enhance, or at least not impair, the stability of the enzymes present in these compositions.

Examples of suitable nonionic, anionic, cationic, amphoteric, zwitterionic and semipolar nonionic surfactants are disclosed in US Pat. Nos. 5,707,950 and 5,576,282. However, the present invention is not limited to these. Other examples of suitable surfactants include McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 199.
7, McCutcheon Division, MC Publishing Company, U.S. Pat.Nos. 3,929,678 and 4,259,217, "Surfactant Science" series, Marcel Dekker, Inc., Ne.
w York and Basel, "Handbook of Surfactants", MR Porter, Chapman and
Hall, 2nd Ed., 1994, "Surfactants in Consumer Products", Ed. J. Falbe,
Springer-Verlag, 1987, and "Surface Active Agents and Detergents" (V
ol. I and II, Schwartz, Perry and Berch).

Highly preferred nonionic cosurfactants are polyhydroxy fatty acid amide surfactants having the formula: R ² -C (O) -N (R ¹ ) -Z wherein R ¹ is H or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof. There, R ² is C _5-31 hydrocarbyl, Z is a linear hydrocarbyl chains, at least three or hydroxyl is a poly hydroxyhydrocarbyl directly connected, or alkoxylated thereof the chain It is a derivative. Preferably, R ¹ is methyl, R ² is a linear C _11-15 alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl, or mixtures thereof, and Z is a reductive amination reaction. Derived from reducing sugars such as glucose, fructose, maltose, lactose.

Highly preferred anionic surfactants include alkylalkoxysulfate surfactants, which are water-soluble salts or acids of formula RO (A) _m SO ₃ M, wherein R is hydroxyalkyl groups having _C 10 _{-C 24} alkyl or _C 10 _{-C 24} alkyl component not substituted, preferably _C 12 _{-C 20} alkyl or hydroxyalkyl, more preferably _C 12 _{-C 18} alkyl or hydroxyalkyl Where A is an ethoxy or propoxy unit and m is greater than 0, typically about 0.5 to about 6, more preferably about 0.5 to about 3,
M can be H or a cation, such as a metal cation (eg sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Alkyl ethoxylated sulphates as well as alkyl propoxylated sulphates are contemplated herein.

When included, the bleaching compositions of the present invention, particularly the laundry detergent compositions, are typically from about 1% by weight, more preferably from about 3% by weight to about 40% by weight, more preferably It comprises up to about 20% by weight of such anionic surfactant.

Highly preferred cationic surfactants useful in the present compositions are water soluble quaternary ammonium compounds having the formula: _{R 1 R 2 R 3 R 4} N + X - wherein, _{R 1} is _C 8 _{-C 16} alkyl, and each of _R 2, _{R 3} and _{R 4, independently,} C 1 -C _{4 alkyl,} C 1 -C ₄ hydroxyalkyl, benzyl, and _- a _{(C 2 H 40) x H} , x has a value of 2 to 5, X is an anion. No more than one of R ₂ , R ₃ or R ₄ should be benzyl.

When included, the bleaching compositions of the present invention will typically be from 0.2% by weight, more preferably from about 1% by weight to about 25% by weight, more preferably up to about 8% by weight. , Of such cationic surfactants.

When included, the bleaching compositions of the present invention will typically be from 0.2% by weight, more preferably from about 1% by weight to about 15% by weight, more preferably up to about 10% by weight. , Of such an ampholytic surfactant.

When included, the bleaching compositions of the present invention will typically be from 0.2 wt%, more preferably from about 1 wt% to about 15 wt%, more preferably up to about 10 wt%. , Such zwitterionic surfactants.

When included, the bleaching compositions of this invention will typically be from 0.2% by weight, more preferably from 1% by weight to about 15% by weight, more preferably up to about 10% by weight. Of such semipolar nonionic surfactants.

The bleaching composition of the present invention comprises about 0.001% to about 100% of one or more (preferably a mixture of two or more) medium chain branched surfactants, preferably medium chain having the formula: Branched alkylalkoxy alcohol,

[Chemical 117] A medium chain branched alkyl sulphate having the formula:

[Chemical 118] A medium chain branched alkylalkoxy sulphate having the formula:

[Chemical formula 119] And the total number of carbon atoms of the branched ^primary alkyl moieties of these formulas (including the R, R ¹ and R ² branches, but not the carbon atoms comprising the EO / PO alkoxy moieties). Is 14 to 20, and for this surfactant mixture, the average total number of carbon atoms in the branched primary alkyl moiety having the above formula is greater than 14.5 and is in the range up to about 17.5, R, R ¹ and R ² are each independently selected from hydrogen, C ₁ -C ₃ alkyl, and mixtures thereof, provided that all of R, R ¹ and R ² are not hydrogen and z is When 1, at least R or R ¹ is not hydrogen. M is a water-soluble cation and can contain two or more kinds of cations, for example, a mixture of sodium and potassium. Index w is 0
To 13; x is an integer from 0 to 13; y is an integer from 0 to 13;
z is an integer of at least 1, while w + x + y + z is an integer of 8-14. E
O and PO are the following ethyleneoxy units and propyleneoxy units, respectively.

[Chemical 120] , But other alkoxy units, especially 1,3-propyleneoxy, butoxy, and mixtures thereof, are suitable as alkoxy units attached to the medium chain branched alkyl moiety.

The medium chain branched surfactant is preferably a mixture comprising a surfactant system.
Thus, when the surfactant system comprises an alkoxylated surfactant, the index m indicates the average degree of alkoxylation in the surfactant mixture. The index m is at least about 0.01, preferably about 0.1, more preferably about 0.5, most preferably about 1 to about 30, preferably about 10, more preferably about 5. is there. Considering a medium chain branched surfactant system comprising only alkoxylated surfactants, the value of the index m represents the distribution of the average degree of alkoxylation corresponding to m or corresponds exactly to m. It may be a single specific chain which is alkoxylated (eg ethoxylated and / or propoxylated) with a number of units.

Suitable medium chain branched surfactants of the invention, suitable for use in the surfactant system of the invention, have the formula:

[Chemical 121] Or the following formula

[Chemical formula 122] And a, b, d, and e have a + b of 10 to 16 and d + e of 8 to 14
Is an integer such that M is selected from sodium, potassium, magnesium, ammonium and substituted ammonium, and mixtures thereof.

The surfactant system of the present invention comprising a medium chain branched surfactant is preferably formulated in two embodiments. The first preferred embodiment comprises a medium chain branched surfactant formed from a feedstock comprising up to 25% medium chain branched alkyl units.
Thus, prior to mixing with any other conventional surfactant, the medium chain branched surfactant component comprises up to 25% of surfactant molecules that are non-linear surfactants.

A second preferred embodiment comprises a medium chain branched surfactant formed from a feedstock comprising about 25% to about 70% medium chain branched alkyl units. Therefore, before mixing with any other conventional surfactant, the medium chain branched surfactant component is approximately 25%.
˜70% comprising surfactant molecules that are non-linear surfactants.

The surfactant system of the bleaching composition of the present invention comprises from about 0.001% by weight of the surfactant system, preferably from about 1% by weight, more preferably from about 5% by weight, most preferably about From 10% to about 100%, preferably up to about 60%, more preferably up to about 30% by weight of one or more (preferably a mixture of two or more) medium chain branched alkylaryl sulfonate surfactants. Agents, preferably surfactants in which the aryl unit is a benzene ring having the formula: may also be included.

[Chemical 123] Wherein L is an acyclic hydrocarbyl moiety comprising 6 to 18 carbon atoms, R ¹ , R ² and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl, However, R ¹ and R ² are not added at the end of the L unit, but M
Is a water-soluble cation having a charge q, where a and b together satisfy the charge neutrality.

Other Detergent Ingredients Additional detergent ingredients (auxiliary ingredients) useful in the bleaching compositions of the present invention, especially laundry detergent compositions, namely builders, optical brighteners, soil release polymers, dye transfer inhibitors, Dispersants, enzymes, foam inhibitors, dyes, fragrances, colorants, filler salts, hydrotropic agents, photoactive agents, fluorescent agents, fabric conditioning agents, hydrolyzable surfactants, preservatives, antioxidants, chelates. Agents, stabilizers, anti-shrinkage agents, anti-wrinkle agents, fungicides, fungicides, corrosion inhibitors, and mixtures thereof are described below, but are not limited thereto.

Builders- The bleaching compositions of the present invention preferably comprise one or more detergent builders or builder systems. When present, the composition typically comprises at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably up to about 50%. , More preferably up to about 30% by weight of detergent builders.

The amount of builder will vary widely depending on the end use of the composition and its desired physical form. When present, the composition generally comprises at least about 1% builder. The formulation is typically about 5 to about 50% by weight, more typically about 5 to about 30%.
% Of detergent-like builder. Granular formulations typically comprise from about 10 to about 80% by weight, more typically from about 15 to about 50% by weight detergent builder. However, larger or smaller amounts of builder can be used.

Inorganic or P-containing detergent builders include alkali metal, ammonium and alkanolammonium polyphosphates (eg tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphates), phosphonates, phytic acid, Examples include, but are not limited to, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. However, there are areas where non-phosphate builders are needed. Importantly, the book is present in the presence of so-called "weak" builders (compared to phosphates), such as citric acid, or in the so-called "low builder" situations that occur with zeolite or layered silicate builders. The composition of the invention functions surprisingly effectively.

Examples of silicate builders are alkali metal silicates, in particular those having a SiO ₂ : Na ₂ O ratio of 1.6: 1 to 3.2: 1, and layered silicates. , Layered sodium silicates as described, for example, in US Pat. No. 4,664,839, Rieck, promulgated 12 May 1987. NaSKS-6 is the trade name for a crystalline layered silicate commercially available from Hoechst (herein generally abbreviated as "SKS").
-6 "). Unlike zeolite builders, NaSKS-6 silicate builders
Does not contain aluminum. NaSKS-6 is a layered silicate delta-Na ₂ S.
It has the iO ₅ form. This product is a German patent DE-A-3,417,649 and DE-A-3
, 742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as the general formula NaMSi _x O _{2x +} 1.yH ₂ O, where M is sodium. Or hydrogen, x is a number from 1.9 to 4, preferably 2, y is a number from 0 to 20,
Silicates having (preferably 0) can also be used here. Various other layered silicates commercially available from Hoechst include Na, as the alpha, beta and gamma forms.
There are SKS-5, NaSKS-7 and NaSKS-11. As mentioned above, Delta-Na ₂ SiO ₅ (NaSKS-6 form) is most preferred for use herein. Other silicates, such as magnesium silicate, are also useful, serving as crispening agents in granular formulations, as stabilizers for oxygen bleaches, and as components of suds suppressor systems.

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

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are very important in most heavy duty granular detergent compositions currently on the market and are also important builder ingredients in liquid detergent formulations. The aluminosilicate builders, empirical formula _{[M z (zAlO 2) y} ] · xH it is a substance having a 2 O, wherein z and y are integers of at least 6, z and y
Has a molar ratio of 1.0 to about 0.5 and x is an integer of about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates are crystalline or amorphous in structure and may be natural aluminosilicates or synthetics. A method for producing an aluminosilicate ion exchange material is described in US Pat.
85,669, Krummel et al., Promulgated October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are zeolite A, zeolite P (B), zeolite MAP and zeolite X.
Is marketed under the name of. 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 from about 20 to about 30, especially It is about 27. This material is called Zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle diameter of about 0.1-10 microns.

Organic detergent builders useful for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" means a compound having multiple carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder is generally added to the composition in the acid form, but can also be added in the neutralized salt form. When used in the salt form, alkali metal salts such as sodium, potassium, and lithium, or alkanol ammonium salts are preferred.

There are various types of useful materials for polycarboxylate builders. An important family of polycarboxylate builders includes U.S. Patent No. 3,128,287, Berg, 196.
Promulgated on April 7, 1974, U.S. Pat.No. 3,635,830, Lamberti et al., Promulgated Jan. 18, 1972, and U.S. Pat.No. 3,936,448, Lamberti, promulgated Feb. 3, 1976. There are various oxydisuccinates. U.S. Pat.No. 4,663,071, Bushet et al., 1
See also "TMS / TDS" builder, promulgated May 5, 987. Suitable ether polycarboxylates include cyclic compounds, especially cycloaliphatic compounds such as U.S. Pat.
923,679, Rapco, promulgated December 2, 1975, 4,158,635, Crutchfield et al.,
Compounds described in June 19, 1979, promulgated No. 4,120,874, Crutchfield et al., Promulgated October 17, 1978, and No. 4,102,903, proclaimed Crutchfield et al., Promulgated July 25, 1978, is there.

Other useful detergent builders include ether hydroxypolycarboxylates,
Copolymer of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5
-Trihydroxybenzene-2,4,6-trisulfonic acid, and various alkali metal, ammonium and substituted ammonium salts of carboxymethyloxysuccinic acid, polyacetic acid such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxy Rate, such as mellitic acid, succinic 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 (particularly the sodium salt), are available from renewable sources and are biodegradable,
It is a polycarboxylate builder of particular importance in heavy duty liquid detergent formulations. Citrates can also be used in granular compositions, especially in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

Detergent compositions of the present invention can be found in US Pat. No. 4,566,984, Bush, January 1986 2
Also suitable are 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds described in Promulgation 8th. Useful succinic acid builders, there is a C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof.
A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of the succinate builder include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred) and 2-pentadecenyl succinate. Lauryl succinate is a preferred builder of this type,
European Patent Application No. 86200690.5 / 0,200263, published Nov. 5, 1986.

Other suitable polycarboxylates are described in US Pat. No. 4,144,226, Crutchfield e.
t al., published March 13, 1979, and U.S. Pat.No. 3,308,067, Diehl, March 7, 1967.
Promulgated on Sunday. See also Diehl U.S. Pat. No. 3,723,322.

Fatty acids, such as C _{12 to} C ₁₈ monocarboxylic acids, are also incorporated into the composition, either alone or in combination with the builders mentioned above, especially the citrate and / or succinate builders, to enhance builder activity. be able to. The use of such fatty acids is
Formulators should take this into account as foaming generally decreases.

When phosphorus-based builders can be used, especially in bar formulations used for hand-washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, Can be used. Phosphonate builders such as ethane-1-hydroxy-1,1
-Diphosphonates and other known phosphonates (e.g. U.S. Pat.
(See No. 3,213,030, No. 3,422,021, No. 3,400,148 and No. 3,422,137)
Can also be used.

Chelating Agents- The bleaching compositions of this invention can optionally include one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof all as described below. Without wishing to be bound by theory, it is believed that the properties of these materials are due in part to their exceptional ability to remove iron and manganese ions from laundry solutions by forming their soluble chelates.

Examples of suitable chelating agents and amounts used are US Pat. Nos. 5,576,282 and 5,728.
Preferred biodegradable chelating agents for use herein are ethylenediamine disuccinate ("EDDS"), particularly U.S. Pat. No. 4,704,233, November 3, 1987, Ha
[S, S] isomer as described in Promulgation to rtman and Perkin.

The composition comprises a water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or, for example, an insoluble builder such as zeolite, layered silicate,
Etc. and as a useful co-builder.

When used, these chelating agents generally comprise from about 0.1% by weight of the bleaching composition to about 15% by weight of the bleaching composition, more preferably up to 3.0% by weight. Make up.

Dye Transfer Inhibitors- The bleaching compositions of this invention prevent dye transfer from one fabric to another by the dissolved and dispersant dyes during fabric washing and conditioning operations involving colored fabrics. One or more dye transfer inhibitors may also be included.

Suitable polymeric dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. However, the present invention is not limited to these. Examples of such dye transfer inhibitors are described in US Pat. Nos. 5,707,950 and 5,707,951.

Other suitable dye transfer inhibitors include, but are not limited to, crosslinked polymers. Cross-linked polymers are polymers in which the backbones are interconnected to some extent, and these bonds can have chemical or physical properties.
Crosslinked polymers are described in Journal of Polymer Science, Volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymer is made to form a steric rigid structure and to allow the dye to be entrapped in the pores formed by the steric structure.

In another embodiment, the dye is entrapped by swelling the crosslinked polymer. Suitable crosslinked polymers are described in pending European patent application No. 94870213.9. The addition of such polymers also enhances the performance of the enzymes in the bleaching composition.

Dye transfer inhibitors have the ability to complex or adsorb washed dyes from dyed fabrics before they are deposited on other objects in the wash solution.

When present in the bleaching composition, the dye transfer inhibitor is present in an amount of about 0.00 of the bleaching composition.
From 0.01% by weight, more preferably from about 0.01% by weight, most preferably from about 0.
It is present in an amount of from 05% by weight to about 10% by weight of the bleaching composition, more preferably up to about 2% by weight and most preferably up to about 1% by weight.

Dispersants- The bleaching compositions of this invention can also include dispersants. Suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl groups separated from each other by not more than two carbon atoms. .

Polymers of this type are described in British Patent GB-A-1,596,756. Examples of such salts are MW 2000-5000 polyacrylates and their copolymers with maleic anhydride, the molecular weight of the copolymers being 1,000-100,000.
00.

In particular, copolymers of acrylates and methacrylates, for example with a molecular weight of 4000
480N can be added to the detergent composition of the present invention in an amount of 0.5 to 20% by weight of the composition.

The composition of the present invention has a lime soap dispersive power (LSDP) defined below of 8 or less,
A lime soap peptizer compound that is preferably 7 or less and most preferably 6 or less can be included. The lime soap peptizer compound is preferably 0-2.
It is present in an amount of 0% by weight.

The effect of lime soap peptizers was demonstrated by HC Borghetty and CA Bergman, J.
Am. Oil. Chem. Soc., 27, 88-90, (1950), which is given numerically by the lime soap dispersancy (LSDP) measured by the lime soap dispersion test. This lime soap dispersion test method is widely used by experts in this field, for example WN Linfield, Surfactant Science Series, Volume 7, page 3, WN.
Linfield, Tenside surf.det., 27, 159-163, (1990), and MK Nagar.
ajan, WF Masler, Cosmetics and Toiletries, 104, 71-73, (1989). LSDP is 333 ppm CaCO ₃ (Ca: Mg = 3
: 2) The weight% ratio of dispersant to sodium oleate required to disperse the lime soap precipitate formed by 0.025 g of sodium oleate in 30 ml of water of equivalent hardness.

Surfactants with good lime soap dispersancy include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulphates and ethoxylated alcohols.

[0214] Exemplary surfactants LSDP than 8 for use according to the present _{invention, C} 1 6 _{-C 18} dimethyl amine oxide, with an average ethoxylation degree of 1 to 5 _C 12 _{-C 18} alkyl ethoxysulfate , in particular _{C 1} 2 _{-C 15} alkyl ethoxysulfate degree of ethoxylation of about 3 (LSDP = 4), and an average ethoxylation degree of 12 (LSDP = 6) or 30 _C 14 _{-C 15} ethoxylated alcohol ( Commercially available from BASF GmbH as Lutensol A012 and Lutensol A030, respectively.

Suitable polymeric lime soap dispersants for use herein are described by MK Nagarajan and WF Masler, Cosmetics and Toiletries, 104, 71-73, (198).
It is described in 9).

Hydrophobic bleaching agents such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl-6- Aminohexanoyl] benzene sulfonate, and mixtures thereof, and nonanoyloxybenzene sulfonate can also be used as a lime soap peptizer compound with hydrophilic / hydrophobic bleach formulations.

The enzyme -bleaching composition may contain, in addition to the amylase of the present invention, one or more detergent enzymes which provide cleaning performance and / or fabric protection properties. Such enzymes include proteases, amylases, cellulases and lipases. These enzymes can be incorporated into the non-aqueous liquid bleaching compositions of the present invention in the form of suspensions, "malmes" or "prills". Another suitable class of enzymes is in the form of enzyme slurries in nonionic surfactants, such as the enzyme marketed under the trade name "SL" by Novo Nordisk or under the trade name "LDP" by Novo Nordisk. The enzyme is contained in a commercially available microcapsule. Suitable enzymes and amounts used are described in US Pat. No. 5,576,282.

For use herein, the enzymes added to the composition in the form of conventional enzyme prills are particularly preferred. Such prills are generally about 100-1,000 microns in size,
More preferably about 200-800 microns and is suspended throughout the non-aqueous liquid phase of the composition. The prill in the composition of the present invention exhibits particularly preferable enzyme stability in that the enzyme activity is retained for a long period of time as compared with other enzyme forms. As such, compositions using enzyme prills do not need to include conventional enzyme stabilizers, which enzymes must frequently be used when incorporated into aqueous liquid detergents.

Examples of suitable enzymes include hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, Examples include, but are not limited to, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and known amylases, or mixtures thereof. A preferred combination is a bleaching composition containing a mixture of the usual enzymes which can be used, such as proteases, lipases, cutinases, and / or cellulases, together with the amylase according to the invention.

Such suitable enzymes are described in US Pat. Nos. 5,576,282, 5,728,671 and 5,707,
No. 950.

A preferred protease is subtilisin (subtilisin BPN and BPN ') obtained from specific strains of B. Subtilis and B. licheniformis. One suitable protease is obtained from Bacillus strains, has maximum activity in the pH range 8-12 and was developed by Novo Industries A / S of Denmark, hereafter "Novo", ESPERASE
It is sold as (product name). The production of this enzyme and similar enzymes is described in Novo's British Patent No. 1,243,784. Other suitable proteases include ALCALASE (trade name), DURAZYM (trade name) and SAVINASE (trade name) commercially available from Novo.
(Commercial name), and MAXATASE (commercial name), MAXACAL (commercial name), PROPERASE (commercial name), and MAXAPEM (commercial name) commercially available from Gist-Brocades (protein-engineered MA
XACAL). Proteolytic enzymes are denatured bacterial serine proteases,
For example, European Patent Application No. 87303761.8, filed Apr. 28, 1987 (especially pages 17, 24 and 98), relates to an enzyme referred to herein as "Protease B", and a modified bacterial serine proteolytic enzyme. European Patent Application No. 199,404
, Venegas, filed October 29, 1986, and which is referred to herein as "Protease A". More preferred is a protease herein referred to as "Protease C", which is a variant of the alkaline serine protease obtained from Bacillus , in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, Serine replaces asparagine at position 123 and alanine replaces threonine at position 274. Protease C is a European Patent No. 90915958: 4 corresponding to International Patent WO91 / 06637, 1991 5
Published on 16th of March, it is described in. Also included herein are genetically modified variants, especially variants of Protease C. Bac described in International Patent WO93 / 18140A to Novo
See also high pH protease from illus sp. NCIMB 40338. Protease,
An enzyme detergent comprising one or more other enzymes and a reversible protease inhibitor
International patent WO 92 / 03529A to Novo. Procter & Gam if desired
There are also proteases with reduced adsorptivity and increased hydrolyzability, as described in International Patent WO 95/07791 to ble. Suitable recombinant trypsin-like proteases for detergents here are described in International Patent WO 94/25583 to Novo.

More specifically, the protease called "Protease D" is a variant of carbonyl hydrolase having an amino acid sequence not found in nature, which is derived from the precursor carbonyl hydrolase from International Patent WO95. / 10615, Genencor Int
Bacillus amylol, as described in ernational, published April 20, 1995.
According to the iquefaciens subtilisin numbering, a plurality of amino acid residues at a position equal to position +76 in the carbonyl hydrolase is preferably +99, +10.
1, +103, +104, +107, +123, +27, +105, +109,
+126, +128, +135, +156, +166, +195, +197, +
204, +206, +210, +216, +217, +218, +222, +2
It is obtained by combining with one or more amino acid residue positions equivalent to the position selected from the group consisting of 60, +265 and / or +274 and substituting different amino acids. Patent application EP 251446 and international patent WO 91/0
Proteases described in 6637 and protease BLAP (trade name) described in International Patent WO91 / 02792 are also suitable. Proteolytic enzymes are
In the bleaching composition of the present invention, 0.0001 to 2% by weight of the composition, preferably 0.0
It is incorporated in an amount of 01 to 0.2% by weight, more preferably 0.005 to 0.1% by weight of pure enzyme.

[0223] Useful proteases are described in the PCT literature, ie WO95 / 30010, The Procter &
Published by Gamble Company on November 9, 1995, WO95 / 30011, The Procter & Gam
Published November 9, 1995 by ble Company, and WO95 / 29979, The Procter
& Gamble Company, published November 9, 1995, in their respective specifications.

Other particularly useful proteases are multiple substituted protease variants, which involve replacing an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin. And Ba
cillus amyloliquefaciens subtilisin 1, 3, 4, 8, 9, 10, 12, 1
3, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 3
8, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 7
6, 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, in combination with substituting amino acid residues with other natural amino acid residues at one or more amino acid residue positions corresponding to positions 103 and 76. 27 of Bacillus amyloliquefaciens subtilisin, including substitution of amino acid residues at
99, 101, 104, 107, 109, 123, 128, 166, 204, 2
06, 210, 216, 217, 218, 222, 260, 265 or 274
There may also be amino acid residue substitutions at one or more amino acid residue positions other than the amino acid residue position corresponding to the position, and / or all October 23, 1998 The Procter &
PCT applications WO99 / 20727, WO99 / 20726 and WO99 / 2 filed from Gamble Company
Multiple-substituted protease variants, as described in No. 0723, are described in Bacillus
Substituting amino acid residues with other natural amino acid residues at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of amyloliquefaciens subtilisin. More preferably, the protease variant is

[Chemical formula 124]

[Chemical 125] A combination of substitutions selected from the group consisting of:

[0225]   More preferably, the protease variant is

[Chemical formula 126]

[Chemical 127] A combination of substitutions selected from the group consisting of:

Most preferably, the protease variant is 101/103/104/159/23
2/236/245/248/252, preferably 101G / 103A / 104
I / 159D / 232V / 236H / 245R / 248D / 252K substitution combinations.

Cellulases useful in the present invention include both bacterial or fungal cellulases. Preferably, these cellulases have an optimum pH of 5 to 9.5. Suitable cellulases are described in Barbesgoard et al., US Pat. No. 4,435,307, which discloses fungal cellulases produced from Humicola insolens. Suitable cellulases are British Patent GB-A-2,075,028, GB-A-2,095,275, German Patent DE-OS-.
It is also described in 2,247,832.

Examples of such cellulases include Humicola insolens (Humicola grisea var. Ther
moidea), in particular Humicola strain DSM 1800.

[0229] Another suitable cellulase is obtained from Humicola insolens, having a molecular weight of about 50 K.
Da, an isoelectric point of 5.5, a cellulase containing 415 amino acids, and Humicola i
It is a ~ 43 kD endoglucanase derived from nsolens, DSM 1800 and exhibiting cellulase activity, the preferred endoglucanase component having the amino acid sequence disclosed in International Patent Application WO 91/17243. International Patent WO94 / 21801, Genencor, 1994 9
EGIII obtained from Trichoderma longibrachiatum, published on May 29th
Cellulases are also suitable cellulases. A particularly suitable cellulase is a cellulase with color-protecting properties. Examples of such cellulases are described in European Patent Application No. 91.
No. 202879.2, filed Nov. 6, 1991 (Novo), is a cellulase. C
The arezymes and Celluzymes (Novo Nordisk A / S) are particularly useful. International patent WO91 / 1
See also 7244.

Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Detergent compositions containing peroxidase are described, for example, in US Pat. Nos. 5,576,282, 5,728,671 and 5,707,950, PC.
T International applications WO89 / 099813, WO89 / 09813 and European patent application No. 9120288
No. 2.6, filed November 6, 1991, and No. 96870013.8, filed February 20, 1996. Laccase enzymes are also suitable.

Preferred fortifiers are substituted phenothiazines and phenoxazines, 10-
Phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10
-Methylphenoxazine (described in WO 94/12621), substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or sodium perborate are the preferred sources of hydrogen peroxide.

The peroxidase is generally present in the bleaching composition in an amount of from 0.0001 to bleaching composition.
Formulated in the amount of 2% by weight pure enzyme.

Other preferred enzymes that can be included in the cleaning compositions of the present invention include lipases. Suitable lipase enzymes for detergents are microorganisms of the Pseudomas family, eg British Patent Nos. 1,3
72,034, including the enzyme produced by Pseudomas stutzeri ATCC 19.154. The preferred lipase is the microorganism Pseudomonas fluorescent IA.
Included are lipases produced by M 1057 that show a positive immunological cross-reactivity with lipase antibodies. This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name of Lipase P "Amano" (hereinafter referred to as "Amano-P"). Other suitable commercially available lipases include Amano-CES, Toyo Jozo Co., Ta.
Chromobacter viscosum, such as Chromobac, commercially available from gata, Japan
ter viscosum var. lipolyticum NRRLB 3673 derived lipase, US Biochem
Chromobacter vis from ical Corp., USA and Disoyynth Co., The Netherlands
There are cosum lipases and lipases derived from Pseudomonas gladioli. Particularly preferred lipases are M1 Lipase (trade name) and Lipomax (trade name) (Gist-Brocad
es) and Lipolase ™ and Lipolase Ultra ™ (Novo) and proved to be very effective when used in combination with the compositions of the present invention.

A cutinase [EC 3.1.1.50] is also suitable, but it is considered to be a special type of lipase, ie a lipase that does not require surface activation. The addition of cutinase to bleaching compositions is described, for example, in International Patent WO 88/09367 (Genencor).

The lipase and / or cutinase is usually added to the bleaching composition in an amount of 0.
It is incorporated in an amount of 0001 to 2% by weight of active enzyme.

Known amylases (α and / or β) can be included to remove carbohydrate-based stains. International Patent WO94 / 02597, Novo Nordisk A / S, 1994 2
Published March 3, describes a cleaning composition that includes a mutant amylase. International patent WO94 / 18314, Genencor, published August 18, 1994, and WO95 / 10603, Nov
See also Nordisk A / S, published August 20, 1995. Other amylases known for cleaning compositions include both α- and β-amylases. α-amylase is
Known in the art, U.S. Patent No. 5,003,257, European Patent No. 252,666,
International patent WO / 91/00353, French patent FR2,676,456, European patent 285,123
Nos. 525,610, 368,341, and British Patent 1,296,839 (Novo). Other suitable amylases are International Patent WO 94/18314,
Amylase with enhanced stability, including PURAFACT OX AM (trade name), described in WO96 / 05295, Genencor, published February 22, 1996, published Aug. 18, 1994, and international patents Novo Nord as described in WO95 / 10603, published April 1995.
Amylase variant commercially available from isk A / S.

Examples of commercially available α-amylase products are all Novo Nordisk A / S, Termamyl ™, BAN ™, FUNGAMYL ™ and DURAMYL ™ available from Denmark.
(Product name). International patent WO 95/26397 describes other suitable amylase, namely Termamyl (trade name), measured at 25 ° C-55 ° C, pH value 8-10 by Phadebas (trade name) α-amylase activity assay. An α-amylase is described which is characterized by having a specific activity which is at least 25% higher than the specific activity. Other amylolytic enzymes with improved properties in terms of activity level and combination of thermostability and high activity level are described in WO95 / 35382.

The compositions of the invention can also include a mannanase enzyme. Preferably, the mannanase is the following three types of mannan degrading enzymes, namely β-mannosidase of EC3.2.1.25 and endo-1,4-β-mannosidase of EC3.2.1.78 (hereinafter referred to as “mannanase”). , And EC4.2.1.100 1,4-β-mannobiosidase and mixtures thereof. (IUPAC Classification-Enzyme Nomenclature, 1992 ISBN 0-12-227165-3 Academic Press)

More preferably, the treatment composition of the present invention comprises β-1,4-mannosidase (EC 3.2.1.78) called mannanase, when mannanase is present.
The terms “mannanase” or “galactomannanase” refer to the mannanase enzymes formally referred to in the art as mannan endo-1,4-beta-mannosidase, also known as beta-mannanase and endo-1,4-mannanase. However, this enzyme catalyzes the random hydrolysis reaction of 1,4-beta-D-mannoside bonds in mannan, galactomannan, glucomannan, and galactoglucomannan.

In particular, mannanases (EC 3.2.1.78) constitute a group of polysaccharases that degrade mannans, capable of cleaving polyose chains containing mannose units,
That is, the glycosidic bond in mannan, glucomannan, galactomannan, and galactoglucomannan can be cleaved. Mannan is β-1,
Glucomannan is a polysaccharide having a skeleton composed of 4-linked mannose, and glucomannan is a polysaccharide having a skeleton of β-1,4-linked mannose and glucose that are more or less regularly alternating. Glucomannans are mannans and glucomannans containing α-1,6-linked galactose side chains. These compounds can be acetylated.

Degradation of galactomannan and galactoglucomannan is facilitated by the complete or partial removal of galactose side chains. Furthermore, the degradation of acetylated mannan, glucomannan, galactomannan and galactogluco-mannan is promoted by complete or partial deacetylation. The acetyl group can be removed by alkali or mannan acetyl esterase. The oligomers released by mannanase or a combination of mannanase and α-galactosidase and / or mannan acetylesterase can be further degraded by β-mannosidase and / or β-galactosidase to release free maltose.

Mannanase has been identified in several Bacillus organisms. For example, Talbot
et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp.3505-3510 (1990) is derived from Bacillus stearothermophilus and has a dimer form and a molecular weight of 162 kD.
and a beta-mannanase with an optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech, Vol.10, No.5, pp.551-55
5 (1994) is derived from Bacillus subtilis and has a molecular weight of 38 kDa and an optimum pH of 5.0.
And a beta-mannanase with 55C and pI 4.8.
Japanese patent JP-03047076 describes a beta-mannanase from Bacillus sp. Having a molecular weight of 373 kDa as measured by gel filtration, an optimum pH of 8-10, and a pI of 5.3-5.4. Japanese Patent No. JP-63056289 describes the production of alkaline thermostable beta-mannanase, for example hydrolyzing the beta-1,4-D-mannopyranoside bond of mannan to produce mannooligosaccharides. . Japanese Patent JP-63036774 relates to Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase at alkaline pH. Japanese Patent No. JP-08051975 is alkalophilic Bacillus.
The alkaline beta-mannanase obtained from sp. AM-001 is described. Baci
A purified mannanase useful for bleaching pulp and paper obtained from Llus amyloliquefaciens and a method for producing the same are described in WO 97/11164. International patent WO 91/18974 describes hemicellulases active at extreme pH and temperature, such as glucanases, xylanases or mannanases. International patent WO94
/ 25576 discloses enzymes obtained from Aspergillus aculeatus, CBS 101.43 which exhibit mannanase activity and are useful in the degradation or denaturation of plant or algae cell wall material. International patent WO 93/24622 describes mannanases isolated from Trichoderma reseei useful for bleaching lignocellulosic pulps. Hemicellulases capable of degrading mannan-containing hemicelluloses are described in International Patent WO91 / 18987,
Purified mannanase obtained from Bacillus amyloliquefaciens is described in WO 97/11164.

Preferably the mannanase enzyme is an alkaline mannanase as defined below, more preferably a mannanase obtained from a bacterial source. In particular, the laundry detergent composition of the present invention comprises a mannanase obtained from Bacillus agaradhaerens NICMB 40482 strain, a Bacillus subtilis strain 168, a mannanase obtained from the gene yght, and a mannanase obtained from Bacillus sp. 1633 and / or Bacillus.
It comprises an alkaline mannanase selected from the mannanases obtained from lus sp. AAI12. The most preferred mannanase for inclusion in the detergent compositions of the present invention is Bacillus sp.
It is a mannanase enzyme obtained from 1633.

The term “alkaline mannanase enzyme” means at least 10% of its maximum activity,
Preferably at least 25%, more preferably at least 40% enzyme activity
It means an enzyme having a specific pH range of -12, preferably 7.5-10.5.

Alkaline mannanase obtained from Baciluus agaradhaerens NICMB 40482 is described in pending US patent application Ser. No. 09 / 111,256. More specifically, the mannanase comprises i) a polypeptide produced by Baciluus agaradhaerens NCIMB 40482, or ii) an amino acid sequence as shown in positions 32-343 of SEQ ID NO: 2 shown in US patent application Ser. No. 09 / 111,256. Or iii) an analogue of the polypeptide defined in i) or ii), which is at least 70% homologous to said polypeptide, or Immunologically reactive with a polyclonal antibody raised against the polypeptide in a purified form, which is induced by amino acid substitutions, deletion mutations or additions).

[0246] Also, (a) SEQ ID NO: 1 having mannanase activity and shown in US Patent Application No. 09 / 111,256.
A polynucleotide molecule encoding a polypeptide comprising a nucleotide sequence as shown in nucleotides 97 to 1029 of (1), (b) a homologue of a variety of (a), (c) having mannanase activity, SEQ ID NO: 2 shown in 09 / 111,256
A polynucleotide molecule encoding a polypeptide which matches at least 70% of the amino acid sequence of amino acid residue 32 to amino acid residue 343 of (d) (a), (b) or (c) , And (e) a corresponding isolated polypeptide having mannanase activity selected from the group consisting of degenerate nucleotide sequences of (a), (b), (c) or (d). Be done.

The plasmid pSJ1678, which comprises the polynucleotide molecule (DNA sequence) encoding the mannanase, has been transformed into a strain of Escherichia coli, which by the inventor of the present invention Budapest Treaty on the International Recog.
nition of the Deposit of Microorganisms for the Purposes of Patent Proce
According to the dure, the Deutsche Sammlung von Mikroorganimen und Zellkulturen Gm
bH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany, 1998
It has been deposited on May 18 with deposit number DSM 12180.

A second, more preferred enzyme is the mannanase from Baciluus subtilis strain 168, described in pending US patent application Ser. No. 09 / 095,163. More particularly, the mannanase is i) encoded by the coding portion of the DNA sequence set forth in SED ID No. 5 shown in US patent application Ser. No. 09 / 095,163, or an analogue of said sequence, or ii. ) A polypeptide comprising the amino acid sequence set forth in SEQ ID NO: 6 set forth in U.S. patent application Ser. No. 09 / 095,163, or iii) an analog of the polypeptide defined in ii), which is Polyclonal antibody which is 70% homologous or is derived from said polypeptide by substitution, deletion mutation or addition of one or several amino acids, or which is raised against said polypeptide in purified form And is immunologically reactive).

[0249] Also, (a) SEQ ID NO: 5 having mannanase activity and shown in US Patent Application No. 09 / 095,163.
A polynucleotide molecule encoding a polypeptide comprising the nucleotide sequence shown in (b), a homologue of a variety of (a), (c) having a mannanase activity and having the sequence of SEQ ID NO: 09 / 095,163 6
A polynucleotide molecule that encodes a polypeptide that matches at least 70% to the amino acid sequence of (d) (a), (b) or (c), and (e) (a), ( Also included are the corresponding isolated polypeptides having mannanase activity selected from the group consisting of the degenerate nucleotide sequences of b), (c) or (d).

A third, more preferred mannanase is Danish patent application No. PA1 under examination.
99801340. More particularly, this mannanase is i) a polypeptide produced by Bacillus sp. 1633, or ii) positions 33 to 340 of SEQ ID NO: 2 shown in Danish patent application PA199801340.
A polypeptide comprising the amino acid sequence set forth in, or iii) an analog of the polypeptide defined in i) or ii), which is at least 65% homologous to said polypeptide, or from said polypeptide, Immunologically reactive with a polyclonal antibody raised against the polypeptide in a purified form, which is induced by the substitution, deletion mutation or addition of one or several amino acids).

(A) a polynucleotide molecule having mannanase activity and encoding a polypeptide comprising the nucleotide sequence set forth in nucleotides 317 to 1243 of SEQ ID NO: 1 of Danish Patent Application No. PA199801340, (b) ) (a) a homologue of a variety, (c) having mannanase activity and having at least 65 amino acid sequences from amino acid residue 33 to amino acid residue 340 of SEQ ID NO: 2 of Danish Patent Application No. PA199801340.
% A polynucleotide molecule encoding a matching polypeptide, a molecule complementary to (d) (a), (b) or (c), and (e) (a), (b), (c) Alternatively, the corresponding isolated polynucleotide selected from the group consisting of the degenerate nucleotide sequence of (d) is also included. The plasmid pBXM3, which comprises the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention, has been transformed into a strain of Escherichia coli, which by the inventor of the present invention Budapest Treaty on the International Rec.
ognition of the Deposit of Microorganisms for the Purposes of Patent Pro
According to the cedure, the Deutsche Sammlung von Mikroorganimen und Zellkulturen
GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany, in 1998
It was deposited on May 29, 2014 under the deposit number DSM 12197.

A fourth, more preferred mannanase is the Danish patent application No. PA 1998 under examination.
It is described in 01341. More specifically, this mannanase is i) a polypeptide produced by Bacillus sp.
A polypeptide comprising the amino acid sequence set forth in, or iii) an analog of the polypeptide defined in i) or ii), which is at least 65% homologous to said polypeptide, or from said polypeptide, Immunologically reactive with a polyclonal antibody raised against the polypeptide in a purified form, which is induced by the substitution, deletion mutation or addition of one or several amino acids).

(A) a polynucleotide molecule having mannanase activity and encoding a polypeptide comprising a nucleotide sequence such as nucleotides 225 to 1236 of SEQ ID NO: 1 shown in Danish Patent Application No. PA199801341 , (B) a homologue of the variety of (a), (c) having mannanase activity and having at least 65 amino acid residues from amino acid residue 25 to amino acid residue 362 of SEQ ID NO: 2 of Danish Patent Application PA199801341.
% A polynucleotide molecule encoding a matching polypeptide, a molecule complementary to (d) (a), (b) or (c), and (e) (a), (b), (c) Alternatively, the corresponding isolated polynucleotide selected from the group consisting of the degenerate nucleotide sequence of (d) is also included.

The plasmid pBXM1 comprising the polynucleotide molecule (DNA sequence) encoding the mannanase of the invention has been transformed into a strain of Escherichia coli, which according to the inventor of the invention Budapest Treaty on the. International Rec
ognition of the Deposit of Microorganisms for the Purposes of Patent Pro
According to the cedure, the Deutsche Sammlung von Mikroorganimen und Zellkulturen
GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany, in 1998
It was deposited on May 29, 2014 under the deposit number DSM 12433.

Mannanase, if present, is preferably present in the treatment composition of the present invention in an amount of 0.0001 to 2% by weight of the composition, more preferably 0.0005 to 0.1% by weight, most preferably 0. 001 to 0.02% by weight.

The composition of the invention may also comprise a xyloglucanase enzyme. Suitable xyloglucanase, for the purposes of the present invention, is an enzyme that exhibits endoglucanase activity specific to xyloglucan, preferably from about 0.001 to about 1% by weight of the composition, more preferably about 0.01. To about 0.5% by weight. As used herein, the term "endoglucanase activity" refers to cellulosic materials such as cellulose, cellulose derivatives, lichenin, β-D-glucan, or xyloglucan,
By the ability of an enzyme to hydrolyze the 1,4-β-glycoside linkages present therein. Endoglucanase activity can be determined by methods known in the art, eg International Patent WO 9
It can be measured by the method described in 4/14953 and explained below. One unit of endoglucanase activity (eg CMCU, AVIU,
XGU or BGU) is defined as the production of 1 μmol reducing sugar / min from a glucan substrate, which can be, for example, CMC (CMCU), an acid swollen Avicell (
AVIU), xyloglucan (XGU) or cereal β-glucan (BGU). Reducing sugars are measured by the methods described in International Patent WO94 / 14953 and described below. The specific activity of endoglucanase for the substrate is in units / m
Defined as g-protein.

An enzyme exhibiting XGU endoglucanase activity as its highest activity (hereinafter “specific for xyloglucan”) is suitable, and the enzyme is i) the following partial sequence:

[Chemical 128]

[Chemical formula 129] Or a DNA similar to them, which constitutes at least one of the sequences encoding a xyloglucan-specific polypeptide with an endoglucanase activity, or is encoded by a DNA contained therein, and which is defined in ii) i) Encoded by sequences, Aspergillus aculeatus, CB
It is immunologically reactive with antibodies raised against the highly purified endoglucanase from S 101.43 and is specific for xyloglucan.

More specifically, the term “specific for xyloglucan” means that the endoglucanase enzyme exhibits the highest endoglucanase activity on xyloglucan substrates, other cellulose-containing substrates such as carboxymethylcellulose, cellulose, or For other glucans, preferably less than 75% active, more preferably 50%
Less than about 25%, and most preferably less than about 25%.

Preferably, the specificity of the endoglucanase for xyloglucan is as a relative activity measured as the release of reducing sugars under optimal conditions obtained by incubating the enzyme with xyloglucan and other test substrates, respectively. Further defined.
For example, specificity is the activity of xyloglucan versus β-glucan (XGU / BGU),
It is defined as the activity of xyloglucan to carboxymethylcellulose (XGU / CMCU) or the activity of xyloglucan to acid swollen Avicell (XGU / AVIU), preferably greater than about 50, eg 75, 90 or 100.

As used herein, the term “derived from” is encoded by a DNA sequence isolated from strain CBS 101.43 as well as an endoglucanase produced by strain CBS 101.43 and transformed with said DNA sequence. Also meant is an endoglucanase produced in the host organism. The term “homolog” as used herein refers to specific conditions (eg, 5
Pre-soaked in xSSC, 5xSCC, 5x Denhardt's solution, and 50 μg of denatured, sonicated calf thymus DNA solution prehybridized at −40 ° C. for 1 hour, followed by 50 μCi32-P-dCTP labeling. Hybridize in the same solution supplemented with the attached probe for 18 hours at -40 ° C and 2xS
A polypeptide encoded by a DNA that hybridizes to the same probe as the DNA encoding for the endoglucanase enzyme specific for xyloglucan under SC, 0.2% SDS, wash at 40 ° C. for 30 minutes). Show.
More specifically, the term refers to a DNA sequence that is at least 70% homologous to any of the above sequences that encodes an endoglucanase specific for xyloglucan, and that is at least 75% homologous to any of the above sequences. , At least 80%, at least 90%, or even at least 95%. This term does not provide for any modification of the DNA sequence set forth above, eg, another amino acid sequence of the polypeptide encoded by the sequence, but a DN comprising any of the DNA sequences.
A protein structure that may result in a nucleotide substitution corresponding to the codon usage of the host organism into which the A structure is introduced, or a different amino acid sequence, and thus an endoglucanase mutant, which probably has different properties than the native enzyme. Nucleotide substitutions that give Other examples of possible modifications include inserting one or more nucleotides into the sequence, adding one or more nucleotides at either end of the sequence, or one or more nucleotides in the sequence. Deletion at either end or internally.

Xyloglucan-specific endoglucanases useful in the present invention preferably have an XGU / BGU, XGU / CMU, and / or XGU / AVIU ratio (defined below) of greater than 50, for example 75, 90 or 100, which is an endoglucanase.

Furthermore, the xyloglucan-specific endoglucanase is preferably substantially devoid of activity against β-glucan and / or up to 25%, when the activity against xyloglucan is 100%, For example, it exhibits up to 10% or about 5% activity against carboxymethylcellulose and / or Avicell. Furthermore, the xyloglucan-specific endoglucanases of the present invention are substantially devoid of transferase activity, ie the activity observed with most endoglucanases specific to plant xyloglucan.

Xyloglucan-specific endoglucanases are described in International Patent No. WO 94/14.
As described in No. 953, it can be obtained from the fungal species A. aculeatus. A microbial endoglucanase specific for xyloglucan is also disclosed in International Patent No. WO94 /
No. 14953. Endoglucanases specific to xyloglucan obtained from plants have also been disclosed, but since these enzymes have transferase activity, xyloglucan-specific microbial endonucleases are required when strongly degrading xyloglucan. It must be considered inferior to glucanase. Another advantage of microbial-based enzymes is that they can generally be produced in larger quantities in microbial hosts than enzymes from other sources.

Xyloglucan, when present, is preferably 0.0001 to 2% by weight of the composition, more preferably 0.0005 to 0.1% by weight, most preferably 0. Formulated in the amount of 001 to 0.02 wt% pure enzyme.

The above-mentioned enzymes may be of any suitable origin, for example plants, animals, bacteria, fungi and yeasts. Purified or unpurified forms of these enzymes can be used. Mutants of the native enzyme are also included in the definition. The mutant is
Chemical and / or natural enzyme synthesis, for example by protein and / or genetic engineering
Alternatively, it can be obtained by physical modification. It is also a common method to express an enzyme through a host organism in which a genetic material that controls the production of the enzyme is cloned.

The enzyme is usually incorporated into the bleaching composition in an amount of 0.0001 to 2% by weight of active enzyme of the bleaching composition. Enzymes can be as separate single components (including one enzyme, prill, granules, stabilized liquid, etc.) or a mixture of two or more enzymes (cogranule).
Can be added as

Other suitable detergent ingredients that can be added are enzymatic oxidative scavengers. An example of such an enzymatic oxidative scavenger is ethoxylated tetraethylene polyamine.

A series of enzyme materials and means of incorporation into synthetic bleaching compositions were described by Genencor Internati.
International patents WO93 / 07263 and WO93 / 07260 to onal, WO89 / 08694 to Novo, and US Pat. No. 3,553,139 to McCarty et al. The enzyme is described in U.S. Patent No. 4,101,457, Place et al, July 18, 1978, and 4,507,219, Hu.
Also disclosed in ghes, 26 March 1985. Enzyme materials that are particularly useful in liquid detergent formulations, and the incorporation of those enzymes into such formulations, is described in US Pat. No. 4,261,868.
No., Hora et al, April 14, 1981.

Enzyme Stabilizers-The enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described, for example, in U.S. Patent No. 3,600,319, August 17, 1971, Gedg.
e et al., European Patents 199,405 and 200,586, October 29, 1986, Ve
disclosed as negas. Enzyme stabilization systems are also described in US Pat. No. 3,519,570. Useful Baci to produce protease, xylanase and cellulase
llus, sp. AC13 is described in International Patent WO9401532 to Novo. The enzyme used herein can be stabilized by a water-soluble source of calcium and / or magnesium ions present in the finished composition that supplies such enzyme to the enzyme. Suitable enzyme stabilizers and amounts used are described in US Pat. No. 5,576,282.

Other Detergent Ingredients- The bleaching composition of the present invention optionally comprises one or more of the following ingredients,
That is, polymeric dispersants, clay stain removal / redeposition inhibitors, brighteners, foam inhibitors, dyes, fragrances, structural elasticity agents, fabric softening agents, carriers, hydrotropic agents, processing aids, and / or Or a pigment can also be included. Suitable examples and amounts of such other detergent ingredients are described in US Pat. No. 5,576,282.

Fabric Washing Methods The organic catalysts of the present invention and compositions containing them include dipping methods, pretreatment methods, and methods involving a rinsing step to which another rinsing aid composition can be added.
It can be used for virtually all washing or washing methods.

The fabric laundering method described herein preferably comprises the treatment of the fabric with an organic catalyst (on its own,
Or in the form of a bleaching composition), and the organocatalyst comprises a controlled activation method as defined by Test Methods I, II and / or III described below. It becomes effective in laundry solutions. Optionally, but preferably, the laundry solution comprises a source of peroxygen.

The method of the present invention is conveniently carried out during the washing step. The washing method is preferably performed at 5 ° C to 95 ° C, particularly 10 ° C to 60 ° C. The pH of the laundry solution is preferably 7-
Eleven.

Organic Catalyst Products The organic catalyst and / or bleaching compositions of the present invention can be used in various products used in laundry processes.

In a preferred embodiment, there is provided a product comprising the organocatalyst of the invention and / or a bleaching composition comprising the organocatalyst of the invention, wherein test methods I, II and And / or by the controlled activation method defined by III
The organic catalyst becomes effective. These products further include instructions for using the organic catalyst and / or the bleaching composition to wash fabrics in need of washing, preferably stained fabrics. The instructions for use include test methods I, II and II, described below, in an amount of product comprising an organic catalyst and / or a cleaning composition, with or without a source of peroxygen, in a solution containing fabric. And / or III so that the organic catalyst is activated by a controlled activation method defined by III.

Controlled Efficacy Determination of Organocatalysts Whether the organocatalysts or bleaching compositions of the invention, or products comprising the organocatalysts or bleaching compositions of the invention, are within the scope of the invention. In order to facilitate the determination of, three test methods, namely test methods I, II and III, are described below.

Case ₁ for Method I, Case II ₁ for Method II, and Method III
As for the case III- ₁ , the product containing the organic catalyst (OCCP
) Does not fall within the scope of the present invention.

Test Method I General Principles / Parameters: Keep all solutions at 25 ° C. The adjustment of pH is carried out using sodium carbonate or an amount thereof as needed. Except for a small amount (1-5 ml) of dye bleaching solution (DBS) aliquot taken to measure absorption,
All solutions are continuously stirred at 250 rpm. The absorption value is based on the standard dye solution (RD
S) is measured at λ _max .

A test is performed to determine if either the parameters d-- _bleach or w-- _OCCP need to be reset from their _undervalues .

D _bleach is a parameter that represents the time elapsed between the formation of the dye bleaching solution (DBS) and the data acquisition in the final test method. Shortage (default) value of the parameter _d bleac _h is 1 minute, but in the following cases I, can be defined as a longer time.

W _OCCP is a parameter representing the weight of the organic catalyst containing product (OCCCP) used to form the organic catalyst containing product solution (OCCCPS) in the final test method.
The deficit value for this parameter is 1.00 grams, but in Case II below it can be defined as a smaller amount or weight.

CDS is a concentrated dye solution defined as a 300 ppm deionized aqueous solution of Amaranth dye (Aldrich), pH 10.

OCCP is a fully formulated organocatalyst containing product (as described above) in which the organocatalyst may be present with various auxiliary components.

OCCPS is an organic catalyst containing product solution prepared by dissolving 1.00 g of an organic catalyst containing product (OCCCP) in 1.0 L of deionized water at 25 ° C., the pH of which is the final solution. It is adjusted in advance so as to have a pH of 9.9 to 10.1. DBS is a dye bleaching solution formed by adding a 100 mL aliquot of OCCPS to 10 mL of CDS.

Measurement of A _max : 100 mL deionized water is added to 10 mL CDS at pH 10. The resulting homogeneous reference dye solution (RDS), the absorption was measured at lambda _{ma x} (approximately 518 nm) by UV- visible spectroscopy is _{A max.}

[0286]   Aliquot collection time: The time to collect an aliquot from OCCPS is fixed (t _f ) And the prescribed period (t_dd) Both are included. t_fValues of 0.5, 1.5,
2.5 and 3.5 minutes. t_ddValues of 0.25D, 0.50D and 0
． 75D, where D is the recommended wash duration. t_ddFor 5 minutes
It is not necessary to take an aliquot prescribed for full duration. For the purpose of this test
, D must not be less than 5 minutes or more than 16 hours. To the manufacturer of OCCP
If less wash duration is recommended, set D to 20 minutes. For example,
If the washing time is 60 minutes, t_fIn addition to t_ddIs 15, 30
And 45 minutes. For a 12 minute wash, the required data point is 0.5
Related to aliquot collection at 1.5, 2.5, 3.5, 6 and 9 minutes
It is the data point.

The test is carried out as follows using d _bleach and w _OCP deficit values. Among all fixed and duration defined aliquots, identify the one that gives the lowest measured absorption value A _min . The time (t _f or t _dd ) when Q is taken from OCCPS is defined as t _Q. This is the maximum δA (A _m
Note that it is the same point indicating _ax- A _min ). 3 depending on the value of A _min
There are two cases.

Case 1: If A _min > 0.9A _max , repeat the test and reset the value of d _bleach . In this new test, aliquots taken at t _Q are treated as before, except that stirring is continued for another 1 minute until the time when the absorption A _min ≦ 0.9A _max . The minimum number of DBS agitation required to satisfy the absorption condition is
_Define a new d- _bleach for the final test method implementation. However, if a d _bleach of more than 30 minutes is required [ie, the time point when δA is maximum (
If 10% bleaching is not achieved in 30 minutes, even when the organocatalyst is present in the highest concentration], it is not shown by Method I that the OCCP is within the scope of the present invention, but the OCCP is not And / or Method III may be shown to be within the scope of the present invention.

Case 2: If A _min > _0.25 A _max , _repeat the test and reset the value of w _OCCP . OCCCPS are prepared from 50% of the OCCCP deficiency. This process is repeated until the absorption conditions described in Case 3 are met (eg OCCP).
From 1.0 g to 0.5 g, then 0.5 g to 0.2 if necessary
5g, etc.).

Case 3: If 0.25A _max ≦ A _min ≦ 0.9A _max , this test can be used as a final test method implementation. Under these conditions, d _bleach and w _{OC CP} do not have to change from the _undervalues used.

Test Method I: The first step is the preparation of OCCPS as described above. Set the time to add OCCP to deionized water to form OCCPS at t = 0. At each of the aliquot collection times (t _f or t _dd ), 100 mL aliquots of OCCPS were collected, between the time t = (t _f or t _dd ) and t = (t _f or t _dd +0.25 min). Immediately, to remove undissolved OCCP, the filtrate is t =
(T _f or t _dd +0.50 min) to 10.0 mL CDS. A 1 to 5 mL aliquot C of the obtained DBS is collected immediately before absorption measurement (data acquisition).
At the end of d _bleach , the absorption of C is measured at λ _max .

The time point at which the absorption measurement (data acquisition) of the aliquot C was performed is defined as t _C.
Therefore, it is necessary that t _C = (t _f or t _dd ) +0.50 min + d _bleach . The absorption values measured at t _C is defined as _{A t (C).} The symbol δA _{t (C)} is defined as A _max −A _{t (C)} . For example, the wash time is 12 minutes, the value of d _bleach is 1 minute, and the aliquot collection time is 0.5, 1.
． At 5, 2.5, 3.5, 6 and 9 minutes, the data acquisition time (t _C ) is 2
3, 4, 5, 7.5 and 10.5 minutes.

The value t _Cα is any data acquisition time t _C acquired before the other data acquisition time t _Cβ . Therefore, t _Cα <t _Cβ . absorption in _t Cα is _{A t
(C) α} and the absorption at t _Cβ is At _{(C) β} . There are two cases, depending on the values of At _{(C) α} and At _{(C) β} .

Case I ₁ : Controlled efficacy if all At _{(C) β} <all At _{(C) α} and by definition δA _{t (C) β} > δA _{t (C) α.} Organic catalyst-containing products (OCCPs) with properties are indicated, and therefore organic catalyst-containing products with controlled efficacy are within the scope of the present invention.

Example Case I ₁ for a 20 minute wash cycle: t t _C A _max A _{t (C)} δA _{t (C)} % Dye 0 0 1.20 100 0.5 2 1.20 1.00 0.20 83 1.5 3 1.20 0.84 0.36 71 2.5 4 1.20 0.70 0.50 58 3.5 5 1.20 0.67 0.53 56 5 6.5 1.20 0.72 0.48 60 10 11.5 1.20 0.78 0.42 65 15 16.5 1.20 0.83 0.37 69

[0296]

[Table 1]

Case I ₂ : If each At _{(C) β} ≧ each At _{(C) α} and by definition δA _{t ( C) β} ≦ δA _{t (C) α} , then the controlled efficacy is The organocatalyst containing product (OCCP) it has is not shown by Method I, but its OCCP is not
And / or Test Method III may fall within the scope of the invention. As an example, this is because OCCP is completely dissolved in OCCCP before the first t _f ,
This can happen with organocatalyst containing products (OCCCP) that do not have controlled efficacy, where the subsequent value of At _(C) is constant. The degradation of the organocatalyst in OCCPS over time (which results in less dye consumption in DBS over time) results in At _{t (C) β} > At _{t (C) α} .

Example of Case I ₂ for a 20 minute wash cycle:

[Table 2]

Test Method II General / Parameter / Method: As defined by Test Method I, except for the additions below.

OCSP is an organocatalyst segregation product prepared so that the overall composition of OCSP is equal to that of OCCP by re-formulating OCCP without organocatalyst and then adding the organocatalyst to the re-formulated product. Is.

OCSPS is an organic catalyst segregation product solution prepared by dissolving 1.00 g of an organic catalyst segregation product (OCSP) in 1.0 L of deionized water at 25 ° C., the pH of which is the final solution. It is adjusted in advance so as to have a pH of 9.9 to 10.1. w _OCCP is a parameter that represents the weight of the organic catalyst containing product (OCCCP) used to form the organic catalyst containing product solution (OCCCPS) in the final test method.
The deficit value for this parameter is 1.00 grams, but in Case II below it can be defined as a smaller amount or weight.

W _OCSP is a parameter that represents the weight of the organic catalyst segregation product (OCSP) used to form the organic catalyst segregation product solution (OCSPS) in the final test method.
The deficit value for this parameter is 1.00 grams, but in Case II below it can be defined as a smaller amount or weight.

DBS2 is a dye bleaching solution formed by adding a 100 mL aliquot of OCSPS to 10 mL CDS.

The time to take an aliquot from OCSPS is equal to the time from OCCPS previously described.

[0305]   Test Method II: The first step is to complete Method I above. Described in Method I
Same as listed d_bleachAnd repeat the same procedure (but with OCCP
Instead of using OCSP). Add OCSP to deionized water to add OCSPS
Set the forming time to t = 0. Aliquot collection time (t_fOr t_dd)of
A 100 mL aliquot of OCSPS was taken at each and t = (t_fOr t _dd ) To t = (t_fOr t_ddImmediate filtration for up to +0.25 minutes)
Then, undissolved OCSP was removed, and the filtrate was t = (t_fOr t_dd+0.50
Min) to 10.0 mL of CDS. 1-5 mL aliquot of the obtained DBS2
The sample S is collected immediately before the absorption measurement (data acquisition). d_bleachAt the end of
The absorption of S is λ_maxTo measure.

The time point at which the absorption measurement (data acquisition) of the aliquot S was performed is defined as t _S.
Therefore, it is necessary that t _S = (t _f or t _dd ) +0.50 min + d _bleach = t _C. The absorption values measured at t _S is defined as _{A t (S).} The symbol δAt _(S) is defined as _{Amax-At (S)} . For example, wash time is 1
2 minutes, d- _bleach value is 1 minute, aliquot collection time is 0.
For 5, 1.5, 2.5, 3.5, 6 and 9 minutes, the data acquisition time (t _S ) is 2, 3, 4, 5, 7.5 and 10.5 minutes. Depending on the value of _{A t (C)} and _{A t (S)} with respect to _{t S} = t _C, there are two cases.

Case II ₁ : At least one At _(S) <At _(C) , and δ by definition
When At _(S) > δAt _(C) , an organocatalyst containing product (OCCCP) with controlled efficacy is indicated, and thus the OCCP is within the scope of the invention.

Example of Case II ₁ for a 20 minute wash cycle:

[Table 3]

[0309] More preferably, with respect to method II, be be at least one when _{1.2xA t (S) <A t} (C), the organic catalyst-containing product having a controlled efficacy (O
CCP) is shown and the OCCP is within the scope of the invention.

Case II ₂ : Each A _{t (S)} ≧ A _{t (C)} , and by definition δA _{t (S)} ≦ δ
If At _(C) , an organocatalyst containing product (OCCCP ₎ with controlled efficacy.
) Is not shown by Method II, but its OCCP is determined by Test Method I and / or Test Method III. It may fall within the scope of the invention by the OCCP.

Test Method III General Principles / Parameters / Methods: Same as specified by Test Method I, except for the additions below. Peracetic acid, 32 wt% solution in diluted acetic acid, commercially available from Aldrich.

OCCPS ′ in Method III is 1.00 g of a product containing organic catalyst (OCCP).
Deionized water containing 100 mg of peracetic acid (based on 100% activity) at 25 ° C.
It is an organic catalyst-containing product solution prepared by dissolving it in 0 L, and its pH is adjusted in advance so that the final solution has a pH of 9.9 to 10.1.

Test Method III: All steps are the same as Method I except OCCPS ′ is used instead of OCCPS.

Case III ₁ : Controlled efficacy if all At _{(C) β} <all At _{(C) α} and by definition δA _{t (C) β} > δA _{t (C) α.} Organic catalyst-containing products (OCCCPs) with properties are indicated, and therefore organic catalyst-containing products with controlled efficacy are within the scope of the present invention.

Case III ₂ : Each At _{(C) β} ≧ each At _{(C) α} , and by definition δAt _{(C)
) If β} ≤ δAt _{(C) α} , an organocatalyst containing product (OCCCP) with controlled efficacy is not shown by Method III, but the OCCP is
And / or Test Method II may fall within the scope of the invention.

The compositions of the present invention can be effectively prepared by any of the methods of choice by the formulator, examples of which are all incorporated herein by reference, US Pat. No. 5,691,297, Nassano.
et al., promulgated November 11, 1997, No. 5,574,005, Welch et al., promulgated November 12, 1996, No. 5,569,645, Dinniwell et al., promulgated October 29, 1996, No. 5,565,422, Del Greco et al., Promulgated October 15, 1996, No. 5,516,448, Capeci et al., 19
May 14, 1996, No. 5,489,392, Capeci et al., February 6, 1996, No. 5,486
, 303, Capeci et al., Promulgated January 23, 1996, but not limited thereto.

In addition to the above embodiments, the organocatalysts of the present invention can be formulated into any suitable laundry detergent composition, examples of which are all incorporated herein by reference, US Pat. No. 5,679,630. , Baeck et al., Promulgated 21 October 1997, No. 5,565,145, Wats
on et al., published October 15, 1996, No. 5,478,489, Watson et al., October 1, 1996.
Promulgated 5th, No. 5,478,489, Fredj et al., Promulgated on December 26, 1995, No. 5,470,507, Fredj et al., Promulgated on November 28, 1995, No. 5,466,802, Panandiker et al., 19
Promulgated November 14, 1995, No. 5,460,752, Fredj et al., Promulgated October 24, 1995, No. 5,4
58,810, Fredj et al., Promulgated October 17, 1995, No. 5,458,809, Fredj et al.
, October 17, 1995, No. 5,288,431, Huber et al., February 22, 1994.

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 without departing from the scope of the present invention. The present invention is not limited by the contents described in the specification.

[Sequence list]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Robert, Richard, Dijkstra             Cleves, Ohio, USA             Mitchell, park, drive, 7715 (72) Inventor Gregory, Scott, Miracle             Hamilton, Ohio, USA             Old, Oxford, Road,             3065 F-term (reference) 4H003 AB01 BA17 DA01 EB19 EC01                       EC02 EC03 EE03 EE05 FA07                       FA43 FA44

Claims (63)

[Claims] 1. A method of laundering, characterized in that the fabric in need of washing is contacted with an organic catalyst by a controlled activation method. 2.   The method according to claim 1, wherein the organic catalyst is selected from the group consisting of a) to i) below.
Law:   a) Aryl having a net charge of about +3 to about -3 represented by formula [I] below.
Iminium cations and aryliminium polyions: [Chemical 1] (In the formula, R^TwoAnd R^ThreeAre independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sul
Select from honato, alkoxy, keto, carboxyl, and carboalkoxy groups
R, selected from selected, substituted or unsubstituted groups, R¹And R ^Four Is H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
Heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and carboalco
Selected from xyl groups, substituted or unsubstituted, saturated or unsaturated.
KM, X⁻Is a counter ion that has a suitable charge balance, and v is an integer of 1 to 3.
Is a number),   b) Aryl having a net charge of about +3 to about -3, represented by formula [II] below.
Iminium Zwitterion: [Chemical 2] (In the formula, R⁵~ R⁷Are independently H, alkyl, cycloalkyl, aryl,
Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfona
Group consisting of alkoxide, alkoxy, keto, carboxyl, and carboalkoxy groups
Selected from substituted, unsubstituted or substituted groups from
In, there is also a group represented by the following formula, [Chemical 3] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is substituted or unsubstituted, saturated or tired
Sum alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and
Selected from the group consisting of heterocycles),   c) a net charge of about -3 to about +3, represented by formulas [V] and [VI] below.
Modified amine: [Chemical 4] (In the formula, R⁹~ R¹⁰Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Nato, alkoxy, keto, carboxyl, and carboalkoxy groups and anions
A substituted or substituted group selected from groups having an ionic and / or cationic charge.
Or a non-substituted group, R⁸And R¹¹Is present, if present
Substituted or unsubstituted, saturated or unsaturated, H, alkyl, sic
Low alkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro,
Halo, cyano, alkoxy, keto and carboalkoxy groups and anions and
And / or a group selected from the group consisting of groups having a cationic charge, R¹² Is a leaving group and its protonated form is pK_aValue (H_TwoO standard) is 37>
pK_aIt falls within the range of> -2, but R⁸~ R¹²If all exist,
Can be combined to form a fused aryl, fused carbocycle or fused heterocycle.
And a group represented by the following formula: [Chemical 5] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is substituted or unsubstituted, saturated or tired
Sum alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and
Selected from the group consisting of heterocycles),   d) A variable having a net charge of about -3 to about +3, represented by the following formulas [VII] to [X].
Amine oxide: [Chemical 6] (In the formula, R⁹~ R¹⁰Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Nato, alkoxy, keto, carboxyl, and carboalkoxy groups and anions
A substituted or substituted group selected from groups having an ionic and / or cationic charge.
Or a non-substituted group, R⁸And R¹¹Was replaced, and also
Is an unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl, aryl
Reel, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano,
Sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups
And a group selected from groups having an anionic and / or cationic charge,
R¹²Is a leaving group and its protonated form is pK_aValue (H_TwoO standard)
37> pK_aIt falls within the range of> -2, but R⁸~ R¹²Is present
Can be combined to form a fused aryl, fused carbocycle or fused heterocycle.
In this formula, a group represented by the following formula also exists, [Chemical 7] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is substituted or unsubstituted, saturated or tired
Sum alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and
Selected from the group consisting of heterocycles),   e) Represented by the following formulas [XXIa], [XXIb], [XXII] and [XXIII], respectively.
, Sulfonimines, phosphonimines, N-acylimines and thiodiazole diamines
Oxide: [Chemical 8] (In the formula, R⁴¹~ R⁴⁴Are, when present, independently H, alkyl, cycloal
Kill, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
Saturated, substituted or unsubstituted, selected from the group consisting of xy groups
Or selected from unsaturated groups with the proviso that R⁴¹~ R⁴⁴Is all other R^{Four 1} ~ R⁴⁴A fused aryl, fused carbocycle or fused heterocycle.
Can form part of a common ring that it includes),   f) an oxa having a net charge of about +3 to about -3 represented by the following formula [III]:
Diridinium cations and polyions: [Chemical 9] (In the formula, R^{2 '}~ R^{3 '}Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Consisting of nato, alkoxy, keto, carboxyl, and carboalkoxy groups
R is selected from the group selected from the group, substituted or unsubstituted, R^{1 '} And R^{4 '}Is a substituted or unsubstituted, saturated or unsaturated
, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, hetero
Ring, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy
A group selected from the group consisting of groups, X⁻Has a good charge balance, preferred
A counter ion that is compatible with bleach).   g) Oxadiene represented by the following formula [IV] and having a net charge of about +3 to about -3.
Lyzinium Zwitterion: [Chemical 10] (In the formula, R^{5 '}~ R^{7 '}Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sul
It consists of phonato, alkoxy, keto, carboxyl, and carboalkoxy groups.
Selected from the group consisting of substituted, unsubstituted or substituted groups,
In the formula, there are also groups represented by the following formula, [Chemical 11] Where Z ′_p ⁻Is T ’₀Covalently bound to Z '_p ⁻Is -CO_Two ⁻, -SO_Three ⁻,
-OSO_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
2 or 3 and T '₀Is saturated, either substituted or unsubstituted.
Or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl
, And a heterocycle),   h) Oxaziridine sulfonimine [XXIVa], phosphon represented as follows:
Imine [XXIVb], N-acylimine [XXV], and thiodiazole dioxide [X
XVI] and [XXVII]: [Chemical 12] (In the formula, R^{41 '}~ R^{44 '}Are, when present, independently H, alkyl, cyclo
Alkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, ha
B, cyano, sulfonate, alkoxy, keto, carboxyl, and carboa
A substituted or unsubstituted group selected from the group consisting of lucoxy groups
Selected from R^{41 '}~ R^{44 '}Is all other R^{41 '}~ R^{44 '} Bound to any of the above and includes fused aryl, fused carbocycle or fused heterocycle
Can form part of a common ring), and   i) a mixture thereof. 3.   The method according to claim 2, wherein the organic catalyst is selected from the group consisting of a) to i) below.
Law:   a) Aryl having a net charge of about +3 to about -3 represented by formula [XI] below.
Iminium cations and aryliminium polyions: [Chemical 13] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R²⁰Are independently H, alkyl,
Chloroalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
From a substituted or unsubstituted group selected from the group consisting of xy groups
Two R selected in close proximity²⁰Substituents are combined and fused aryl
, Fused carbocycles or fused heterocycles can be formed, R¹⁸Is H, alkyl
, Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, di
Toro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of carboalkoxy groups, substituted or substituted
R may be a non-group¹⁹Is a substituted or unsubstituted, saturated or
Unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl
Is a group selected from the group consisting of a ring and a heterocycle, G is (1) -O-, (2
) -N (R²³)-, And (3) -N (R²³R²⁴)-Selected from the group consisting of
And R²¹~ R²⁴Are independently H, oxygen, linear or branched C₁~
C₁₂Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl
Substituted, substituted, or selected from the group consisting of
Or an unsubstituted group, provided that R is¹⁸, R¹⁹, R²⁰, R²¹~ R ²⁴ Is all R¹⁸, R¹⁹, R²⁰, R²¹~ R²⁴Combined with any of
Can form part of a common ring, all gem-R²¹~ R²²Is a combination
Can form a carbonyl, all vic-R²¹~ R²⁴Is a bond
To form an unsaturation, the substituent R²¹~ R²⁴Any group of
To form fused unsaturated moieties that can be substituted or unsubstituted.
, X⁻Is a suitable charge-balancing counterion and v is an integer from 1 to 3)
,   b) an aryl having a net charge of about +3 to about -3, represented by formula [XII] below.
Ruiminium twin ion: [Chemical 14] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R²⁶Are independently H, alkyl,
Chloroalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
From a substituted or unsubstituted group selected from the group consisting of xy groups
All 2 vic-Rs selected²⁶The substituents are combined to form a fused aryl,
Fused carbocycles or fused heterocycles can be formed, R²⁵Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nit
B, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of ruvoalkoxy groups, substituted or substituted
The group represented by the following formula also exists in this formula, [Chemical 15] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 16] Is selected from the group consisting of: wherein q is an integer from 1 to 8;²⁹Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R^Thirty)-, And (3) -N (R^ThirtyR³¹) -Selected from the group consisting of ²⁷ , R²⁸, R^ThirtyAnd R³¹Are independently H, oxygen, alkyl, cyclo
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alco
Group consisting of xy, arylcarbonyl group, carboxyalkyl group and amido group
R is a substituted or unsubstituted group selected from R²⁵, R^{Two 6} , R²⁷, R²⁸, R^ThirtyAnd R³¹Is all R²⁵, R²⁶, R²⁷,
R²⁸, R^ThirtyAnd R³¹To form part of a common ring with any of
And all gem-R²⁷~ R²⁸Combine to form carbonyl
Can and all vic-R²⁷~ R³¹Can combine to form unsaturation
Yes, substituent R²⁷~ R³¹Substituted or combined with any group of
Uncondensed fused unsaturated moieties can be formed),   c) Modified amines represented by the following formulas [XV] and [XVI]: [Chemical 17] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is or has been replaced
Unsaturated or unsaturated hydroxy, perhydroxy, alkoxy, pera
Lucoxy, carboxyl, percarboxyl, sulfonate, persulfonate
R is a group selected from the group consisting of³⁵Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs³⁵Substituents are combined and fused aryl
, Fused carbocycles or fused heterocycles can be formed, R³²Is H, alkyl
, Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, di
Toro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of carboalkoxy groups, substituted or substituted
R may be a non-group³³Is H, alkyl, cycloalkyl, alkaryl, a
Selected from the group consisting of reel, aralkyl, and heterocycle, substituted or substituted
It may be a saturated or unsaturated group which is not converted, and this formula is represented by the following formula.
There is also a group that is [Chemical 18] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 19] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R³⁹)-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of ³⁶ , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloalkyl
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
A group consisting of cis, arylcarbonyl group, carboxyalkyl group and amido group
R is a group selected from, substituted or unsubstituted, R³², R³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R ³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with either
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a group
Can be combined to form a carbonyl, all vic-R³⁶, R³⁷,
R³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R ³⁷ , R³⁹And R⁴⁰All of the groups are substituted or substituted.
Uncondensed unsaturated moieties can be formed),   d) Modified amine oxide represented by the following formulas [XVII] to [XX]: [Chemical 20] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is or has been replaced
Unsaturated or unsaturated hydroxy, perhydroxy, alkoxy, pera
Lucoxy, carboxyl, percarboxyl, sulfonate, persulfonate
R is a group selected from the group consisting of³⁵Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs³⁵Substituents are combined and fused aryl
, Fused carbocycles or fused heterocycles can be formed, R³²Is H, alkyl
, Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, di
Toro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of carboalkoxy groups, substituted or substituted
R may be a non-group³³Is H, alkyl, cycloalkyl, alkaryl, a
Selected from the group consisting of reel, aralkyl, and heterocycle, substituted or substituted
It may be a saturated or unsaturated group which is not converted, and this formula is represented by the following formula.
There is also a group that is [Chemical 21] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical formula 22] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R³⁹)-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of ³⁶ , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloalkyl
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
A group consisting of cis, arylcarbonyl group, carboxyalkyl group and amido group
R is a group selected from, substituted or unsubstituted, R³², R³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R ³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with either
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a group
Can be combined to form a carbonyl, all vic-R³⁶, R³⁷,
R³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R ³⁷ , R³⁹And R⁴⁰All of the groups are substituted or substituted.
Uncondensed unsaturated moieties can be formed), e) Sulfonimine [XXVIIIa], Phosphonimine [XXVI] represented by the following formula
IIb], N-acylimine [XXIX]: [Chemical formula 23] (In the formula, each R⁴⁶Are independently H, alkyl, cycloalkyl, aryl, condensed
Fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, ar
Selected from the group consisting of coxy, keto, carboxyl, and carboalkoxy groups
Selected from selected, substituted or unsubstituted groups, all two vi
c-R⁴⁶The substituents are combined to form a fused aryl, fused carbocycle or fused heterocycle.
Can form R⁴⁵Is H, alkyl, cycloalkyl, alkali
Ru, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfona
Group consisting of alkoxide, alkoxy, keto, carboxyl, and carboalkoxy groups
Can be a substituted or unsubstituted group selected from
In case of (1) -O-, (2) -N (R⁴⁷)-, And (3) -N (R⁴⁷R ⁴⁸ ) -Selected from the group consisting of⁴⁷~ R⁴⁸Independently, H, oxygen, direct
Chain or branched C₁~ C₁₂Alkyl, alkylene, alkoxy, ally
From the group consisting of alkaryl, alkaryl, aralkyl, cycloalkyl, and heterocycle.
A selected, substituted or unsubstituted group),   f) Oxa represented by the following formula [XIII] and having a net charge of about +3 to about -3.
Diridinium cations and polyions: [Chemical formula 24] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R^{20 '}Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs^{20 '}The substituents are combined to form a condensed aryl.
R, a fused carbocycle or a fused heterocycle can be formed, R^{18 '}Is H, Al
Kill, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl
, Nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl,
And carboalkoxy groups selected from the group consisting of, substituted or substituted
R may be a group that is not^{19 '}Is saturated, substituted or unsubstituted
Or unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aryl
A group selected from the group consisting of aralkyl and heterocycle, G being (1) -O-
, (2) -N (R^{23 '})-, And (3) -N (R^{23 '}R^{24 '})-
Selected from the group R^{21 '}~ R^{24 '}Are independently H, oxygen, straight chain or
Branched chain C₁~ C₁₂Alkyl, alkylene, alkoxy, aryl, alk
Selected from the group consisting of reel, aralkyl, cycloalkyl, and heterocycle
, A substituted or unsubstituted group, with the proviso that R is^{18 '}, R^{19 '} , R^{21 '}~ R^{24 '}Is all R^{18 '}, R^{19 '}, R^{21 '}~ R^{24 '}Noi
Can be combined with a gap to form part of a common ring, and all gem-R^{21 '}
~ R^{22 '}Can combine to form a carbonyl, and all vic-
R^{21 '}~ R^{24 '}Can combine to form unsaturation, the substituent R^{21 '}~
R^{24 '}Any of the above groups in combination with a substituted or unsubstituted
Can form a saturated moiety and has a substituent R^{21 '}~ R^{24 '}Any group of
Can form fused unsaturated moieties that can be substituted or unsubstituted.
X⁻Is a suitable charge-balancing counterion and v is an integer from 1 to 3.
),   g) an oxa having a net charge of about +3 to about -3 represented by the following formula [XIV]:
Zyridinium Zwitterion: [Chemical 25] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R^{26 '}Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs^{26 '}The substituents are combined to form a condensed aryl.
R, a fused carbocycle or a fused heterocycle can be formed, R^{25 '}Is H, Al
Kill, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl
, Nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl,
And carboalkoxy groups selected from the group consisting of, substituted or substituted
The group represented by the following formula also exists in this formula, [Chemical formula 26] Where Z ′_p ⁻Is T ’₀Covalently bound to Z '_p ⁻Is -CO_Two ⁻, -SO_Three ⁻,
-OSO_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 2 and T '₀Is [Chemical 27] Is selected from the group consisting of: wherein q is an integer from 1 to 8;^{29 '}Is independent
, Linear or branched, H, alkyl, cycloalkyl, alkali-
Ru, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbo
A substituted, selected from the group consisting of nyl, carboxyalkyl and amido groups.
Or a group not substituted, G is (1) -O-, (2) -N
(R^{30 '})-, And (3) -N (R^{30 '}R^{31 '})-Selected from the group consisting of
And R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Are independently H, oxygen,
Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene
, Heterocycles, alkoxy, arylcarbonyl groups, carboxyalkyl groups and
A substituted or unsubstituted group selected from the group consisting of
R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}All
And R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Nozu
Can bind to it to form part of a common ring, and all gem-R^{27 '}~
R^{28 '}Can combine to form a carbonyl, and all vic-R
^{27 '}~ R^{31 '}Can combine to form unsaturation, the substituent R^{27 '}~ R ^{31 '} Any of the groups of the above may be combined and substituted or unsubstituted
A sum part can be formed),   h) oxazolidine sulfonimine [XXXIa], phosphine represented by the following formula
Hongimine [XXXIb], N-acylimine [XXXII]: [Chemical 28] (In the formula, each R^{46 '}Are independently H, alkyl, cycloalkyl, aryl,
Fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, a
Selected from the group consisting of lucoxy, keto, carboxyl, and carboalkoxy groups
Selected from the substituted, substituted or unsubstituted groups, all two
vic-R^{46 '}The substituents may be combined to form a fused aryl, fused carbocycle or fused
Can form a ring, R^{45 '}Is H, alkyl, cycloalkyl, ar
Caryl, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, su
From Ruphonate, Alkoxy, Keto, Carboxyl, and Carboalkoxy groups
May be a substituted or unsubstituted group selected from the group consisting of
If present, (1) -O-, (2) -N (R^{47 '})-, And (3) -N (
R^{47 '}R^{48 '}) -Selected from the group consisting of^{47 '}~ R^{48 '}Is independent
, H, oxygen, linear or branched C₁~ C₁₂Alkyl, alkylene, a
Lucoxy, aryl, alkaryl, aralkyl, cycloalkyl, and hetero
A substituted or unsubstituted group selected from the group consisting of rings)
,and   i) a mixture thereof. 4.   The method of claim 1, wherein the fabric comprises a stain. 5. A bleaching composition comprising (a) a source of peroxygen, and (b) an organic catalyst, wherein the organic catalyst is in a cleaning solution containing the bleaching composition by a controlled activation method. A bleaching composition characterized by being effective in. 6. A peroxygen source is selected from the group consisting of (i) percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. A preformed peracid compound, and (ii) a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and a bleach activator. A bleaching composition according to claim 5 selected from the group consisting of: 7. The peroxygen source is a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and bleach activators. A bleaching composition according to claim 6, which is selected. 8. A bleaching composition according to claim 7, wherein the bleaching activator is selected from the group consisting of hydrophobic bleaching activators. 9.   Bleach activator is tetraacetylethylenediamine (TAED), benzodolphin
Prolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chloro
Benzoyl caprolactam, benzoyloxybenzene sulfonate (BOBS
), Nonanoyloxybenzene sulfonate (NOBS), phenyl benzoate (
PhBz), decanoyloxybenzene sulfonate (C₁₀-OBS), Ben
Zoyl valerolactam (BZVL), octanoyloxybenzene sulfonate
(C₈-OBS), perhydrolyzable ester, 4- [N- (no
Nanoyl) aminohexanoyloxy] -benzenesulfonate sodium salt (
NACA-OBS), lauryloxybenzene sulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzene sulfonate (UDOB)
S or C containing unsaturation at position 10₁₁-OBS), decanoyloxybenzoic acid
8. A composition according to claim 7, selected from the group consisting of (DOBA) and mixtures thereof.
Bleaching composition. 10.   The drift according to claim 5, wherein the organic catalyst is selected from the group consisting of a) to i) below.
White composition.   a) Aryl having a net charge of about +3 to about -3 represented by formula [I] below.
Iminium cations and aryliminium polyions: [Chemical 29] (In the formula, R¹And R^TwoAre independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sul
Select from honato, alkoxy, keto, carboxyl, and carboalkoxy groups
R, selected from selected, substituted or unsubstituted groups, R¹And R ^Four Is H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
Heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and carboalco
Selected from xyl groups, substituted or unsubstituted, saturated or unsaturated.
KM, X⁻Is a counter ion that has a suitable charge balance, and v is an integer of 1 to 3.
Is a number),   b) Aryl having a net charge of about +3 to about -3, represented by formula [II] below.
Iminium Zwitterion: [Chemical 30] (In the formula, R⁵~ R⁷Are independently H, alkyl, cycloalkyl, aryl,
Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfona
Group consisting of alkoxide, alkoxy, keto, carboxyl, and carboalkoxy groups
Selected from substituted, unsubstituted or substituted groups from
In, there is also a group represented by the following formula, [Chemical 31] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is substituted or unsubstituted, saturated or tired
Sum alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and
Selected from the group consisting of heterocycles),   c) a net charge of about -3 to about +3, represented by formulas [V] and [VI] below.
Modified amine: [Chemical 32] (In the formula, R⁹~ R¹⁰Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Nato, alkoxy, keto, carboxyl, and carboalkoxy groups and anions
A substituted or substituted group selected from groups having an ionic and / or cationic charge.
Or a non-substituted group, R⁸And R¹¹Is present, if present
Substituted or unsubstituted, saturated or unsaturated, H, alkyl, sic
Low alkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro,
Halo, cyano, sulfonate, alkoxy, keto and carboalkoxy groups and
And a group selected from the group consisting of groups having anionic and / or cationic charges
And R¹²Is a leaving group and its protonated form is pK_aValue (H_TwoO
Standard) is 37> pK_aIt falls within the range of> -2, but R⁸~ R¹²Is all
When present, they combine to form a fused aryl, fused carbocycle or fused heterocycle.
And a group represented by the formula: [Chemical 33] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is substituted or unsubstituted, saturated or tired
Sum alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and
Selected from the group consisting of heterocycles),   d) A variable having a net charge of about -3 to about +3, represented by the following formulas [VII] to [X].
Amine oxide: [Chemical 34] (In the formula, R⁹~ R¹⁰Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Nato, alkoxy, keto, carboxyl, and carboalkoxy groups and anions
A substituted or substituted group selected from groups having an ionic and / or cationic charge.
Or a non-substituted group, R⁸And R¹¹Was replaced, and also
Is an unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl, aryl
Reel, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano,
Alkoxy, keto, carboalkoxy groups and anions and / or cations
R is a group selected from a group having a charge,¹²Is a leaving group and its proton
The modified form is pK_aValue (H_TwoO standard) is 37> pK_aWithin the range of> -2
, But R⁸~ R¹²Are, when present, combined with condensed aryl, condensed carbon
It can form an elementary ring or a fused heterocycle, which is represented by the formula
There is also a group [Chemical 35] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is substituted or unsubstituted, saturated or tired
Sum alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and
Selected from the group consisting of heterocycles),   e) Represented by the following formulas [XXIa], [XXIb], [XXII] and [XXIII], respectively.
, Sulfonimines, phosphonimines, N-acylimines and thiodiazole diamines
Oxide: [Chemical 36] (In the formula, R⁴¹~ R⁴⁴Are, when present, independently H, alkyl, cycloal
Kill, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
Saturated, substituted or unsubstituted, selected from the group consisting of xy groups
Or selected from unsaturated groups with the proviso that R⁴¹~ R⁴⁴Is all other R^{Four 1} ~ R⁴⁴A fused aryl, fused carbocycle or fused heterocycle.
Can form part of a common ring that it includes),   f) an oxa having a net charge of about +3 to about -3 represented by the following formula [III]:
Diridinium cations and polyions: [Chemical 37] (In the formula, R^{2 '}~ R^{3 '}Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Consisting of nato, alkoxy, keto, carboxyl, and carboalkoxy groups
R is selected from the group selected from the group, substituted or unsubstituted, R^{1 '} And R^{4 '}Is a substituted or unsubstituted, saturated or unsaturated
, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, hetero
Ring, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy
A group selected from the group consisting of groups, X⁻Is a suitable charge balancing counter-ion
And v is an integer of 1 to 3),   g) Oxadiene represented by the following formula [IV] and having a net charge of about +3 to about -3.
Lyzinium Zwitterion: [Chemical 38] (In the formula, R^{5 '}~ R^{7 '}Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sul
It consists of phonato, alkoxy, keto, carboxyl, and carboalkoxy groups.
Selected from the group consisting of substituted, unsubstituted or substituted groups,
In the formula, there are also groups represented by the following formula, [Chemical Formula 39] Where Z ′_p ⁻Is T ’₀Covalently bound to Z '_p ⁻Is -CO_Two ⁻, -SO_Three ⁻,
-OSO_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
2 or 3 and T '₀Is saturated, either substituted or unsubstituted.
Or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl
, And a heterocycle),   h) Oxaziridine sulfonimine [XXIVa], phosphon represented as follows:
Imine [XXIVb], N-acylimine [XXV], and thiodiazole dioxide [X
XVI] and [XXVII]: [Chemical 40] (In the formula, R^{41 '}~ R^{44 '}Are, when present, independently H, alkyl, cyclo
Alkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, ha
B, cyano, sulfonate, alkoxy, keto, carboxyl, and carboa
A substituted or unsubstituted group selected from the group consisting of lucoxy groups
Selected from R^{41 '}~ R^{44 '}Is all other R^{41 '}~ R^{44 '} Bound to any of the above and includes fused aryl, fused carbocycle or fused heterocycle
Can form part of a common ring), and   i) a mixture thereof. 11.   The organic catalyst according to claim 10, wherein the organic catalyst is selected from the group consisting of a) to i) below.
Bleaching composition.   a) Aryl having a net charge of about +3 to about -3 represented by formula [XI] below.
Iminium cations and aryliminium polyions: [Chemical 41] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R²⁰Are independently H, alkyl,
Chloroalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
From a substituted or unsubstituted group selected from the group consisting of xy groups
All 2 vic-Rs selected²⁰The substituents are combined to form a fused aryl,
Fused carbocycles or fused heterocycles can be formed, R¹⁸Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nit
B, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of ruvoalkoxy groups, substituted or substituted
R may be a non-group¹⁹Is a substituted or unsubstituted, saturated or unsaturated
Saturated, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl
And a group selected from the group consisting of heterocycles, G is (1) -O-, (2)
-N (R²³)-, And (3) -N (R²³R²⁴) -Selected from the group
R²¹~ R²⁴Are independently H, oxygen, linear or branched C₁~ C ₁₂ Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl
Selected from the group consisting of :, a cycloalkyl, and a heterocycle, a substituted, and
Is an unsubstituted group, provided that R is¹⁸, R¹⁹, R²⁰, R²¹~ R^{Two Four} Is all R¹⁸, R¹⁹, R²⁰, R²¹~ R²⁴Combined with any of
Can form part of a ring, all gem-R²¹~ R²²Are combined
Can form carbonyls and all vic-R²¹~ R²⁴Is united
To form an unsaturation, the substituent R²¹~ R²⁴All the groups of
To form a fused unsaturated moiety, substituted or unsubstituted,
X⁻Is a suitable charge-balancing counterion and v is an integer from 1 to 3),   b) an aryl having a net charge of about +3 to about -3, represented by formula [XII] below.
Ruiminium twin ion: [Chemical 42] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R²⁶Are independently H, alkyl,
Chloroalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo,
Cyano, sulfonate, alkoxy, keto, carboxyl, and carboalco
From a substituted or unsubstituted group selected from the group consisting of xy groups
All 2 vic-Rs selected²⁶The substituents are combined to form a fused aryl,
Fused carbocycles or fused heterocycles can be formed, R²⁵Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nit
B, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of ruvoalkoxy groups, substituted or substituted
The group represented by the following formula also exists in this formula, [Chemical 43] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 44] Is selected from the group consisting of: wherein q is an integer from 1 to 8;²⁹Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R^Thirty)-, And (3) -N (R^ThirtyR³¹) -Selected from the group consisting of ²⁷ , R²⁸, R^ThirtyAnd R³¹Are independently H, oxygen, alkyl, cyclo
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alco
Group consisting of xy, arylcarbonyl group, carboxyalkyl group and amido group
R is a substituted or unsubstituted group selected from R²⁵, R^{Two 6} , R²⁷, R²⁸, R^ThirtyAnd R³¹Is all R²⁵, R²⁶, R²⁷,
R²⁸, R^ThirtyAnd R³¹To form part of a common ring with any of
And all gem-R²⁷~ R²⁸Combine to form carbonyl
Can and all vic-R²⁷~ R³¹Can combine to form unsaturation
Yes, substituent R²⁷~ R³¹Substituted or combined with any group of
Uncondensed fused unsaturated moieties can be formed),   c) Modified amines represented by the following formulas [XV] and [XVI]: [Chemical formula 45] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is or has been replaced
Unsaturated or unsaturated hydroxy, perhydroxy, alkoxy, pera
Lucoxy, carboxyl, percarboxyl, sulfonate, persulfonate
R is a group selected from the group consisting of³⁵Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs³⁵Substituents are combined and fused aryl
, Fused carbocycles or fused heterocycles can be formed, R³²Is H, alkyl
, Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, di
Toro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of carboalkoxy groups, substituted or substituted
R may be a non-group³³Is H, alkyl, cycloalkyl, alkaryl, a
Selected from the group consisting of reel, aralkyl, and heterocycle, substituted or substituted
It may be a saturated or unsaturated group which is not converted, and this formula is represented by the following formula.
There is also a group that is [Chemical formula 46] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 47] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R³⁹)-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of ³⁶ , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloalkyl
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
A group consisting of cis, arylcarbonyl group, carboxyalkyl group and amido group
R is a group selected from, substituted or unsubstituted, R³², R³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R ³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with either
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a group
Can be combined to form a carbonyl, all vic-R³⁶, R³⁷,
R³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R ³⁷ , R³⁹And R⁴⁰All of the groups are substituted or substituted.
Uncondensed unsaturated moieties can be formed),   d) Modified amine oxide represented by the following formulas [XVII] to [XX]: [Chemical 48] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is or has been replaced
Unsaturated or unsaturated hydroxy, perhydroxy, alkoxy, pera
Lucoxy, carboxyl, percarboxyl, sulfonate, persulfonate
R is a group selected from the group consisting of³⁵Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs³⁵Substituents are combined and fused aryl
, Fused carbocycles or fused heterocycles can be formed, R³²Is H, alkyl
, Cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, di
Toro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and
Selected from the group consisting of carboalkoxy groups, substituted or substituted
R may be a non-group³³Is H, alkyl, cycloalkyl, alkaryl, a
Selected from the group consisting of reel, aralkyl, and heterocycle, substituted or substituted
It may be a saturated or unsaturated group which is not converted, and this formula is represented by the following formula.
There is also a group that is [Chemical 49] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 50] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group, G is (1) -O-, (2) -N (
R³⁹)-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of ³⁶ , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloalkyl
Alkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
A group consisting of cis, arylcarbonyl group, carboxyalkyl group and amido group
R is a group selected from, substituted or unsubstituted, R³², R³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R ³³ , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with either
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a group
Can be combined to form a carbonyl, all vic-R³⁶, R³⁷,
R³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R ³⁷ , R³⁹And R⁴⁰All of the groups are substituted or substituted.
Uncondensed unsaturated moieties can be formed), e) Sulfonimine [XXVIIIa], Phosphonimine [XXVI] represented by the following formula
IIb], N-acylimine [XXIX]: [Chemical 51] (In the formula, each R⁴⁶Are independently H, alkyl, cycloalkyl, aryl, condensed
Fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, ar
Selected from the group consisting of coxy, keto, carboxyl, and carboalkoxy groups
Selected from selected, substituted or unsubstituted groups, all two vi
c-R⁴⁶The substituents are combined to form a fused aryl, fused carbocycle or fused heterocycle.
Can form R⁴⁵Is H, alkyl, cycloalkyl, alkali
Ru, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfona
Group consisting of alkoxide, alkoxy, keto, carboxyl, and carboalkoxy groups
Can be a substituted or unsubstituted group selected from
In case of (1) -O-, (2) -N (R⁴⁷)-, And (3) -N (R⁴⁷R ⁴⁸ ) -Selected from the group consisting of⁴⁷~ R⁴⁸Independently, H, oxygen, direct
Chain or branched C₁~ C₁₂Alkyl, alkylene, alkoxy, ally
From the group consisting of alkaryl, alkaryl, aralkyl, cycloalkyl, and heterocycle.
A selected, substituted or unsubstituted group),   f) Oxa represented by the following formula [XIII] and having a net charge of about +3 to about -3.
Diridinium cations and polyions: [Chemical 52] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R^{20 '}Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs^{20 '}The substituents are combined to form a condensed aryl.
R, a fused carbocycle or a fused heterocycle can be formed, R^{18 '}Is H, Al
Kill, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl
, Nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl,
And carboalkoxy groups selected from the group consisting of, substituted or substituted
R may be a group that is not^{19 '}Is saturated, substituted or unsubstituted
Or unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aryl
A group selected from the group consisting of aralkyl and heterocycle, G being (1) -O-
, (2) -N (R^{23 '})-, And (3) -N (R^{23 '}R^{24 '})-
Selected from the group R^{21 '}~ R^{24 '}Are independently H, oxygen, straight chain or
Branched chain C₁~ C₁₂Alkyl, alkylene, alkoxy, aryl, alk
Selected from the group consisting of reel, aralkyl, cycloalkyl, and heterocycle
, A substituted or unsubstituted group, with the proviso that R is^{18 '}, R^{19 '} , R^{21 '}~ R^{24 '}Is all R^{18 '}, R^{19 '}, R^{21 '}~ R^{24 '}Noi
Can be combined with a gap to form part of a common ring, and all gem-R^{21 '}
~ R^{22 '}Can combine to form a carbonyl, and all vic-
R^{21 '}~ R^{24 '}Can combine to form unsaturation, the substituent R^{21 '}~
R^{24 '}Any of the above groups in combination with a substituted or unsubstituted
Can form a saturated moiety and has a substituent R^{21 '}~ R^{24 '}Any group of
Can form fused unsaturated moieties that can be substituted or unsubstituted.
X⁻Is a suitable charge-balancing counterion and v is an integer from 1 to 3.
),   g) an oxa having a net charge of about +3 to about -3 represented by the following formula [XIV]:
Zyridinium Zwitterion: [Chemical 53] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, and each R^{26 '}Are independently H, alkyl,
Cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo
, Cyano, sulfonate, alkoxy, keto, carboxyl, and carboar
Is a substituted or unsubstituted group selected from the group consisting of coroxy groups
Selected from all 2 vic-Rs^{26 '}The substituents are combined to form a condensed aryl.
R, a fused carbocycle or a fused heterocycle can be formed, R^{25 '}Is H, Al
Kill, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl
, Nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl,
And carboalkoxy groups selected from the group consisting of, substituted or substituted
The group represented by the following formula also exists in this formula, [Chemical 54] Where Z ′_p ⁻Is T ’₀Covalently bound to Z '_p ⁻Is -CO_Two ⁻, -SO_Three ⁻,
-OSO_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 2 and T '₀Is [Chemical 55] Is selected from the group consisting of: wherein q is an integer from 1 to 8;^{29 '}Is independent
, Linear or branched, H, alkyl, cycloalkyl, alkali-
Ru, aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarbo
A substituted, selected from the group consisting of nyl, carboxyalkyl and amido groups.
Or a group not substituted, G is (1) -O-, (2) -N
(R^{30 '})-, And (3) -N (R^{30 '}R^{31 '})-Selected from the group consisting of
And R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Are independently H, oxygen,
Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene
, Heterocycles, alkoxy, arylcarbonyl groups, carboxyalkyl groups and
A substituted or unsubstituted group selected from the group consisting of
R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}All
And R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Nozu
Can bind to it to form part of a common ring, and all gem-R^{27 '}~
R^{28 '}Can combine to form a carbonyl, and all vic-R
^{27 '}~ R^{31 '}Can combine to form unsaturation, the substituent R^{27 '}~ R ^{31 '} Any of the groups of the above may be combined and substituted or unsubstituted
A sum part can be formed),   h) oxazolidine sulfonimine [XXXIa], phosphine represented by the following formula
Hongimine [XXXIb], N-acylimine [XXXII]: [Chemical 56] (In the formula, each R^{46 '}Are independently H, alkyl, cycloalkyl, aryl,
Fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, a
Selected from the group consisting of lucoxy, keto, carboxyl, and carboalkoxy groups
Selected from the substituted, substituted or unsubstituted groups, all two
vic-R^{46 '}The substituents may be combined to form a fused aryl, fused carbocycle or fused
Can form a ring, R^{45 '}Is H, alkyl, cycloalkyl, ar
Caryl, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, su
From Ruphonate, Alkoxy, Keto, Carboxyl, and Carboalkoxy groups
May be a substituted or unsubstituted group selected from the group consisting of
If present, (1) -O-, (2) -N (R^{47 '})-, And (3) -N (
R^{47 '}R^{48 '}) -Selected from the group consisting of^{47 '}~ R^{48 '}Is independent
, H, oxygen, linear or branched C₁~ C₁₂Alkyl, alkylene, a
Lucoxy, aryl, alkaryl, aralkyl, cycloalkyl, and hetero
A substituted, or unsubstituted group selected from the group consisting of rings,
n is an integer of 0 to 4), and   i) a mixture thereof. 12. A surfactant, a solvent, a buffer, an enzyme, a soil release agent, a clay soil remover, a dispersant,
Brighteners, foam inhibitors, fabric softeners, foam organic catalysts, enzyme stabilizers, builders, chelating agents, other bleaches including metal catalysts, other organic catalysts, dyes,
6. The bleaching composition of claim 5, further comprising one or more detergent ingredients selected from the group consisting of dye transfer inhibitors, perfumes, and mixtures thereof. 13. A product comprising an organic catalyst, further comprising instructions for cleaning fabrics in need of cleaning with said compound, the instructions comprising the product. Contacting the cloth with the cleaning solution consisting of
Article, characterized in that it comprises a step in which the organocatalyst becomes effective in the washing solution by a controlled activation method. 14.   14. A product according to claim 13 which is a laundry detergent. 15.   14. The product of claim 13 which is a laundry additive. 16. A modified amine compound selected from the group consisting of modified amine oxides having the following general formulas [VII] to [X]: [Chemical 58] (In the formula, R ^{8 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy group and anion. And / or selected from groups having a cationic charge, selected from substituted or unsubstituted groups, R ¹¹ , if present, is substituted or unsubstituted, saturated or unsaturated. Selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy groups and groups having anionic and / or cationic charges. a ^{group, R 12} is a leaving group, the protonated form pK _a value _(H 2 O
Reference), but falls within the range of 37> _pK a> -2, provided that ^R 8 ^{to R 12,} if present, can be combined to form a fused aryl, fused carbocyclic or fused heterocyclic ring). 17. The modified amine compound according to claim 16, wherein R ¹¹ is represented by the following formula: (Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is _{^{-CO 2 -, -SO 3 -,}} -O
Selected from the group consisting of SO ₃ ⁻ , —SO ₂ ^−, and —OSO ₂ ⁻ , and p is 1, 2
Or 3 and T ₀ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle. 18. The modified amine compound according to claim 18, which has _a pK _a value of more than 3 and less than 23 with respect to R ¹² . 19. The modified amine compound according to claim 17, which has _a pK _a value of more than 9 and less than 21 with respect to R ¹² . Respect 20. R ^12, pK _a value is greater than 11 and less than 17, claim 18
The modified amine compound described in 1. 21. The modified amine according to claim 16, wherein R ¹² is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups. Compound. 22. The R ¹² is selected from the group consisting of hydroxy or perhydroxy.
The modified amine compound according to claim 21. 23.   The modified amine compound according to claim 16, which has the following general formulas [XVII] to [XX]: [Chemical 60] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is a leaving group and its protonated
The morphology is pK_aValue (H_TwoO standard) is 37> pK_a> R, each R ³⁵ Are independently H, alkyl, cycloalkyl, aryl, fused aryl,
Heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto
A substituted, selected from the group consisting of, carboxyl, and carboalkoxy groups.
All two vic-R selected from a substituted or unsubstituted group.³⁵Setting
The substituents may combine to form a fused aryl, fused carbocycle or fused heterocycle.
Can be done, R³²Is H, alkyl, cycloalkyl, alkaryl, aryl
, Aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, arco
Selected from the group consisting of xy, keto, carboxyl, and carboalkoxy groups.
, A substituted or unsubstituted group, R³³Is H, alkyl,
From the group consisting of cycloalkyl, alkaryl, aryl, aralkyl, heterocycle
It may be a selected, substituted or unsubstituted, saturated or unsaturated group.
I). 24.   R³³Is represented by the following formula, [Chemical formula 61] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical formula 62] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group,   G is (1) -O-, (2) -N (R³⁹)-, And (3) -N (R³⁹R ⁴⁰ )-Is selected from the group consisting of   R³⁶, R³⁷, R³⁹And R⁴⁰Independently of H, oxygen, alkyl,
Roalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, ar
Consists of koxy, arylcarbonyl groups, carboxyalkyl groups and amide groups
A group selected from the group, substituted or unsubstituted,   R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Gasp
All R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰ Can be combined with any of the above to form part of a common ring, and all gem-R^Three
6~ R³⁷Can combine to form a carbonyl, and all vic-
R³⁶, R³⁷, R³⁹And R⁴⁰Can combine to form unsaturation,
Substituent R³⁶, R³⁷, R³⁹And R⁴⁰Any of the groups can be combined and substituted
Or a fused unsaturated moiety which can be substituted can be formed.
The modified amine compound according to item 3. 25. The modified amine compound according to claim 23, which has _a pK _a value of more than 3 and less than 23 with respect to R ³⁴ . 26. The modified amine compound according to claim 25, which has _a pK _a value of more than 11 and less than 17 with respect to R ³⁴ . 27. The modified amine according to claim 23, wherein R ³⁴ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups. Compound. 28. The modified amine compound according to claim 27, wherein R ³⁴ is selected from the group consisting of hydroxy or perhydroxy. 29.   The modified amination according to claim 16, represented by the following formulas [XV] and [XVI]:
Compound: [Chemical formula 63] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is a leaving group and its protonated
The morphology is pK_aValue (H_TwoO standard) is 20> pK_aWithin the range of> 10, each R ³⁵ Are independently H, alkyl, cycloalkyl, aryl, fused aryl,
Heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto
All selected from the group consisting of, carboxyl, and carboalkoxy groups
2 vic-R³⁵The substituents may be combined in a fused aryl, fused carbocycle or condensed ring.
Can form a heterocyclic ring, R³²Is selected from the group consisting of H or Me
R is a group³³Is C_Three~ C₁₈Alkyl, C_Three~ C₁₈Cycloalkyl
And selected from the group consisting of groups having anionic and / or cationic charges.
Saturated, unsaturated groups, substituted, unsubstituted, or substituted). 30.   R³³Is represented by the following formula, [Chemical 64] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 65] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group,   G is (1) -O-, (2) -N (R³⁹)-, And (3) -N (R³⁹R ⁴⁰ )-Is selected from the group consisting of   R³⁶, R³⁷, R³⁹And R⁴⁰Independently of H, oxygen, alkyl,
Roalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, ar
Consists of koxy, arylcarbonyl groups, carboxyalkyl groups and amide groups
A group selected from the group, substituted or unsubstituted,   R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Gasp
All R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰ Can be combined with any of the above to form part of a common ring, and all gem-R^Three
6~ R³⁷Can combine to form a carbonyl, and all vic-
R³⁶, R³⁷, R³⁹And R⁴⁰Can combine to form unsaturation,
Substituent R³⁶, R³⁷, R³⁹And R⁴⁰Any of the groups can be combined and substituted
Or a fused unsaturated moiety which can be substituted can be formed.
9. The modified amine compound according to item 9. 31. The modified amine compound according to claim 29, wherein R ³⁴ is selected from the group consisting of hydroxy or perhydroxy groups. 32. A bleaching composition comprising a modified amine compound with or without a peroxygen source, wherein the modified amine compound has the following general formulas [V] and / or [VI]: A bleaching composition characterized by being selected from the group consisting of modified amines having the following formulas, modified amine oxides having the following general formulas [VII] to [X], and mixtures thereof: [Chemical formula 67] (In the formula, R ^{8 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy group and anion. And / or selected from groups having a cationic charge, selected from substituted or unsubstituted groups, R ¹¹ , if present, is substituted or unsubstituted, saturated or unsaturated. Selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy groups and groups having anionic and / or cationic charges. a ^{group, R 12} is a leaving group, the protonated form pK _a value _(H 2 O
Reference), but falls within the range of 37> _pK a> -2, provided that ^R 8 ^{to R 12,} if present, can be combined to form a fused aryl, fused carbocyclic or fused heterocyclic ring). 33. A bleaching composition according to claim 32, wherein R ¹¹ is represented by the formula: (Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is _{^{-CO 2 -, -SO 3 -,}} -O
Selected from the group consisting of SO ₃ ⁻ , —SO ₂ ^−, and —OSO ₂ ⁻ , and p is 1, 2
Or 3 and T ₀ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle. 34. The bleaching composition according to claim 32, which has _a pKa value of greater than 3 and less than 23 for R ¹² . 35. The bleaching composition according to claim 34, which has _a pKa value of greater than 9 and less than 21 for R ¹² . 36. For R ¹² , the pK _a value is greater than 11 and less than 17.
The bleaching composition described in. 37. The bleaching composition according to claim 32, wherein R ¹² is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups. object. 38. The bleaching composition according to claim 37, wherein R ¹² is selected from the group consisting of hydroxy or perhydroxy. 39. The modified amine compound comprises from about 0.001 to about 10% by weight of the bleaching composition, and the peroxygen source, if present, from about 0.01 to about 60% by weight of the bleaching composition. 33. The bleaching composition of claim 32, which comprises: 40. A peroxygen source, if present, comprises (a) percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. A preformed peracid compound selected from the group, and (b) a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, 33. The bleaching composition of claim 32, selected from the group consisting of and bleach activators. 41.   Bleaching characterized in that the modified amine compound has the following general formula [XV] to [XX]
Composition: [Chemical 69] (In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to
4, n is an integer of 0 to 4, R³⁴Is a leaving group and its protonated
The morphology is pK_aValue (H_TwoO standard) is 37> pK_a> R, each R ³⁵ Are independently H, alkyl, cycloalkyl, aryl, fused aryl,
Heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto
A substituted, selected from the group consisting of, carboxyl, and carboalkoxy groups.
All two vic-R selected from a substituted or unsubstituted group.³⁵Setting
The substituents may combine to form a fused aryl, fused carbocycle or fused heterocycle.
Can be done, R³²Is H, alkyl, cycloalkyl, alkaryl, aryl
, Aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, arco
Selected from the group consisting of xy, keto, carboxyl, and carboalkoxy groups.
, A substituted or unsubstituted group, R³³Is H, alkyl,
From the group consisting of cycloalkyl, alkaryl, aryl, aralkyl, heterocycle
Substitutions, including selected groups with anionic and / or cationic charges
Saturated or unsaturated groups, which may be substituted or unsubstituted). 42.   R³³Is represented by the following formula, [Chemical 70] Where Z_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OS
O_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Is selected from the group consisting of
Or 3 and T₀Is [Chemical 71] Is selected from the group consisting of: wherein q is an integer from 1 to 8;³⁸Independently
, Linear or branched, H, alkyl, cycloalkyl, alkaryl
, Aryl, aralkyl, alkylene, heterocycle, alkoxy, arylcarboni
A substituted, selected from the group consisting of
, Or an unsubstituted group,   G is (1) -O-, (2) -N (R³⁹)-, And (3) -N (R³⁹R ⁴⁰ )-Is selected from the group consisting of   R³⁶, R³⁷, R³⁹And R⁴⁰Independently of H, oxygen, alkyl,
Roalkyl, alkaryl, aryl, aralkyl, alkylene, heterocycle, ar
Consists of koxy, arylcarbonyl groups, carboxyalkyl groups and amide groups
A group selected from the group, substituted or unsubstituted,   R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Gasp
All R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰ Can be combined with any of the above to form part of a common ring, and all gem-R^Three
6~ R³⁷Can combine to form a carbonyl, and all vic-
R³⁶, R³⁷, R³⁹And R⁴⁰Can combine to form unsaturation,
Substituent R³⁶, R³⁷, R³⁹And R⁴⁰Any of the groups can be combined and substituted
5. A fused unsaturated moiety, which may be substituted or unsubstituted, may be formed.
The bleaching composition according to 1. 43. A bleaching composition according to claim 41 having _a pK _a value of greater than 3 and less than 23 with respect to R ³⁴ . 44. A bleaching composition according to claim 43 having _a pKa value of greater than 11 and less than 17 for R ³⁴ . 45. A bleaching composition according to claim 41, wherein R ³⁴ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy groups. object. 46. The bleaching composition according to claim 45, wherein R ³⁴ is selected from the group consisting of hydroxy or perhydroxy. 47. The bleaching composition comprises a surfactant, a solvent, a buffer, an enzyme, a soil release agent, a clay soil remover, a dispersant, a brightener, a foam inhibitor, a fabric softening agent, and a foam enhancer. , Enzyme stabilizers, builders, chelating agents, other bleaching agents, dyes, dye transfer inhibitors,
33. The bleaching composition of claim 32, further comprising one or more detergent ingredients selected from the group consisting of perfumes and mixtures thereof. 48.   48. The bleaching composition of claim 47, further comprising a surfactant. 49.   49. The bleaching composition of claim 48, wherein the surfactant is a branched chain surfactant. 50. The bleaching composition according to claim 49, wherein the branched-chain surfactant is a medium-chain branched surfactant. 51.   49. The bleaching composition according to claim 48, wherein the surfactant is an anionic surfactant. 52.   42. The bleaching composition of claim 41, further comprising a chelating agent. 53. The bleaching composition of claim 41, further comprising other bleaching agents selected from the group consisting of perborate salts, percarbonate salts, perphosphate salts and mixtures thereof. 54.   54. The bleaching composition of claim 53, further comprising a bleach activator. 55. The bleaching composition of claim 54, wherein the bleaching activator is selected from the group consisting of hydrophobic bleaching activators. 56. The hydrophobic bleaching activator is tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-
Chlorobenzoylcaprolactam, benzoyloxybenzene sulfonate (B
OBS), nonanoyloxybenzene sulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzene sulfonate (C ₁₀ -OBS).
, Benzoyl valerolactam (BZVL), octanoyloxybenzene sulfonate (C ₈ -OBS), perhydrolyzable ester, 4- [N
-(Nonanoyl) aminohexanoyloxy] -benzenesulfonate sodium salt (NACA-OBS), lauryloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzenesulfonate (U
DOBS or C ₁₁ -OBS containing unsaturation at position 10), decanoyloxybenzoic acid (DOBA) and mixtures thereof.
The bleaching composition according to 5. 57.   42. The bleaching composition of claim 41, further comprising an enzyme. 58. The bleaching composition according to claim 57, wherein the enzyme is selected from the group consisting of cellulase, lipase, amylase, phospholipase, protease, peroxidase and mixtures thereof. 59. A method of laundering a fabric in need of cleaning comprising contacting the fabric with a laundry solution having the bleaching composition of claim 32. 60. A laundry additive product comprising a modified amine compound selected from the group consisting of modified amine compounds having the following general formulas [V]-[X], and mixtures thereof: embedded image ] [Chemical formula 73] (In the formula, R ^{8 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy group and anion. And / or selected from groups having a cationic charge, selected from substituted or unsubstituted groups, R ¹¹ , if present, is substituted or unsubstituted, saturated or unsaturated. Selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy groups and groups having anionic and / or cationic charges. a ^{group, R 12} is a leaving group, the protonated form pK _a value _(H 2 O
Reference), but falls within the range of 37> _pK a> -2, provided that ^R 8 ^{to R 12,} if present, can be combined to form a fused aryl, fused carbocyclic or fused heterocyclic ring). 61. A laundry additive product according to claim 60, wherein R ¹¹ is represented by the formula: (Wherein, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is _{^{-CO 2 -, -SO 3 -,}} -O
Selected from the group consisting of SO ₃ ⁻ , —SO ₂ ^−, and —OSO ₂ ⁻ , and p is 1, 2
Or 3 and T ₀ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle. 62. The laundry additive product of claim 60 which is a dosage form selected from the group consisting of prills, tablets, caplets, gelcaps or other single dose forms. 63. The laundry additive product of claim 60, further comprising a suitable carrier.