JP2003508585A - Stable formulation components, compositions using those components and washing methods - Google Patents

Abstract

  (57) [Summary] The present invention relates to formulation components, such as organic catalyst compounds with enhanced stability, compositions using such organic catalyst compounds, and washing methods. More particularly, the present invention relates to organic catalyst compounds, such as quaternary imine bleach booster compounds, quaternary oxaziridinium bleaching materials, modified amines and amine oxides, and compositions using such organic catalyst compounds. And a washing method.

Description

Detailed Description of the Invention

[0001]

FIELD The present invention relates ingredients of the Invention Background of the Invention, e.g., an organic catalyst compound with enhanced stability, compositions and laundry methods of using such organic catalyst compounds. More particularly, the present invention relates to organocatalyst compounds, such as quaternary imine bleach enhancer compounds, quaternary oxaziridinium bleaching agents, modified amines and amine oxides, compositions using such organocatalyst compounds. And concerning the washing method.

[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,
Particularly desirable for cleaning, whitening and bactericidal properties of lightly soiled fabrics. 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 drawbacks are poor fabric color safety and a tendency 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 with leaving groups such as oxybenzene sulfonate, react with active oxygen groups, typically hydrogen peroxide, or its anions to make it more effective. It forms a stable peroxyacid oxidant. The peroxyacid compound then oxidizes the stained or soiled substrate. However, bleach activators are also somewhat temperature dependent. Bleach activator is about 4
Warm water temperatures of 0 ° C to about 60 ° C are more effective. At water temperatures below about 40 ° C, peroxyacid compounds lose some of their bleaching efficacy.

All Madison et al. US Pat. Nos. 5,360,568, 5,360,569 and 5,37.
No. 0,826, an attempt to develop a bleaching system comprising an organic catalyst that is effective under low temperature water conditions and safe against color, and more specifically, an iminium-based organic catalyst. It is done, but it is unsuccessful. The cationic quaternary imine salts, which are the organic catalysts disclosed in these applications, are not entirely satisfactory for laundry bleaching applications. In particular, quaternary imine salts, when combined with peroxygen compounds, cause unacceptable levels of color damage on the fabric. Further, the quaternary imine salt has low stability at high washing temperature and may lose its effect.

US Pat. Nos. 5,576,282 and 5,817,614, both to Miracle et al., Disclose another bleach system that comprises a color-safe organocatalyst that is effective under cold water conditions. The attempt of is described. The bleaching system disclosed in this patent has enhanced color safety in cold water conditions over traditional organic catalyzed bleaching systems, but it does achieve such bleaching even at high wash temperatures. Is preferred.

Many iminium and dihydroquinolinium representatives in the field, and quaternary oxaziridinium bleaches formed therefrom, have an organocatalyst lifetime as measured by the test method described below. It is less than 30 minutes at 20 ° C. At higher temperatures, for example 40 ° C., the lifetime of these organocatalysts is less than 3 minutes. At higher temperatures, such as 60 ° C, the life of the organocatalyst is less than 20 seconds. Due to such instability at high wash temperatures, the effect can be drastically diminished.

[0007] From the above, researchers have found that effective bleaching at both low (cold) and high (warm or hot) water temperature, good stability against undesired decomposition of organic catalysts, effective Pursuing organic catalyst bleach system.

Therefore, compared to the bleach systems disclosed in the prior art, the stability against undesired organic catalyst decomposition is excellent, not only bleaching effectively under low water temperature conditions, but also under high water temperature conditions. It is clear that there is still a need for organocatalytic bleach systems that bleach more effectively.

[0009]

[Outline of the Invention]

The present invention satisfies the above demands. The present invention provides formulation ingredients, such as organocatalyst compounds, having an organocatalyst life of greater than 30 minutes as measured by the test methods described below. Such an organocatalyst compound is not only effective for a long time under low temperature water conditions, for example at a temperature of 20 ° C. or lower described in the test method, for example, 5 ° C.,
It has a long catalyst life, even under high temperature water conditions, eg above 40 ° C., up to about 60 ° C., or even higher temperatures, compared to organic catalysts in prior art bleaching systems,
The stability of the organic catalyst is excellent.

For example, an organic catalyst compound having an organic catalyst life (OCL) of only 20 minutes at 20 ° C. as measured by the test method described below has an OCL of only about 2 minutes at 40 ° C. OCL is 1 at 20 ° C as measured by the test method described below.
An organocatalyst compound that is 0 hour has an OCL of about 1 hour at 40 ° C. Similarly,
Organocatalytic compounds having an OCL of 40 minutes at 20 ° C have an OCL of about 4 minutes at 40 ° C as measured by the test method described below. The performance advantage of 1 hour at 40 ° C is clear compared to 2 minutes at 40 ° C. For example, for a 10 minute wash cycle, at 40 ° C., if a stain-laden fabric that needs to be washed is added to the wash water after the OCL of the prior art catalyst is exhausted (ie, 2 minutes). Four
It can be said that the performance of the organocatalyst compound having a lifetime of minutes is far greater than that at 40 ° C. for 2 minutes. Whereas prior art organocatalysts do little or no bleaching (end of life), the organocatalysts provided by the invention (2 minutes OCL left) demonstrate effective bleaching. Will continue to do.

The present invention discloses, in addition to organocatalyst compounds, compositions and washing methods using such organocatalyst compounds. More specifically, the present invention relates to organocatalyst compounds, such as quaternary imine bleach enhancer compounds, quaternary oxaziridinium bleaching agents, modified amines and amine oxides, compositions using such organocatalytic compounds. And laundry methods.

Examples of the advantages offered by the formulation ingredients, in particular the organocatalytic compounds, are the bleaching effect in low and high temperature water, eg the possibility of various addition modalities such as stain removal, whitening, unfavorable organic Minimize the loss of peracid AvO due to bleaching of the catalytic decomposition products and the resulting decomposition products, and increase the efficiency of the organic catalyst (
That is, lowering the amount of organic catalyst used, thereby reducing the cost of the bleaching composition,
The effects on the environment are reduced and the formula space is reduced), but the invention is not limited thereto.

According to one aspect of the present invention, there is provided an organic catalyst compound which can be effectively bleached at low and high water temperatures and can be used in a wide temperature range, as compared with a formulation component, preferably a conventional organic catalyst. To do.

In another aspect of the present invention, one or more of the above formula ingredients is combined with a source of peroxygen.
A bleaching composition comprising, with or without, is provided.

In yet another aspect of the invention, there is provided a method of laundering a fabric, comprising contacting the fabric in need of cleaning with a laundry solution comprising one or more of the bleaching compositions described herein. To do.

In yet another aspect of the present invention, there is provided a laundry additive product comprising one or more of the formulation components described herein.

Accordingly, it is an object of the present invention to provide a bleaching composition comprising a formulation component, preferably an organocatalyst compound that exhibits excellent performance in low and high temperature water wash solutions, one or more of the formulation components described herein. , A method of laundering fabrics using one or more of the bleaching compositions described herein, and a laundry additive product comprising one or more of the formulation ingredients described herein.

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

[0020]

[Detailed Description of the Invention]

The present invention provides highly useful formulation ingredients, such as organocatalyst compounds (“bleach enhancer compounds”, “bleaching agents”, “modified amines”, “modified amine oxides” and mixtures thereof), compositions using formulation ingredients. Disclosed are articles and methods.

The formulation components of the present invention, especially the organocatalytic compounds, enhance the bleaching effect in low and high temperature water, such as stain removal, whitening, etc., as compared to conventional organocatalytic bleaching systems,
Allows various modes of addition, minimizes loss of peracid available oxygen (AvO) due to bleaching of undesired organocatalytic degradation products and the resulting degradation products, and enhances organic catalyst efficiency (eg, organic Lowering the amount of catalyst used, thereby lowering the cost of the bleaching composition, reducing the environmental impact and lowering the formulation space).
The formulation components of the present invention act in association with, or not associated with, a conventional source of peroxygen, preferably in association, to improve the stability of the organic catalyst as described above, To enhance bleaching efficiency.

Definitions 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 peroxyacids such as peroxycarboxylic acid and / or peroxymonosulfuric acid (trade name OXONE) and salts thereof.

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
No. 5,652,207 and 5,817,614, published PCT patent application WO98 / 23602,
WO95 / 13352, WO95 / 13353, WO95 / 13351, WO97 / 06147 and WO
98/23717 and European Patent No. 728182, but is not limited thereto.

The organocatalyst compounds of the present invention that are particularly useful in the compositions and methods of the present invention are those that have an organocatalyst life of greater than 30 minutes as measured by the test methods described below.

Preferably, the organocatalytic compounds of the present invention, more preferably the iminium-based organocatalytic compounds of the present invention, include bleach enhancer compounds, bleaching agents, modified amines, modified amine oxides and mixtures thereof. It is not limited to these.

Bleach Boosting Compounds The bleach boosting compounds of the present invention, preferably the iminium-based bleach boosting compounds, include:
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.

Aryliminium cations and aryliminium polyions with a net charge of about +3 to about −3 are represented by formula [I] below.

[Chemical 44] Wherein R ^{2 to} R ³ are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy. Selected from the group consisting of, substituted or unsubstituted, saturated or unsaturated groups, R ¹ and R ⁴ are substituted or unsubstituted, saturated or unsaturated A group selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy groups, provided that R ¹ or R ⁴ is isopropyl, ^{R 2} or ^{R 3} is not the ArCOCH _3, X ^- is a suitable charge Bas Taking Nsu, preferably it is bleach compatible counterion, v
Is an integer of 1 to 3.

Preferably, the aryliminium cation and aryliminium polyion having a net charge of about +3 to about −3 are represented by the following formula [XI].

[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
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
A carbocycle or a fused heterocycle may be formed provided that R²⁰Is pheny
R not R¹⁹R is isopropyl, R²⁰Is COCH_Threenot,
R¹⁸Is H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl
Le, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto
A substituted, selected from the group consisting of, carboxyl, and carboalkoxy groups.
A substituted or unsubstituted group, R¹⁹Is or has been replaced
Unsaturated, saturated or unsaturated, H, alkyl, cycloalkyl, alkali-
Is a group selected from the group consisting of: aryl, aryl, aralkyl and heterocycle;
Is (1) -O-, (2) -N (R²³)-, And (3) -N (R²³R²⁴ ) -Selected from the group consisting of²¹~ R²⁴Are independently H, oxygen, linear
Or branched chain C₁~ C₁₂Alkyl, alkylene, alkoxy, aryl,
Selected from the group consisting of alkaryl, aralkyl, cycloalkyl, and heterocycle
A substituted, substituted or unsubstituted group with the proviso that R¹⁸, R^{1 9} , R²⁰, R²¹~ R²⁴Is all R¹⁸, R¹⁹, R²⁰, R²¹~ R^{Two Four} Can be combined with any of the above to form part of a common ring, and all gem-R
²¹~ R²²Can combine to form carbonyls, and all vic
-R²¹~ R²⁴Can combine to form unsaturation, the substituent R²¹~ R^{Two Four} Substituted or unsubstituted fused unsaturated moieties in combination with any of the groups
Can form a minute, X⁻Is a suitable charge-balancing counterion, preferably
Is a counterion compatible with the bleaching agent, and v is an integer from 1 to 3.

With regard to cationic organocatalytic compounds, we have surprisingly found that substitution or branching on R ¹⁹ increases stability. More preferably, the branch is in the alpha (α) and / or beta (β) position (relative to the nitrogen atom), even more preferably in the alpha (α) position, most preferably the substitution or branch is in the alpha ( At the α) position, the following formula

[Chemical formula 46] As represented by the formula, wherein R ¹⁹ is present in the form of paired di-substitution, in which R ¹⁹ is preferably

[Chemical 47] Wherein R ^{50 to} R ⁵⁴ are independently H, linear or branched, substituted or unsubstituted alkyl, cycloalkyl, alkaryl,
Aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy,
Selected from the group consisting of keto and carboalkoxy radicals, are selected from substituted or unsubstituted group, provided that all R ⁵⁰ to R ⁵⁴ is coupled with any of R ^{5 0} to R ⁵⁴ Can form part of a common ring, and when R ⁵⁴ is an unsubstituted linear alkyl group, R ^{50 to} R ⁵³ are all H
However, when R ⁵⁴ is H, R ^{50 to} R ⁵¹ do not combine with any of R ^{52 to} R ⁵³ to form an aromatic moiety. Preferably, at least ^one of R ^{50 to} R ^{5 1} , more preferably 2 of R ^{50 to} R ⁵¹ is not H. More ^preferably, R 50 ^{to R 51} are independently selected from the group consisting of alkyl and cycloalkyl groups, and most ^preferably, R 50 ^{to R 51} are independently selected from methyl or ethyl group .

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

Aryliminium zwitterions with a net charge of about +3 to about −3 have the formula:
Represented by [II].

[Chemical 48] 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 49] 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 having a net charge of about +3 to about −3 is represented by formula [XII] below.

[Chemical 50] 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 51] 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 52] 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, provided that all R²⁹Is independent
And is not selected to be H, but G is (1) -O-, (2) -N (R ^Thirty )-, And (3) -N (R^ThirtyR³¹) -Selected from the group consisting of^{Two 7} , R²⁸, R^ThirtyAnd R³¹Are 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, R²⁵, R²⁶ , R²⁷, R²⁸, R^ThirtyAnd R³¹Is all R²⁵, R²⁶, R²⁷, R ²⁸ , R^ThirtyAnd R³¹May form a part of a common ring with any of
Yes, all gem-R²⁷~ R²⁸Can combine to form a carbonyl
And all the vic-R²⁷~ R³¹Can combine to form unsaturation
The substituent R²⁷~ R³¹All of the groups are substituted or substituted.
Unfused unsaturated moieties can be formed, provided that

[Chemical 53] Groups represented by the _{^{CH 2 CH (OSO 3 -)}} R 41 (R 41 is gem- dimethyl substituted alkyl, and the selected from the group consisting of alkyl and phenyl unsubstituted) not.

With respect to zwitterionic organocatalytic compounds, we have surprisingly found that substitution or branching on R ¹⁹ increases stability. Branch is alpha (α)
Or more preferably in the beta (β) position (relative to the nitrogen atom), even more preferably in the alpha (α) position, most preferably the substitution or branching in the alpha (α) and (β) positions. , The following formula

[Chemical 54] Wherein R ^{41 to} R ⁴⁴ are independently H, linear or branched, substituted or unsubstituted alkyl, cycloalkyl, alka Selected from the group consisting of a reel, an aryl, an aralkyl, an alkylene, an alkoxy group, a substituted or an unsubstituted group, provided that R ^{41 to} R ⁴⁴ are all R ^{41 to} R ⁴⁴ It is possible to combine with any of them to form a part of a common ring, more preferably at least one of R ^{41 to} R ⁴⁴ , and further preferably 2 is H. More preferably R ^{41 to} R ⁴⁴ are H and R ⁴³ or R ^{43 to} R ⁴⁴ are independently selected from the group consisting of C _{1 to} C ₁₆ alkyl or cycloalkyl, and more preferably R ⁴³ and the total number of carbon atoms in R ⁴⁴ is 2-20. Most preferably R ⁴³ and R ^{4 4} are of the formula

[Chemical 55] It is arranged as shown in.

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 56] With respect to the groups represented by_p ⁻Is -CO_Two ⁻, -SO_Three ⁻Or -OSO _Three ⁻ And p is 1 or 2, more preferably Z_p ⁻Is -SO_Three ⁻Also
Is -OSO_Three ⁻And a substance in which p is 1 is included.

Examples of suitable zwitterionic organic catalysts include, but are not limited to, the following materials.

[Chemical 57] In the formula,

[Chemical 58] Is.

Bleaching substances Bleaching substances (oxaziridinium) can also be used directly according to the invention.
Bleaching agents of the present invention include oxaziridinium cations having a net charge of about +3 to about -3, oxaziridinium polyions, and oxaziridinium zwitterions having a net charge of about +3 to about -3. However, the present invention is not limited to these.

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

[Chemical 59] Wherein R ^{2 ′ to} R ^{3 ′} are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and Selected from the group consisting of carboalkoxy groups, selected from substituted or unsubstituted groups, R ^{1 ′} and R ^{4 ′} are substituted or unsubstituted, saturated or unsaturated, A group selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy groups, provided that R ^1'or R ^'If is isopropyl, R ^{2' 4} or R ^{3 'is} not the ArCOCH _3, X ^- take suitable charge balance, Mashiku is there counterions bleach compatible, v is 1
Is an integer of ˜3. Preferably, the oxaziridinium cations and polyions having a net charge of about +3 to about -3 are represented by formula [XIII] below.

[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
And n is an integer from 0 to 4, and each R ^{20 ′} 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 ^{20 '} substituents being combined. Can be fused to form a fused aryl, fused carbocycle or fused heterocycle, provided that R ^{20 ′} is not COCH ₃ and R ^{18 ′} is H, alkyl, cyclo, when R ^{19 ′} is isopropyl. Alkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl,
And a carboalkoxy group, which may be a substituted or unsubstituted group, R ^{19 ′} may be substituted or unsubstituted, saturated or unsaturated, H, alkyl, Cycloalkyl, alkaryl, 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 ') - is selected from the group consisting of, ^{R 21'} ~R ^{24 'are,} independently, H Selected from the group consisting of oxygen, linear or branched C ₁ -C ₁₂ alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl, and heterocycle, substituted or substituted. However, R ^{18 ′} , R ^{19 ′} , R ^{21 ′ to} R ^{24 ′} are all bonded to any one of R ^{18 ′} , R ^{19 ′} and R ^{21 ′ to} R ^{24 ′} to form a common ring. Can form part of all gem-R ^21
' ~ R22 ^' can combine to form a carbonyl, and all vic
-R ^{21 'to} R ^24' can combine to form an unsaturation, and any of the substituents R ^{21 'to} R ^24' can be combined to form a substituted or unsubstituted fused unsaturated moiety. And any of the substituents R ^{21 ′ to} R ^{24 ′} can be combined to form a substituted or unsubstituted fused unsaturated moiety, and X ⁻ is a suitable charge balance. Is a counterion compatible with the bleaching agent, 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.

Oxaziridinium zwitterions with a net charge of about +3 to about −3 are represented by the formula:
Represented by [IV].

[Chemical formula 61] 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 formula 62] 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 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
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,
A group selected from the group consisting of nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups, which may be substituted or unsubstituted and is represented by the formula:

[Chemical 64] In, Z _'p ^- is T' is covalently bound to _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
Or 2 and T ′ ₀ is

[Chemical 65] 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.
Selected from all the groups that are substituted or unsubstituted, provided that all R^{29 '}But
It is not independently selected to be H, and 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
The sum part can be formed, provided that

[Chemical formula 66] Groups represented by the _{^{CH 2 CH (OSO 3 -)}} R 41 (R 41 is gem- dimethyl substituted alkyl, and the selected from the group consisting of alkyl and phenyl unsubstituted) not.

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 67] With respect to the group represented by_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OSO_Three ⁻ And p is 1 or 2 are included.

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

[0045]   The modified amine is represented by the following formulas [V] and [VI].

[Chemical 68] In the formula, R ^{9 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl,
Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups and substituted, selected from the group consisting of groups having anionic and / or cationic charges. R ⁸ and R ¹¹ are substituted or unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic Ring, silyl, nitro, halo,
Cyano, alkoxy, keto and carboalkoxy radicals and anionic and / or group selected from the group consisting of groups having a cationic charge, R ¹² is a leaving group, the protonated form pK _a value (H ₂ O basis) falls within the range of 37> pK _a > -2, provided that all R ^{8 to} R ¹² , when present, combine to form a fused aryl, fused carbocycle or fused heterocycle. Can be the formula below

[Chemical 69] In the group represented by, _{Z p} ^- is covalently bonded to _{T 0, Z p} ^- is -CO ₂ ^-, -
Selected from the group consisting of SO ₃ ⁻ , —OSO ₃ ⁻ , —SO ₂ ^— and —OSO ₂ ^— , p is 1, 2 or 3, and T ₀ is substituted or unsubstituted, saturated. Alternatively, it is selected from the group consisting of unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocycle.

[0046]   Preferably, the modified amine is represented by the following formulas [XV] and [XVI].

[Chemical 70] 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 ³⁵ is independently H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, alkoxy. , Keto, carboxyl, and carboalkoxy groups, selected from substituted or unsubstituted groups, all two vic-R ³⁵ substituents in combination are fused aryl, fused Carbocycles or fused heterocycles can be formed and R ³² 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, 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, wherein: There is also a group represented by the formula below,

[Chemical 71] 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 72] 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, provided that all R³⁸Is independent
And is not selected to be H, but G is (1) -O-, (2) -N (R ³⁹ )-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of^{Three 6} , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloal
Kill, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
, An arylcarbonyl group, a carboxyalkyl group and an amide group
A selected, substituted or unsubstituted group, R³², R³³,
R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R^{Three Three} , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with one of
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a combination
Vic-R that can form a carbonyl³⁶, R³⁷, R
³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R^{Three 7} , R³⁹And R⁴⁰Any of the groups are substituted or substituted.
Not fused unsaturated moieties can be formed.

[0047]   More preferred modified amines represented by formulas [XV] and [XVI] include a net charge
Is about +1 to about -1, and R³²Is H and / or Z_p ⁻Is -CO_Two ⁻ , -SO_Three ⁻Or -OSO_Three ⁻The modified amine is

[0048]   The modified amine oxide of the present invention is represented by the following formulas [VII] to [X].

[Chemical formula 73]

[Chemical 74] In the formula, R ^{8 to} R ¹⁰ are independently H, alkyl, cycloalkyl, aryl,
Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups and substituted, selected from the group consisting of groups having anionic and / or cationic charges. R ¹¹ is a substituted or unsubstituted group, a substituted or unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl. A nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy group and a group having an anionic and / or cationic charge, R ¹² is a leaving group, its protonated form is pK _a value _(H 2 O
Criteria) falls within the range of 37> pK _a > -2, provided that R ^{8 to} R ¹² , when present, can be combined to form a fused aryl, fused carbocycle or fused heterocycle, There is also a group represented by the following formula in the formula.

[Chemical 75] 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 modified amine oxide is represented by the following formulas [XVII]-[XX].

[Chemical 76]

[Chemical 77] 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 ³⁵ is independently H, alkyl, cycloalkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano, sulfonate, alkoxy. , Keto, carboxyl, and carboalkoxy groups, selected from substituted or unsubstituted groups, all two vic-R ³⁵ substituents in combination are fused aryl, fused Carbocycles or fused heterocycles can be formed and R ³² 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, 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, wherein: There is also a group represented by the formula below,

[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

[Chemical 79] 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, provided that all R³⁸Is independent
Is not selected to become H, and G is (1) -O-, (2) -N (R ³⁹ )-, And (3) -N (R³⁹R⁴⁰) -Selected from the group consisting of^{Three 6} , R³⁷, R³⁹And R⁴⁰Are independently H, oxygen, alkyl, cycloal
Kill, alkaryl, aryl, aralkyl, alkylene, heterocycle, alkoxy
, An arylcarbonyl group, a carboxyalkyl group and an amide group
A selected, substituted or unsubstituted group, R³², R³³,
R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Is all R³², R^{Three Three} , R³⁴, R³⁵, R³⁶, R³⁷, R³⁹And R⁴⁰Combined with one of
Can form part of a common ring, and all gem-R³⁶~ R³⁷Is a combination
Vic-R that can form a carbonyl³⁶, R³⁷, R
³⁹And R⁴⁰Can combine to form unsaturation, the substituent R³⁶, R^{Three 7} , R³⁹And R⁴⁰Any of the groups are substituted or substituted.
Not fused unsaturated moieties can be formed.

Preferred modified amines represented by formulas [XVII] and [XX] have a net charge of about +
1 about ^{-1, R 32} is H or methyl, and / or _{Z p} ^- is -
CO ₂ ^-, -SO ₃ ^- or -OSO ₃ ^- modified amines is.

[0051] For the modified amine ^{compounds, R 12} is a leaving group (LG), the protonated form pK _a value _{(H 2} O basis) _37> pK a> -2, preferably 30>
pK _a > 0, more preferably 23> pK _a > 3, even more preferably 17> pK _a > 11, and most preferably R ¹² is substituted or unsubstituted, saturated or hydroxy unsaturated, leaving group consisting perhydroxy, alkoxy and Peruarukokishi groups can R ⁸ to R ¹² are combined to form a fused aryl, fused carbocyclic or fused heterocyclic.

Suitable examples of X ⁻ , anionic counterions include BF ₄ ⁻ , OTS ^−, and other international patents WO 97/06147, WO 95/13352, WO 95/13353, WO95 / 13351
No. WO98 / 23717, U.S. Pat. Examples include, but are not limited to, the disclosed anionic counterions. Anionic counterions are
It is preferably compatible with the bleach.

[0053]   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 wt% (100 ppm), preferably about 0.0001 wt% (0.001 ppm) to about 2 wt% (20 ppm) of the composition, more preferably about 0.005 wt% (0. 05 ppm) to about 0.5 wt% (5 ppm)
And more preferably about 0.01 wt% (0.1 ppm) to about 0.2 wt% (2 p
pm), most preferably about 0.02 wt% (0.2 ppm) to about 0.1 wt% (
1 ppm) can be added.

Preferably, the bleaching composition of the present invention comprises an amount of organocatalyst compound 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. A 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, 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 wt% of an organocatalyst compound results in an organocatalyst compound concentration of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2 wt% of organocatalyst compound has an organocatalyst compound concentration of 6.5.
It becomes 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 to 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 about 2 ppm, most preferably about 0.2 ppm to about 1 ppm of the organocatalyst compound.

Such a preferred method for bleaching a stained substrate in an aqueous medium using a peroxygen source and an organocatalytic 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.

Degradation of Organocatalysts Organocatalysts, especially 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 a 6-membered ring bleach-enhancing compound is described in Hanquet et al., Tetrahedron 1993, 49,
pp. 423-438, which is not bound by theory, but is well known in the art. Other decomposition means include hydroxide anions and perhydroxides present under washing conditions.
(but not limited to) attack by (perhydroxide) anions, carboxylate anions, percarboxylate anions, and other nucleophiles.
, But not limited to, attack of the bleach-enhancing compound and / or bleach by a nucleophile. 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 80]

Delayed (Controlled) Addition Method for Organic Catalysts Surprisingly, for organic catalysts that have a limited lifespan, compared to adding the organic catalyst to the wash solution before adding the fabric to the wash solution by some dosing means. It was then found that the bleaching was enhanced by adding the organic catalyst to the wash solution after adding the fabric to the wash solution. Without being bound by theory, the organocatalytic compound is
It is believed to decompose before adding fabric. One way to enhance the performance of the organocatalyst compound is to delay the addition of the organocatalyst compound of the present invention to the wash solution. Another way to improve the performance of organocatalyst compounds is to add organocatalyst compounds with enhanced stability to the wash solution. The present invention relates to the latter method,
Performance can be further improved by using both the latter and the former methods. The method of delayed (controlled) addition of organocatalyst compounds is under review and is owned together.
US provisional patent application entitled "Controlled Activation of Prescription Ingredients, Compositions and Laundering Methods Using the Same" filed August 27, 1999 (P & G Attorney Document No. 77).
49P).

Bleaching Compositions Comprising Organocatalysts In addition to the use of organocatalyst compounds, the organocatalyst compounds of the present invention, regardless of their form, may also be used in other bleaching compositions with a peroxygen source. You can For example, organocatalyst compounds can be used in laundry additive products.

In the bleaching composition of the present invention, the source of peroxygen is from about 0.1 (1 ppm) to about 60% by weight (600 ppm) of the composition, preferably from about 1 (10 ppm) to about 40 of the composition.
The organocatalytic compound may be present in an amount of wt% (400 ppm) and the organocatalyst compound is from about 0.00001 (0.0001 ppm) to about 10 wt% (100 ppm) of the composition, preferably about 0.0001 (0 ppm of the composition. 0.001 ppm) to about 1% by weight (10 pp
m), more preferably about 0.001 (0.01 ppm) to about 0.5 wt% (5 p
pm), and more preferably about 0.004 (0.04 ppm) to about 0.25% by weight.
(2.5 ppm), most preferably about 0.01 (0.1 ppm) to about 0.1 wt% (1 ppm).

The organocatalytic compounds of the present invention and bleaching compositions comprising the organocatalytic compounds are advantageously used in laundry applications, hard surface cleaning, automatic dishwashing applications, wood pulp and / or
Alternatively it can be used for whitening and / or bleaching applications related to textiles, bactericidal and / or disinfectant applications, and cosmetic applications such as dentures, teeth, hair and skin. However, because of the unique advantage of being highly effective in cold water and, due to its high stability, in hot aqueous solutions, the organocatalyst compounds of the present invention are useful in laundry applications, such as detergent-containing bleaches or laundry bleach additives. Ideally suited for bleaching fabrics by using. Further, the bleach-enhancing compounds of the present invention can be used in granular, powder, bar,
It can be used in pastes, foams, gels 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 detergent surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other detergent ingredients. Compositions including any of these various additional detergent ingredients preferably have a pH in a 1% solution of the bleaching composition of from about 6 to about 12, more preferably from about 8 to.
It is about 10.5. The bleaching composition preferably includes at least one detersive surfactant, at least one chelating agent, at least one enzyme, and the pH of a 1% solution of the bleaching composition is preferably about 6 to about 12. , More preferably about 8 to about 1
It is 0.5.

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 include at least one additional detergent ingredient selected from the group consisting of detergent surfactants, chelating agents, detergent enzymes and mixtures thereof. Preferably, the laundry solution has a pH in a 1% solution of the bleaching composition of about 6 to about 12, more preferably about 8 to about 10.5.

Another aspect of the invention provides a laundry additive product. Laundry additive products are
It comprises an organocatalyst compound 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, low and medium temperature solution laundry applications.

The laundry additive product preferably further comprises a source of peroxygen as detailed above. 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 above.

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 detailed above.

Preferably, the laundry additive product is packaged in dosage form, using a source of peroxygen,
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 peroxygen source, and (b) one or more organocatalyst compounds, wherein the peroxygen source is in a wash solution containing the bleaching composition. A bleaching composition in which the organocatalyst compound becomes effective after becoming active. The peroxygen source as described above preferably comprises 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 selected from, and (ii) a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and It is selected from the group consisting of bleach activators.

Preferably, the peroxygen source comprises a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof, and a bleach activator. To be selected.

More preferably, the bleach activator is selected from the group consisting of the hydrophobic bleach activators described herein.

The time from activation of the peracid to activation of the organocatalyst compound in the wash solution may be from about 1 second to about 24 hours. Alternatively, the peracid may be active after the organocatalyst compound is active or active in the wash solution, as the organocatalyst compound is relatively stable in the wash solution.

Delayed Addition Bleaching Composition, Which may or may not be Used in Conjunction with the Present Invention
The purpose of is to maximize the bleaching performance of peracid on fabrics that need to be washed in the wash solution prior to introducing the organocatalytic compound, such as stained fabrics. That is, the bleaching composition comprises an organocatalyst compound that becomes active after the fabric that needs to be washed is added to the wash solution. Alternatively, use of a bleaching composition comprising an organocatalyst compound that becomes active in the wash solution prior to adding the fabric that needs to be washed to the wash solution because the organocatalyst compound can enhance stability. You can

The bleaching composition of the present invention, in addition to one or more of the organic catalysts described above, is compatible with one or more of the organic catalysts and / or enzymes preferably present in the bleaching composition. It also comprises some cleaning aids. As used herein, the term "compatible" means that the bleaching composition is used to determine the bleaching activity of the organocatalyst and / or the enzymatic activity of the enzyme present in the bleaching composition, as the organic catalyst and / or enzyme normally use. It does not mean that the desired effect in the situation cannot be achieved. As used herein, the term "cleansing aid" was selected for a particular type of bleaching composition and product form (eg, liquid, granule, powder, bar, paste, spray, tablet, gel, foam composition). It means all liquid, solid or gaseous materials, which are preferably compatible with the protease enzymes and bleaches used in the composition. The granular composition may be in "compact" form and the liquid composition may be in "concentrated" form.

The specific choice of cleaning adjunct material will depend on the surface to be cleaned, the object or fabric, and the desired form of the composition for the cleaning conditions in use (eg detergent used by washing).
It can be easily done by considering. Examples of suitable cleaning aids include:
U.S. Pat.Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,
686,017 and 5,646,101, such as surfactants, builders,
Bleach, bleach activator, bleach catalyst, other enzymes, enzyme stabilizing systems, chelating agents, optical brighteners, soil release polymers, dye transfer inhibitors, dispersants, foam inhibitors, dyes, fragrances, coloring Agents, filler salts, hydrotropic agents, photoactive agents, fluorescent agents, fabric conditioning agents, hydrolyzable surfactants, preservatives, antioxidants, anti-shrink agents, anti-wrinkle agents, bactericides, fungicides, Color speckles, silverware protectors, antifog and / or corrosion inhibitors, alkalinity sources, solubilizers, carriers, processing aids, pigments and pH
Examples include, but are not limited to, modifiers. Specific bleaching composition materials are exemplified in detail below.

If the cleaning adjunct material is incompatible with the protease variant in the bleaching composition, the cleaning adjunct material and the protease variant are separated until the combination of these two components is suitable (not in contact with each other). Any suitable method can be used. All methods known in the art, such as gelcaps, encapsulation, tablets,
Physical separation, etc. are preferred.

Such bleaching compositions include detergent compositions in all forms (eg liquids, granules, pastes, foams, sprays, etc.) for cleaning hard surfaces, all forms for washing fabrics (eg. For example, granular, liquid, bar formulations, etc.) detergent compositions, dishwashing compositions (any form including both granular and liquid automatic dishwashing), all forms of mouthwash compositions (Eg, toothpaste, toothpaste and mouthwash formulations), and all forms of denture cleansing compositions (eg, liquids, tablets).

The fabric bleaching composition of the present invention is primarily intended for use in the washing cycle of a washing machine, but other applications are also envisaged, for example pretreatment products for heavily soiled fabrics, or dipping products. However, use is not necessarily limited to washing machines and the compositions of the present invention may be used alone or in combination with compatible hand washing compositions.

The bleaching composition can include from about 1 to about 99.9% by weight of the composition of a cleaning adjunct material.

As used herein, “non-fabric bleaching compositions” include hard surface bleaching compositions, dishwashing compositions, mouthwash compositions, denture cleansing compositions and cosmetic cleansing compositions.

When the bleaching composition of the present invention is formulated as a composition suitable for use in a washing machine process, the composition of the present invention preferably comprises both a surfactant and a builder compound,
And preferably one or more cleaning aids selected from organic polymeric compounds, bleaching agents, other enzymes, foam inhibitors, dispersants, lime soap dispersants, soil dispersants and anti-redeposition agents and corrosion inhibitors. Further includes materials. The laundry composition may also include a softening agent as an additional cleaning adjunct material.

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

When formulated as a composition for use in a manual dishwashing process, the composition of the present invention comprises:
It is preferred to include a surfactant and preferably other cleaning adjunct materials selected from organic polymeric compounds, foam enhancers, Group II metal ions, solvents, hydrotropic agents and other enzymes.

If desired, the laundry detergent composition has a density of 400 to 120, measured at 20 ° C.
The composition is 0 g / liter, preferably 500 to 950 g / liter.

The “compact” form of the bleaching composition of the present invention is best reflected by the density and, with respect to the composition, by the amount of inorganic filler salt, the inorganic filler salt of the detergent composition being in powder form. A conventional ingredient, in conventional detergent compositions, filler salts are present in significant amounts, typically in amounts of 17-35% by weight of the total composition. In compact compositions, the filler salt is present in an amount not exceeding 15% by weight of the total composition, preferably not exceeding 10%, most preferably not exceeding 5%. The inorganic filler salt used in the composition is selected from alkali and alkaline earth metal sulfates and hydrochlorides. The preferred filler is sodium sulfate.

The liquid bleaching composition of the present invention may be in “concentrated form”, in which case the liquid bleaching composition of the present invention will contain a small amount of water as compared to conventional liquid detergents. Typically,
The water content of the concentrated liquid bleaching composition is preferably less than 40% by weight of the bleaching composition, more preferably less than 30% by weight and most preferably less than 20% by weight.

Cleaning Auxiliary Materials Although not essential for the purposes of the present invention, some conventional cleaning auxiliary materials exemplified below are suitable for use in the present bleaching composition, and in preferred embodiments of the invention: For example, it may be formulated to aid or enhance cleaning performance, to treat the substrate to be cleaned, or to improve the aesthetics of the bleaching composition, such as perfumes, colorants, dyes, etc. desirable. 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 in granular or powder form, in particular laundry detergents, general detergents in the form of liquids, gels or pastes, especially the so-called heavy detergents. Duty liquid types, liquid high-grade fabric detergents, hand or dishwashing detergents, especially high-foaming detergents, household and commercial tablets, granules, liquids and rinsing aid types. Including machine dishwashing agents, germicidal handwash, laundry bars, mouthwashes, denture cleaners,
Liquid cleaning and disinfecting agents, including car or carpet shampoos, bathroom cleaners, hair shampoos and hair rinses, shower gels and foam baths and metal cleaners, and cleaning aids such as bleach additives and "stain remover sticks" or before It can be formulated as a processed form.

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 perate 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
described in U.S. Pat. No. 5,576,282 to Al.) can be used in conjunction with a preformed peracid compound selected from the group consisting of:

[0095]   One group of suitable organic peroxycarboxylic acids has the general formula:

[Chemical 81] 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.

Organic peroxyacids suitable 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 formula 82] In the formula, Y is, for example, H, CH ₃ , CH ₂ Cl, —C (O) OH or —C (O).
OOH and n is an integer of 0-20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[Chemical 83] In the formula, Y is, for example, hydrogen, alkyl, alkylhalogen, halogen, or -C (O).
OH 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, promulgated 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 source is Kirk Othmer's Encyclopedia of Chemical Technology,
4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleach (Survey)"
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 from 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.

C. 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 (LO
BS or C ₁₂ -OBS), 10-undecenoyloxybenzene sulfonate (UDOBS or C ₁₁ -OBS containing unsaturation at the 10 position), and decanoyloxybenzoic acid (DOBA). Not a thing.

Preferred bleach activators are all US Pat. No. 5,698,504, incorporated herein by reference.
Issue, Christie et al., Promulgated December 16, 1997, No. 5,695,679, Christie et al.
, Promulgated December 9, 1997, No. 5,686,401, Willey et al., Promulgated November 11, 1997,
No. 5,686,014, Hartshorn et al., Promulgated November 11, 1997, No. 5,405,412, Will
ey et al., published April 11, 1995, No. 5,405,413, Willey et al., April 11, 1995.
Promulgated by Japan, No. 5,130,045, Mitchell et al., Promulgated on July 14, 1992, and No. 4,412.
, 934, Chung et al., Promulgated November 1, 1983, and pending US patent application 08 /
709,072, 08 / 064,564 activators.

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 published in Dec. 17, 996, and in No. 5,578,136, Taylor et al., Proposed Nov. 26, 1996.

Highly preferred bleach activators useful herein are each of the US Pat.
Amide substituted materials such as those 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 them. A mixture of

US Pat. Nos. 5,698,504, 5,695,679, and 5,68, respectively, described above.
No. 6,014, and No. 4,966,723, Hodge et al., 10 October 30, 1990 issued, other useful active agents disclosed, the benzoxazine type active agents, for example, C ₆ H ₄ ring 1 Material in which the --C (O) OC (R ¹ ) ═N-moiety is fused in position.

Depending on the activator and the particular application, good bleaching results can be obtained from a bleaching system 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 6,014, especially acyl caprolactam (see, eg, WO 94-28102A) and acyl valerolactam (US Pat. No. 5,503,639, incorporated herein by reference) Willey et al., 1996. Promulgated 2 April, see) 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 having a specific bleach catalyst activity, for example, a cation of copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese, and 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.
No. 0,243, Bragg, promulgated February 2, 1982.

I. Manganese Metal Complex -If desired, the composition can be catalyzed by a manganese compound. Such compounds and amounts used are well known in the art, for example U.S. Pat.No. 5,576,282, Miracle et al., Promulgated Nov. 19, 1996, No. 5,246,621, Favre et al., Sep. 1993. Promulgated 21st, No. 5,244,594, Favre e
t al., promulgated September 14, 1993, No. 5,194,416, Jureller et al., promulgated March 16, 1993, No. 5,114,606, van Vliet et al., promulgated May 19, 1992, and published Europe. Patent applications 549,271A1, 549,272A1, 544,440A2, and 544,4
The manganese-based catalysts disclosed in 90A1 are listed. Preferred examples of these _{^{catalysts, Mn IV 2 (u-O}} ) 3 (1,4,7- _{trimethyl-1,4,7-triazacyclononane) 2 - (PF 6) 2} , Mn III 2 ( u-O) ₁ (u-OAc) ₂ (1
, 4,7-Trimethyl-1,4,7-triazacyclononane) _2- (ClO ₄ ) ₂ ,
Mn ^IV ₄ (u—O) ₆ (1,4,7-triazacyclononane) ₄ — (ClO ₄ ) ₄ ,
Mn ^III Mn ^IV ₄ (u-O) ₁ (u-OAc) ₂ (1,4,7-trimethyl-
1,4,7-Triazacyclononane) _2- (ClO ₄ ) ₃ , Mn ^IV (1,4,7-
Trimethyl-1,4,7-triazacyclononane _{(OCH 3) 3 - (PF} 6) , and mixtures thereof. Other metal-based bleach catalysts include the materials described in US Pat. Nos. 4,430,243 and 5,114,611, van Kralingen, promulgated May 19, 1992, incorporated by reference above. A method of enhancing bleaching using manganese and various complexing ligands is disclosed in U.S. Pat.No. 4,728,455, Rerek, promulgated March 1, 1988, 5,
284,944, Madison, promulgated February 8, 1994, No. 5,246,612, van Dijik et al., 1
Promulgated 21 September 993, No. 5,256,779, Kerschner et al. Promulgated 26 October 1993,
No. 5,280,117, Kerschner et al., Promulgated January 18, 1994, No. 5,274,147, Kersc
hner et al., December 28, 1993, No. 5,153,161, Kerschner et al., 1992.
Promulgated October 6, and No. 5,227,084, Martens et al., Promulgated July 13, 1993.

[0119]     ii.Cobalt metal complex-Cobalt bleach catalysts useful herein are known,
For example, U.S. Pat.No. 5,597,936, Perkins et al., Promulgated January 28, 1997, 5,595,
967, Miracle et al., Promulgated January 21, 1997, No. 5,703,030, Perkins et al.
, Promulgated December 30, 1997, and M.L.Tobe, "Base Hydrolysis of Transition-M.
etal Complexes '',Adv. Inorg. Bioinorg. Mech., (1983), pp. 2, 1-94.
Has been. The most preferred cobalt catalyst here is of the formula [Co (NH_Three)₅OAc] T_y Wherein “OAc” represents an acetate salt moiety and “Tac”_yIs an anion
Ruptentaamine acetate, especially cobalt chloride pentaamine acetate [Co (NH_Three)
₅OAc] Cl_Two, And [Co (NH_Three)₅OAc] (OAc)_Two, [Co (NH_Three) ₅ OAc] (PF₆)_Two, [Co (NH_Three)₅OAc] (SO_Four), [Co (NH_Three)₅OA
c] (BF_Four)_Two, And [Co (NH_Three)₅OAc] (NO_Three)_Two(Here, "PAC
)).

These cobalt catalysts are prepared according to the above-mentioned US Pat. Nos. 5,597,936, 5,595,967 and 5,5,97,936.
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 Characterization of In
organic Compounds, WL Jolly... ... (Prentice Hall; 1970), pp 461-3, Inorg C hem, 18, 1497-1502 (1979), Inorg Chem, 21, 2881-2885 (1982), Inorg C hem., 18, 2023-2025 (1979 ), Inorg. Synthesis, 173-176 (1960), and Jour nal of Physical Chemistry, 56, 22-25 by known procedures such as disclosed in (1952), It can be easily manufactured.

Iii. Macropolycyclic Rigid Ligand Transition Metal Complexes -The present compositions preferably include a transition metal complex of a macropolycyclic rigid ligand as a bleach catalyst. In the description below, the term "macrocyclic rigid ligand" refers to "MRL.
May be abbreviated. The amount used is a catalytically effective amount of about 1 pp.
b or higher is preferred, for example up to about 99.9%, more typically about 0.001 p.
pm or more, preferably about 0.05 ppm to about 500 ppm (where "ppb" represents parts per billion and "ppm represents parts per 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.

Preferred MRLs here are cross-bridged special types of super-rigid ligands. “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 portion bridges N ¹ and N ⁸ in the illustrated structure. By comparison,
"Same side" bridge, when introducing a bridge so as across the N ¹ and N ¹² in example 1.11, the "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 present invention 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, for example, the Busch article in “Chemical Review”).

The preferred superstructures here not only strengthen the rigidity of the parent macrocycle, but also facilitate 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 84] In the formula, n is an integer, for example 2 to 8, preferably less than 6, typically 2 to 4.
Or

[Chemical 85] 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 exemplified by, but not limited to, the compounds below.

[Chemical 86]

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: Recommendatio
ns 1993 '', R. Panico, WH Powell and JC Richer (Eds.), Blackwell Scient.
See ific Publications, Boston, 1993, especially Section R-2.4.2.1.

Transition metal bleach catalysts suitable for use in the compositions of the present invention are generally designed specifically for known compounds according to the definition of the invention, and more preferably 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 by way of limitation, the present compositions and washing methods may include:
At least one hundred millionth, preferably about 0.01 ppm to about 25 pp
m, more preferably about 0.05 ppm to about 10 ppm, most preferably about 0.1.
It can be adjusted to provide from ppm to about 5 ppm of active bleach catalyst in the 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%. To about 0.08 wt.% Bleach catalyst, especially 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 to reduce the undesired decomposition of the organic catalyst in the wash solution before it becomes effective and to fabrics that need to be washed, such as spotted fabrics. To achieve the peracid bleaching performance.

Surfactant Systems The cleaning surfactants included in the fully formulated bleaching compositions provided by this invention will contain at least about 0.0 of the bleaching composition, depending on the particular surfactant used and the effect desired.
1 wt%, preferably at least about 0.1 wt%, more preferably at least about 0.5 wt%, most preferably at least about 1 wt% up to about 60 wt%,
More preferably it comprises up to about 35% by weight, most preferably up to about 30% by weight.

The detergent surfactant may be nonionic, anionic, amphoteric, zwitterionic, cationic, semipolar nonionic, and mixtures thereof, examples of which are described in US Pat. No. 5,707,950. And No. 5,576,282, but is not limited thereto. Preferred detergents and bleaching compositions comprise anionic detersive surfactants or a mixture of anionic surfactants and other surfactants, especially nonionic surfactants.

Anionic surfactants are highly preferred for use with the organic catalysts and bleaching compositions of this invention.

[0137]   Examples of surfactants useful herein include conventional C₁₁~ C₁₈Alkylbenzenes
Ruphonate and primary, secondary and random alkyl sulphates, C₁₀ ~ C₁₈Alkylalkoxy sulphate, C₁₀~ C₁₈Alkyl polyglyco
Sides and their corresponding sulfated polyglycosides, C₁₂~ C₁₈Alpha-
Sulfonated fatty acid ester, C₁₂~ C₁₈Alkyl and alkylphenol
Alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ ~ C₁₈Betaine and sulfobetaine (“sultaine”), C₁₀~ C_{1 8}   Examples include, but are not limited to, amine oxides. other
Common, useful surfactants are described in standard textbooks.

Surfactants are preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated to enhance, or at least not degrade, all enzymes in these compositions.

Nonionic Surfactants Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are suitable for use as the surfactant-based nonionic surfactants of the present invention, with polyethylene oxide condensates being preferred. preferable. Commercially available nonionic surfactants of this type include Igepal (trade name) CO-630, which is commercially available from GAF Corporation, and Triton (commercially available from Rohm & Haas Company.
Trade name) X-45, X-114, X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (eg alkylphenol ethoxylates).

Condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant in the nonionic surfactant system of the present invention. It is suitable. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (C _{11 to} C ₁₅ linear alcohols and 9 both available from Union Carbide Corporation). Condensation product of moles of ethylene oxide), Tergitol (trade name) 24-L-6 NMW (condensation product of C _{12 to} C ₁₄ primary alcohol and 6 moles of ethylene oxide with narrow molecular weight distribution), Shell Chemic
Neodol (trade name) 45-9 (condensation product of C _{14 to} C ₁₅ straight chain alcohol and 9 moles of ethylene oxide), Neodol (trade name) 23-3 (C ₁₂ to
Condensation product of C ₁₃ linear alcohol and 3.0 mol of ethylene oxide), Neod
ol (trade name) 45-7 (condensation product of C _{14 to} C ₁₅ straight chain alcohol and 7 moles of ethylene oxide), Neodol (trade name) 45-5 (C _{14 to} C ₁₅ straight chain alcohol and 5 moles) Condensation product of ethylene oxide), and The Procter & Gamble Compa
from ny commercial Kyro (trade name) EOB (C ₁₃ ~C ₁₅ condensation products of alcohols with 9 moles of ethylene oxide), and from Hoechst commercial Genapol LA 030 or 050
_(C 12 _{-C 14} condensation products of alcohols with 3 or 5 moles of ethylene oxide) and the like. The preferred HLB range in these products is 8-11, most preferably 8-10.

Examples of the surfactant-based nonionic surfactant of the present invention include US Pat.
The alkyl polysaccharides described in 5,647 are also useful.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) t (glycosyl) _{x wherein} R ² is an alkyl, alkylphenyl, hydroxy group in which the alkyl group contains from about 10 to about 18, preferably from about 12 to about 14 carbon atoms. Selected from the group consisting of alkyl, hydroxyalkylphenyl, and mixtures thereof, n is 2 or 3, preferably 2, t is 0 to about 10, preferably 0, and x is about 1.3.
To about 10, preferably about 1.3 to about 3, and most preferably about 1.3 to about 2.7.

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. Examples of compounds of this type include Plurafac® LF404 and Pluronic® surfactants commercially available from BASF.

A condensation product of ethylene oxide and a product obtained by the reaction of propylene oxide and ethylenediamine is also suitable as the nonionic surfactant of the nonionic surfactant system of the present invention. Examples of this type of nonionic surfactant include the Tetronic® compounds commercially available from BASF.

Preferred materials for use as the surfactant-based nonionic surfactants of the present invention are polyethylene oxide condensates of alkylphenols, primary and secondary aliphatic alcohols and from about 1 to about 25 moles. Condensation products of ethylene oxide, alkyl polysaccharides, and mixtures thereof. The most preferred material is 3-15 _C 8 having ethoxy groups _{-C 14} alkyl phenol ethoxylates and 2-10 _C 8 having ethoxy groups _{-C 18} alcohol ethoxylates (preferably C1
0 average) and mixtures thereof.

Highly preferred nonionic surfactants have the formula R ² —C (O) —N (R ¹ ) —Z.
A polyhydroxy fatty acid amide surfactant having R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ² is C _5-31 hydrocarbyl, Z is a hydrocarbyl straight, at least three hydroxyl groups or a direct bond poly hydroxyhydrocarbyl the chain, or an alkoxylated derivative thereof. Preferably ^{R 1} is methyl, ^{R 2} is a linear _{C 11 -15} alkyl or _{C 16-18} alkyl or alkenyl chain such coconut alkyl or mixtures thereof, Z is in the reductive amination reaction , Reducing sugars such as glucose, fructose, maltose, lactose.

Anionic Surfactants Suitable anionic surfactants to use are linear alkylbenzene sulfonates,
C ₈ -C ₂₀ linear esters of carboxylic acids (i.e. fatty acids), "The Journal o
f American Oil Chemists Society ", 52 (1975), pp.323-329.
Alkyl ester sulfonate surfactants, including O ₃ sulfonated materials. Suitable starting materials include natural fatty substances derived from tallow, palm oil, and the like.

Particularly preferred alkyl ester sulfonate surfactants for laundry applications comprise an alkyl ester sulfonate surfactant having the formula:

[Chemical 87] Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is an alkyl ester sulfonate. It is a cation that forms a water-soluble salt with. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, ^{R 3} is _C 10 _{-C 16} alkyl, ^{R 4} is methyl, ethyl or isopropyl. A particularly preferred material is a methyl ester sulfonate in which R ³ is C ₁₀ -C ₁₆ alkyl.

[0149]   Other suitable anionic surfactants have the formula RSO_ThreeIs a water-soluble salt or acid of M
Alkylsulfate surfactants are included, where R is preferably C₁₀~ C_{Two Four} A hydrocarbyl, preferably C₁₀~ C₂₀Alkyl having an alkyl component
Or hydroxyalkyl, more preferably C₁₂~ C₁₈Alkyl or hydr
Roxyalkyl and M is H or a cation. Typically C₁₂~ C ₁₆ Alkyl chains are preferred for low wash temperatures (eg less than about 50 ° C.), and C_16-18 Alkyl chains are preferred for high wash temperatures (eg, above about 50 ° C).

[0150] Other anionic surfactants useful in cleaning purposes include salts of _soap, primary or secondary alkane sulfonates of _{C 8 ~C 2 2, C 8} ~C 24 olefin sulfonates, for example the United Kingdom Sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates described in US Pat. No. 1,082,179, C ₈ -C ₂₄ alkyl polyglycol ether sulphates (up to 10 mol. Of ethylene oxide), alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulphates, alkylphenol ethylene oxide ether sulphates, paraffin sulphonates, alkyl phosphates, isethionates, eg acyl isethionates, N
- acyl taurates, alkyl succinamates and sulfosuccinates, sulfosulfuron monoesters of succinate (especially C ₁₂ -C ₁₈ monoesters of saturated and unsaturated) and sulfosuccinates diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), the acyl sarcosinates, alkyl polysaccharides sulfates, such as alkyl polyglucosides sulfate (nonionic nonsulfated compounds described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula _{RO (CH 2 CH 2 O)} k -CH 2 COO
-M ⁺ (In the formula, R is C ₈ -C ₂₂ alkyl, k is an integer of 1-10,
M is a cation that forms a soluble salt). Also suitable are resin acids and hydrogenated resin acids, such as rosins, hydrogenated rosins, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Another example is “Surface Active Agents and Detergents” (Vol. I and II).
, Schwartz, Perry and Berch). A variety of such surfactants are described in US Pat. No. 3,929,678 (incorporated herein by reference), Dec. 30, 1975, Lau.
Promulgated by ghlin et al., paragraph 23, line 58 to paragraph 29, line 23 generally.

[0152]   Highly preferred anionic surfactants are alkylalkoxylated sulphates.
And surfactants of the formula RO (A)_mIt is a water-soluble salt of SO3M,
In the formula, R is C which is not substituted₁₀~ C₂₄Alkyl or C₁₀~ C₂₄Al
A hydroxyalkyl group having a kill component, preferably C₁₂~ C₂₀Alkyl
Or hydroxyalkyl, more preferably C₁₂~ C₁₈Alkyl or hydro
Xyalkyl, A is an ethoxy or propoxy unit, and m is greater than 0.
And typically about 0.5 to about 6, more preferably about 0.5 to about 3, and M is
H or a cation, wherein the cation is, for example, a metal cation (eg sodium
, Potassium, lithium, calcium, magnesium, etc.), ammonium or
It may be a substituted ammonium cation. Alkyl ethoxylated sulphate
And alkyl propoxylated sulphates are intended here. Replaced
Specific examples of ammonium cations include methyl-, dimethyl-, trimethyl-ane.
Monium cations and quaternary ammonium cations such as tetramethyl-a
Ammonium and dimethyldipiperidinium cations, and alkylamines,
Positive ions derived from, for example, ethylamine, diethylamine, triethylamine.
On, mixtures thereof, and the like. A typical surfactant is C₁₂~ C_{1 8} Alkyl polyethoxylate (1.0) sulfate (C₁₂~ C₁₈E (1
． 0) M), C₁₂~ C₁₈Alkyl polyethoxylate (2.25) sulphate
(C₁₂~ C₁₈E (2.25) M), C₁₂~ C₁₈Alkyl polyethmium
Sylate (3.0) Sulfate (C₁₂~ C₁₈E (3.0) M), and C ₁₂ ~ C₁₈Alkyl polyethoxylate (4.0) sulfate C₁₂~ C_{1 8} E (4.0) M), where M is selected from sodium and potassium
Is advantageous.

The bleaching composition of the present invention, when containing an anionic surfactant, is typically from about 1% by weight, preferably from about 3% by weight to about 40% by weight, preferably about 20% by weight. Up to% such anionic surfactant is comprised.

Cationic Surfactants Suitable cationic detersive surfactants for use in the bleaching compositions of the present invention are surfactants having one long chain hydrocarbyl group. Examples of such cationic surfactants are ammonium surfactants, such as alkyltrimethylammonium halides, and the formula [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ^+. X ^- include a surfactant having a formula, ^{R 2} is alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each ^{R 3} is _-CH 2 CH _{2 -, - CH 2 CH (CH} 3) -, - CH 2 CH (CH 2 OH) -, - C
H ₂ CH ₂ CH ₂ -, and is selected from the group consisting of mixtures thereof, each ^{R 4} _is, C 1 -C _{4 alkyl,} C 1 -C ₄ hydroxyalkyl, formed by combining two ^{R 4} groups benzyl ring _structures, -CH 2 CHOH-CHOHCOR ⁶ CHOH
CH ₂ OH (wherein R ⁶ is a hexose or a hexose polymer having a molecular weight of less than about 1000), and hydrogen if y is not 0, R ⁵ is the same as R ⁴ , Or an alkyl chain, wherein the total carbon number of R ² and R ⁵ is about 18 or less, each y is 0 to about 10, and the sum of y values is 0 to about 15
And X is all compatible anions.

Highly preferred cationic surfactants are water-soluble quaternary ammonium compounds useful in the present composition and have the formula (i) R ₁ R ₂ R ₃ R ₄ N ⁺ X ⁻ below. In the formula,
R ₁ is C ₈ -C ₁₆ alkyl, and each of R ₂ , R ₃ and R ₄ is independently C ₁ -C _{4 alkyl, C 1} -C ₄ hydroxyalkyl, benzyl, and-(
C ₂ H ₄₀₎ are _x H (where x has a value of 2 to 5), X is an anion. No two or more of R ₂ , R ₃ or R ₄ should be benzyl. Preferred alkyl chain lengths for R ₁ are C ₁₂ especially when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthetically by olefin accumulation or when made by OXO alcohol synthesis. ~C is _15. R ₂ ,
Preferred groups for R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X can be selected from halide, methosulfate, acetate and phosphate ions.

Examples of quaternary ammonium compounds of formula (i) suitable for use herein include coconut trimethylammonium chloride or bromide, coconut methyldihydroxyethylammonium chloride or bromide, decyltriethylammonium chloride, decyl dimethyl hydroxyethyl ammonium chloride or bromide, C _{1 2-15} dimethyl hydroxyethyl ammonium chloride or bromide, coconut dimethyl hydroxyethyl ammonium chloride or bromide, myristyl trimethyl ammonium methyl sulphate, lauryl dimethyl benzyl ammonium chloride or bromide, lauryl Dimethyl (ethenoxy) ₄ ammonium chloride or bromide, choline ester (of the formula (i), R ₁ is

[Chemical 88] And R ₂ R ₃ R ₄ is methyl), and a di-alkyl imidazoline [(i)].

Other cationic surfactants useful herein are US Pat. No. 4,228,044, Cambre, promulgated October 14, 1980, and European Patent Application EP00.
No. 0,224.

Ampholytic Surfactants Amphoteric surfactants, examples of which are described in US Pat. No. 3,929,678, are also suitable for the bleaching compositions of the present invention.

When included, the bleaching composition of the present invention typically comprises from 0.2% by weight, preferably from about 1% by weight to about 15% by weight, preferably up to about 10% by weight. It comprises such an amphoteric surfactant.

Zwitterionic Surfactants Zwitterionic surfactants, examples of which are described in US Pat. No. 3,929,678, are also suitable for bleaching compositions.

When included, the bleaching composition of the present invention typically comprises from 0.2% by weight, preferably from about 1% by weight to about 15% by weight, preferably up to about 10% by weight. It comprises such a zwitterionic surfactant.

Semipolar Nonionic Surfactants Semipolar nonionic surfactants are a special group of nonionic surfactants,
Water-soluble amine oxide having the formula

[Chemical 89] Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group containing about 8 to about 22 carbon atoms or mixtures thereof, and R ⁴ is about 2 to about 3
An alkylene or hydroxyalkylene group containing 4 carbon atoms, or a mixture thereof, wherein x is 0 to about 3 and each R ⁵ is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms. Or a polyethylene oxide group containing 1 to 3 ethylene oxide groups (R ⁵ groups can also be attached to each other, for example through an oxygen or nitrogen atom, to form a ring structure)], about 10 to about 1
A water-soluble phosphine oxide containing one moiety having 8 carbon atoms and two moieties selected from the group consisting of alkyl groups containing from about 1 to about 3 carbon atoms and hydroxyalkyl groups, and about Included are water soluble sulfoxides containing one moiety selected from the group consisting of one alkyl moiety having 10 to about 18 carbon atoms and alkyl and hydroxyalkyl moieties having about 1 to about 3 carbon atoms. To be

These amine oxide surfactants include in particular C _{10 to} C ₁₈ alkyldimethylamine oxides, and C _{8 to} C ₁₂ alkoxyethyldihydroxyethylamine oxides.

When included, the cleaning compositions of the present invention typically comprise from 0.2% by weight, preferably from about 1% by weight to about 15% by weight, preferably up to about 10% by weight. It comprises such a semipolar nonionic surfactant.

[0165] Co-surfactant (cosurfactants) bleaching compositions of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines. Suitable primary amines for use herein include amines having the formula R ₁ NH ₂ , where R ₁ is a C _{6 to} C ₁₂ , preferably a C _{6 to} C ₁₀ alkyl chain or R _4. X (CH ₂ ) _n , X is —O—,
-C (O) NH- or a -NH-, _{R 4} is a _C 6 _{-C 12} alkyl chains, n represents 1-5, preferably 3. The R ₁ alkyl chain may be linear or branched and may be interrupted by up to 12, preferably less than 5, ethylene oxide moieties.

Preferred amines according to the above formula are n-alkyl amines. Suitable amines for use herein can be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2
-Ethylhexyl-oxypropylamine, laurylamidopropylamine and amidopropylamine. The most preferred amines for use in the composition are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly desirable are n-dodecyldimethylamine and bishydroxyethylcoconut alkylamine and 7-fold ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

LFNI Particularly preferred surfactants for the automatic dishwashing composition (ADD) of the present invention are the low-foaming nonionic surfactants (LFNI) described in US Pat. Nos. 5,705,464 and 5,710,115. Is. LFNI can be present in an amount of 0.01 to about 10% by weight, preferably about 0.1 to about 10% by weight, most preferably about 0.25 to about 4% by weight. LFNI is most typically used in ADD to improve the water-covering effect (especially from glass) that LFNI imparts to ADD products.
LFNI also includes the non-silicone, non-phosphate based polymeric materials described in detail below which are known to defoam food stains that occur in automatic dishwashing.

Preferred LFNIs are described in nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and their more complex surfactants, such as those described in US Pat. Nos. 5,705,464 and 5,710,115. Such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / P
O) a reverse block polymer.

POLY-TERGENT® SLF-18, commercially available from Olin Corp., and LFNI, including all biodegradable LFNIs having the melting point characteristics described above, can also be used.

These and other nonionic surfactants are well known in the art and are included herein by reference Kirk Othmer's Encyclopedia of Chemical Technolog.
y, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems"
Are described in detail in.

Optional Detergent Enzymes The detergent and bleaching compositions of the present invention can also include one or more detergent enzymes. Such enzymes include other proteases, amylases, cellulases and lipases. Such materials are known in the art and are marketed under such trade names. 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 the form of enzyme slurries in nonionic surfactants, such as Novo Nor.
The enzyme marketed under the trade name "SL" from disk, or "L" from Novo Nordisk
The enzyme contained in microcapsules marketed under the trade name "DP". Suitable enzymes and amounts used are described in US Pat. Nos. 5,576,282, 5,705,464 and 5,710,115.

Particularly preferred for use herein are enzymes that are added to the composition in the form of conventional enzyme prills. 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.

[0173]   However, the enzyme added to the composition may be in the form of granules, preferably T-granules.

As used herein, "detergent enzyme" means any enzyme that has a beneficial effect in washing, stain removal or other laundry, hard surface cleaning or personal care detergent compositions. Preferred detergent enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred enzymes for automatic dishwashing are amylase and / or proteases, which are now more and more compatible with bleach, due to the types currently on the market and a series of improvements, but still due to bleach. Includes both improved versions that remain sensitive to deactivation.

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.

Examples of such suitable enzymes are described in US Pat. Nos. 5,705,464, 5,710,115, 5,576,
282, 5,728,671 and 5,707,950.

Cellulases useful in the present invention include both bacterial or fungal cellulases. Preferably, these cellulases have an optimum pH of 5-12 and a specific activity of about 50 CEVU / mg (cellulose viscosity unit). Suitable cellulases disclose fungal cellulases produced from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively, described in U.S. Pat.No. 4,435,307, Japanese Patent J61078384 and International Patent WO96 / 02653. There is. European Patent 739982 discloses cellulases isolated from a novel Bacillus variety. Suitable cellulases are British Patents GB-A-2,075,028, GB-A-2,095,275.
No. DE-OS-2,247,832 and International Patent No. WO 95/26398.

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

Another suitable cellulase is obtained from Humicola insolens, having a molecular weight of about 50 KD.
a, a cellulase containing 415 amino acids with an isoelectric point of 5.5, and Humicola in
It is a ~ 43 kD endoglucanase derived from solens, DSM 1800 and exhibiting cellulase activity, the preferred endoglucanase component having the amino acid sequence disclosed in WO 91/17243. A suitable cellulase is also the EGIII cellulase obtained from Trichoderma longibrachiatum described in International Patent No. WO94 / 21801 to Genencor. A particularly suitable cellulase is a cellulase with color-protecting properties. Examples of such cellulases are described in European Patent Application No. 91202879.2, 1991.
Cellulase described in Nov. 6 (Novo). Carezyme and Cellu
The enzyme (Novo Nordisk A / S) is particularly useful. See also International Patent No. WO 91/17244. Other cellulases suitable for fabric protection and / or cleaning properties are described in WO 96/340.
92, WO 96/17994 and WO 95/24471.

Cellulase, when present, is present in an amount of 0.0001 to 2% pure enzyme by weight of the cleaning composition.

Peroxidase enzymes are used in combination with oxygen sources such as percarbonates, perborates, persulfates, hydrogen peroxide, etc., and phenolic substrates as bleach enhancing molecules. These enzymes are used to "solution bleach", ie to prevent dyes or pigments removed from the substrate during the washing operation from migrating to other substrates present in the laundry solution. Peroxidase enzymes are known in the art, such as horseradish peroxidase, ligninase, and haloperoxidase,
Examples include chloro- and bromoperoxidase. Suitable peroxidases and detergent compositions containing peroxidases are described, for example, in US Pat.
No. 4, No. 5,710,115, No. 5,576,282, No. 5,728,671 and No. 5,707,950, P
CT International Application Nos. WO89 / 099813, WO89 / 09813, and European Patent Application No. 9
No. 1202882.6, filed Nov. 6, 1991, and No. 96870013.8, filed Feb. 20, 1996. Laccase enzymes are also suitable.

Reinforcing agents are generally included in amounts of 0.1 to 5% by weight of the total composition. Suitable toughening agents are substituted phenothiazine and phenoxazine, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (E).
PC), 10-phenoxazine propionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621), substituted syringates (C3 to C5 substituted alkyl syrinates) and phenols. . Sodium percarbonate or sodium perborate are the preferred sources of hydrogen peroxide. The peroxidase is typically incorporated in an amount of 0.0001 to 2% pure enzyme by weight of the cleaning composition.

The enzyme system can be used as a bleaching agent. Hydrogen peroxide is also present by the addition of an enzyme system capable of generating hydrogen peroxide at the beginning of or during the washing and / or rinsing steps (ie an enzyme and a substrate for that enzyme). be able to. Such an enzyme system is described in European Patent Application No. 91202655.6.
Specification, filed October 9, 1991.

Other preferred enzymes that can be included in the laundry composition of the present invention include lipases.
Suitable lipase enzymes for detergents are microorganisms of the Pseudomas family, such as British Patent No. 1,372.
Enzymes produced by Pseudomas stutzeri ATCC 19.154, described in US Pat. A preferred lipase is the microorganism Pseudomonas fluorescent IAM.
Included are lipases produced by 1057 that exhibit 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., Taga.
Chromobacter viscosum, eg Chromobacte, commercially available from Ta, Japan
r viscosum var. lipolyticum NRRLB 3673 derived lipase, US Biochemic
Chromobacter visco from al Corp., USA and Disoyynth Co., The Netherlands
There are sum lipase and lipase derived from Pseudomonas gladioli. Particularly preferred lipases are M1 Lipase (trade name) and Lipomax (trade name) (Gist-Brocades).
) And Lipolase ™ and Lipolase Ultra ™ (Novo) and have been found to be very effective when used in combination with the compositions of the present invention. European Patent No. 258068, International Patent No. WO by Novo Nordisk
92/05249 and WO95 / 22615, and Unilever International Patent WO94 / 0357
The lipolytic enzyme described in each specification of No. 8, WO95 / 35381 and WO96 / 00292 is also suitable.

A cutinase [EC 3.1.1.50] is also suitable, but is considered to be a special type of lipase, namely a lipase that does not require surface activation. Addition of cutinase to detergent compositions is described, for example, in WO-A-88 / 09367 (Genencor), WO9.
0/09446 (Plant Genetic System) and WO94 / 14963 and WO94 / 14964 (
Unilever).

The lipase and / or cutinase is typically used in 0.0001-2 of the cleaning composition.
Formulated in the amount of wt% pure enzyme.

In addition to the above lipases, phospholipases can be incorporated into the laundry compositions of the present invention. Examples of suitable phospholipases include EC 3.1.1.32 phospholipase A1
, EC3.1.1.4 phospholipase A2, EC3.1.1.5 phospholipase, EC3.1.4.3 phospholipase C, EC3.1.4.4. Phospholipase D, but are not limited thereto. Commercially available phospholipases include LECITASE (trade name) supplied by Novo Nordisk A / S, Denmark and Phospholipase A2 commercially available from Sigma. When phospholipase is included in the composition of the present invention, it is preferred that it also includes amylase. Without wishing to be bound by theory, the combined action of phospholipase and amylase removes adherent dyes, especially grease / oiliness, starchy and highly colored dyes and stains. Preferably, the phospholipase and amylase, if present, are incorporated into the composition of the invention in a pure enzyme weight ratio of 4500: 1 to 1: 5, more preferably 50: 1 to 1: 1.

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. Proteolytic enzymes are described in modified bacterial serine proteases, such as European Patent Application No. 87303761.8, filed April 28, 1987 (especially pages 17, 24 and 98), herein referred to as "Protease B". And European Patent Application No. 199,404, relating to modified bacterial serine proteolytic enzymes, 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 described in European Patent No. 90915958: 4, published May 16, 1991, which corresponds to International Patent No. WO 91/06637. Also included herein are genetically modified variants, especially variants of Protease C.

A preferred protease, termed "Protease D," is described in US Pat. No. 5,677,27.
It is a carbonyl hydrolase described in No. 2 and International Patent No. WO95 / 10591. Also suitable is the carbonyl hydrolase variant of the protease described in WO95 / 10591, which is used in the precursor enzyme
A plurality of amino acid residues corresponding to the +210 position are replaced with the following residues: +33,
+62, +67, +76, +100, +101, +103, +104, +107
, +128, +129, +130, +132, +135, +156, +158,
+164, +166, +167, +170, +209, +215, +217, +
218, and +222, obtained by substituting in combination with one or more of the following, wherein the numbered positions are the natural subtilisins or other carbonyl hydrolases or subtilisins obtained from Bacillus amyloliquefaciens, such as Baci
llus lentus subtilisin (US Patent Application No. 60 / 048,550 pending, filed June 4, 1997, and PCT International Application No. PCT / IB98 / 00853) corresponds to the equivalent amino acid residue.

In the present invention, the proteases described in patent application EP 251446 and international patent WO 91/06637 and the protease BL described in international patent WO 91/02792.
AP (trade name) and variants thereof described in International Patent No. WO 95/23221 are also suitable.

See also the high pH protease obtained from Bacillus sp. NCIMB 40338 described in International Patent No. WO 93 / 18140A to Novo. An enzymatic detergent comprising a protease, one or more other enzymes, and a reversible protease inhibitor is described in International Patent No. WO92 / 03529 to Novo.
It is described in No. A. If desired, International Patent No. WO95 / 0779 to Procter & Gamble
There are also proteases with reduced adsorptivity and increased hydrolyzability as described in No. 1. Suitable recombinant trypsin-like proteases for detergents here are described in WO 94/25583 to Novo. Other suitable proteases are described in Unilever EP 516200.

Particularly useful proteases are described in PCT applications WO95 / 30010, WO95 / 30011, and WO95 / 29979. Suitable proteases are ESPERASE (trade name), ALCALASE (trade name), DURAZYM (trade name), SAVINASE (trade name), EVERLAS
Novo Nordi in Denmark as E (trade name) and KANNASE (trade name)
From sk A / S and as MAXATASE (trade name), MAXACAL (trade name), PROPERASE (trade name), and MAXAPEM (trade name), all Genencor International (previous G
ist-Brocades, The Netherlands).

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 substitution of amino acid residues at one or more amino acid residue positions other than the amino acid residue position corresponding to the position, and / or all PCT applications WO99 / 20727, WO99 / owned by The Procter & Gamble Company As described in 20726 and WO99 / 20723, multiple substituted protease mutants are Bacillus amyloliquefac.
comprising 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 iens subtilisin.

[0194]   More preferably, the protease variant is

[Chemical 90] A combination of substitutions selected from the group consisting of:

[0195]   More preferably, the protease variant is

[Chemical Formula 91] 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.

When present, such proteolytic enzymes are present in the cleaning compositions of the present invention in an amount of 0.0001 to 2% by weight of the composition, preferably 0.001 to 0.2% by weight, more preferably It is incorporated in an amount of 0.005-0.1% by weight pure enzyme.

Amylases (α and / or β) can be included to remove carbohydrate-based stains. International Patent No. WO 94/02597 describes a cleaning composition comprising a mutant amylase. See also International Patent No. WO 95/10603. Other amylases known for cleaning compositions include both α- and β-amylases. α-
Amylases are known in the art and are known from U.S. Patent No. 5,003,257, European Patent No. 252,666, International Patent No.WO91 / 00353, French Patent No.FR2,676,456, European Patent No. 285,123, No. 525,610, No. 368,341 and British Patent No. 1,296,839
No. (Novo). Other suitable amylases are described in WO 94/18314 and WO 96/05295, Genencor, with enhanced stability of amylase, and in WO 95/10603 Novo. N
It is an amylase mutant further modified with the immediate parent, commercially available from ordisk A / S. Amylases described in EP 277216 are also suitable.

Examples of commercially available α-amylase products are Purafect Ox Am (trade name) from Genencor, and all Novo Nordisk A / S, Termamyl (trade name), Ban (trade name), Fungamyl from Denmark. (Trade name) and Duramyl (trade name). International Patent No. WO 95/26397 describes other suitable amylases, namely temperatures between 25 ° C and 55 ° C.
Described is an α-amylase having a specific activity of at least 25% higher than that of Termamyl (trade name) as measured by Phadebas (trade name) α-amylase activity assay at a pH value of 8 to 10. is doing. International Patent WO 96/23873 (Novo No
The variants of the abovementioned enzymes described in rdisk) are preferred. Other amylolytic enzymes with improved properties in terms of activity level and combination of thermostability and high activity level are described in WO95 / 35382.

Such amylolytic enzyme, when present, is present in the cleaning composition of the present invention in an amount of 0.0001 to 2% by weight of the composition, preferably 0.00018 to 0.06%, more preferably Formulated in an amount of 0.00024-0.048% by weight pure enzyme.

The above enzymes may be from any suitable source, eg plants, animals, bacteria, fungi and yeast. The origin may further be mesophilic or exstremophilic (cryotrophic, psychrotrophic, thermophilic, pressureophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes can be used. It is common today to denature wild-type enzymes by protein / genetic engineering techniques and optimize their performance efficiency with the laundry detergent and / or fabric protection compositions of the present invention. . For example, variants can be designed to increase the compatibility of the enzyme with the components commonly used in such compositions. Alternatively, the variants can be designed such that the optimum pH of the enzyme variant, stability to bleaching or chelating agents, catalytic activity, etc. are compatible with a particular cleaning application.

In particular, attention should be paid to amino acids that are sensitive to oxidation in the case of bleach stability and to surface charge for compatibility of surfactants. The isoelectric point of such an enzyme can be changed by substituting a part of charged amino acids, and for example, the increase of the isoelectric point may improve the compatibility with an anionic surfactant. Enzyme stability can be further enhanced by, for example, forming additional salt bridges, forcing calcium binding sites, and increasing chelator stability.

These optional detergent enzymes, if present, are present in the cleaning composition
It is formulated in an amount of 0.0001 to 2% pure enzyme by weight of the composition. The enzyme can be added as a separate single component (prill, granules, stabilized liquid, etc.) or as a mixture of two or more enzymes (eg co-granule).

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

A series of enzymatic materials are described in International Patents WO9307263 and WO9307260, WO8908694 to Genencor International, and US Pat. No. 3,553, to McCarty et al.
No. 139. Enzymes are also disclosed in US Pat. Nos. 4,101,457 and 4,507,219. Enzyme materials particularly useful in liquid detergent formulations, and the incorporation of those enzymes into such formulations, is described in US Pat. No. 4,261,868.

Enzyme Stabilizer The enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed, for example, in US Pat. No. 3,600,319, European Patents 199,405 and 200,586. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. A useful Bacillus, sp. AC13 for producing proteases, xylanase and cellulase is described in International Patent No. WO9401532. 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. Nos. 5,705,464, 5,710,115 and 5,576,282.

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

Preferred builders for use in the detergent and bleaching compositions described herein, especially in the dishwashing compositions, are US Pat. Nos. 5,695,679, 5,705,464 and 5,710,115.
Water-soluble builder compounds (eg polycarboxylates) as described in No.
But is not limited to these. Other suitable polycarboxylates are described in US Pat. Nos. 4,144,226, 3,308,067 and 3,723,322. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially titrates.

Inorganic or P-containing detergent builders include alkali metal, ammonium and alkanolammonium polyphosphates (eg tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphates), phosphonates (eg US Pat. Third 3,15
9,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates However, the present invention is not limited to these.

However, there are areas where non-phosphate builders are needed. Importantly, even in the presence of so-called "weak" builders (compared to phosphate), eg citric acid,
Alternatively, the compositions of the present invention work surprisingly effectively even in the so-called "low builder" situations that occur with zeolites or layered silicate builders.

Suitable silicates are water soluble with a SiO ₂ : Na ₂ O ratio of about 1.0 to 2.8, preferably about 1.6 to 2.4, most preferably about 2.0. Includes sodium silicate. The silicate may be in the form of an anhydrous salt or a hydrated salt. SiO ₂ : Na ₂ O
Most preferred is sodium silicate with a ratio of 2.0. The silicate, if present, is present in the detergent and laundry compositions described herein, preferably from about 5 to about 5 of the composition.
It is present in an amount of 0% by weight, more preferably about 10 to about 40% by weight.

Partially soluble or insoluble builder compounds suitable for use in detergents and bleaching compositions, especially granular detergent compositions, are crystalline layered silicates, preferably US Pat. No. 4,664,839. And the crystalline layered sodium silicates (partially water-soluble) and sodium aluminosilicates (water-insoluble) described in US Pat. When present in the detergent and bleaching compositions, these builders typically represent about 1-80% by weight of the composition, preferably about 10-70%.
Most preferably present in an amount of about 20-60% by weight.

The general formula NaMSi _x O _{2x + 1} · yH ₂ O, wherein M is sodium or hydrogen, and x is a number from about 1.9 to about 4, preferably about 2 to about 4, most preferably 2. And y is a number from about 0 to about 20, preferably 0) can be used in the compositions described herein. Crystalline layered sodium silicates of this kind are described in EP-A-0164514 and their method of manufacture is described in German patents DE-A-3417649 and DE-A-3742043. Has been done. The most preferred material is Delta-Na ₂ S commercially available from Hoechst AG as NaSKS-6.
iO ₅ (generally abbreviated as “SKS-6”). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSK
S-6 has the delta-Na ₂ SiO ₅ form of the layered silicate. SKS-6 is a highly preferred layered silicate for use in the compositions described herein,
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 and y is a number from 0 to 20, preferably 0). Can be used in the composition. Various other layered silicates commercially available from Hoechst include the alpha, beta and gamma forms of NaSKS-5, NaSKS-7 and Na.
SKS-11 is mentioned. 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 and are a crispening agent in granular formulations.
As a stabilizer for oxygen bleaches and as a component of foam control systems.

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

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 builder has the following empirical formula. [M _z (AlO ₂ ) _y ] .xH ₂ O In the formula, z and y are integers of at least 6, and the molar ratio of z and y is 1.0 to about 0.
． 5 and x is an integer from about 15 to about 264. Preferably, the aluminosilicate builder is an aluminosilicate zeolite having the unit cell formula: Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]. In the formula XH ₂ O, z and y are at least 6, the molar ratio of z and y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276, more preferably 10. 26
It is 4. The aluminosilicate builder is preferably in the hydrated form, preferably crystalline, and comprises about 10% to about 28%, more preferably about 18% to about 22% bound form of water.

These aluminosilicate ion exchange materials may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetic products. A method of making an aluminosilicate ion exchange material is disclosed in US Pat. No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP and Zeolite HS,
And commercially available as a mixture thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. xH ₂ O wherein x is about 20 to about 30, especially about 27. This material is called Zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle diameter of about 0.1-10 microns. Zeolite X
Has the formula: _{Na 86 [(AlO 2) 86} (SiO 2) 106] · 276H 2 O

Since 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.

The detergent compositions described herein include those described in US Pat. No. 4,566,984.
, 3-Dicarboxy-4-oxa-1,6-hexanedioate and related compounds are also suitable. Useful succinic acid builders include the 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), 2-pentadecenyl succinate, and the like. . Lauryl succinate is a preferred builder of this type and is described in European Patent Application No. 86200690.5 / 0,200263, published November 5, 1986.

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 described 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.

Dispersants One or more suitable polyalkyleneimine dispersants can be incorporated into the cleaning compositions of the present invention. Examples of such suitable dispersants are described in European Patent Application No. 111,
965, 111,984, and 112,592, U.S. Pat.Nos. 4,597,898, 4,548,74
Seen in No. 4 and No. 5,565,145. However, any suitable clay / soil dispersant or anti-redeposition agent can be used in the laundry composition of the present invention.

Further, polymeric dispersants including polymeric polycarboxylates and polyethylene glycols are suitable for use in the present invention. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid,
Maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,
Included are mesaconic acid, citraconic acid and methylenemalonic acid. A particularly suitable polymeric carboxylate can be derived from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of the polymer in such acid form is preferably about 2,000 to 10,000.
0, more preferably about 4,000 to 7,000, most preferably about 4,000 to
It is 5,000. Water-soluble salts of such acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this kind are known materials. The use of this type of polyacrylate in detergent compositions is described, for example, in US Pat. No. 3,308,067.

Acrylic acid / maleic acid copolymers can also be used as a preferred component of the dispersion / redeposition preventing agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of the copolymer in such acid form is preferably about 2
5,000 to 100,000, more preferably about 5,000 to 75,000, most preferably about 7,000 to 65,000. The ratio of acrylate to maleate moieties in such copolymers is generally about 30: 1 to about 1: 1 and more preferably about 10: 1 to 2: 1. Water-soluble salts of such acrylic acid / maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this kind are known materials and are described in European Patent Application No. 66915, published Dec. 15, 1982, as well as such polymers comprising hydroxypropyl acrylate. European Patent EP 193,360, published September 3, 1986. Still other useful dispersants include maleic acid / acrylic acid / vinyl alcohol terpolymers. Such materials are also described in European Patent EP 193,360,
For example, a 45/45/10 terpolymer of acrylic acid / maleic acid / vinyl alcohol is included.

Another polymeric material that can be included is polyethylene glycol (PEG). P
EG exhibits dispersant performance and also acts as a clay soil removal-redeposition inhibitor. Typical molecular weight ranges for these purposes are about 500 to about 100,000,
Preferably about 1,000 to about 50,000, more preferably about 1,500 to about 1.
It is 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants such as polyaspartate preferably have an (average) molecular weight of about 10,000.

Soil Release Agent The compositions of the present invention can optionally comprise one or more soil release agents. When used, the soil release agent will generally be from about 0.01% by weight of the composition, preferably from about 0.1% by weight, more preferably from about 0.2% to about 10% by weight, preferably Comprises up to about 5% by weight, more preferably up to about 3% by weight. Suitable soil release polymers are described in U.S. Patent Nos. 5,728,671, 5,691,298, 5,599,782.
No., 5,415,807, 5,182,043, 4,956,447, 4,976,879, 4,968,
No. 451, No. 4,925,577, No. 4,861,512, No. 4,877,896, No. 4,771,730, No. 4,7
No. 11,730, No. 4,721,580, No. 4,000,093, No. 3,959,230, and No. 3,893,929
And European patent application No. 0219048, but is not limited thereto.

Other suitable soil release agents are US Pat. Nos. 4,201,824, 4,240,918, 4,525,
524, 4,579,681, 4,220,918 and 4,787,989, European Patent No.
279,134A, 457,205A and German Patent 2,335,044.

Chelating Agents The compositions of the present invention can also optionally include chelating agents that chelate metal ions and metallic impurities that tend to deactivate the bleaching agent. Useful chelating agents include aminocarboxylates, phosphonates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Other examples and amounts of suitable chelating agents are described in US Pat. Nos. 5,705,464, 5,7.
No. 10,115, No. 5,728,671 and No. 5,576,282.

The present compositions are useful as chelating agents or co-builders useful with, for example, insoluble builders such as zeolites, layered silicates, and the like.
MGDA) may also be included.

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

Foam Inhibitors Another optional ingredient is silicones and foam inhibitors represented by silica-silicone mixtures. Examples of suitable suds suppressors are described in US Pat.
707,950 and 5,728,671. These foam control agents are generally used in an amount of 0.001 to 2% by weight of the composition, preferably 0.01 to 1% by weight.

Softening Agent A fabric softening agent can also be added to the laundry detergent composition of the present invention.
Inorganic softening agents are represented by the smectite clays described in British Patent GB-A-1400898 and US Pat. No. 5,019,292. Organic softening agents include water-insoluble tertiary amines described in British Patent GB-A-1514276 and European Patent EP-B-011340, and their European Patent EP-B. -026527
And mono-C12 to C14 quaternary ammonium salts described in EP-B-026528 and the di-long chain amides described in EP-B-0242919. . Other useful organic components of fabric softening systems include polymeric polyethylene oxide materials such as those described in EP-A-0299575 and 0313146.

Particularly suitable fabric softening agents are disclosed in US Pat. Nos. 5,707,950 and 5,728,673.

The amount of smectite clay is usually 2 to 20% by weight, more preferably 5 to 15%.
% By weight, this material is added to the rest of the formulation as a dry mix ingredient. Organic fabric softening agents, such as water insoluble tertiary amines or dilong chain amide materials, are compounded in amounts of 0.5 to 5% by weight, usually 1 to 3% by weight, but high molecular weight polyethylene oxide materials. And the water-soluble cation-based material is 0.1 to 2% by weight, usually 0.1.
It is mixed in an amount of 5 to 1.5% by weight. These materials are usually added to the spray-dried part of the composition, but more often are added as dry mixed particles or sprayed on as molten liquid onto other solid components of the composition. It can be convenient.

The biodegradable quaternary ammonium compounds described in EP-A-040562 and EP-A-239910 are the traditionally used di-long alkyl chain ammonium chlorides and Developed as an alternative to methylsulfate.

Examples of aniones compatible with the softeners for quaternary ammonium compounds and amine precursors include chloride and methylsulfate,
It is not limited to these.

Dye Transfer Inhibition The detergent compositions of the present invention prevent the transfer of solubilized, floating dyes from one fabric to another during fabric washing and conditioning operations involving colored fabrics. For this reason, dye transfer inhibiting compounds can also be included.

Polymeric Dye Transfer Inhibitor The detergent composition of the present invention contains 0.001 to 10% by weight, preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight of a polymeric dye. Dye transfer inhibitors can also be included. The polymeric dye transfer inhibitors are typically incorporated into detergent compositions to prevent dye transfer from the dyed fabric to the fabric being laundered with the dyed fabric. These polymers have the ability to complex or absorb the stray dyes washed from the dyed fabric before they adhere to other articles in the wash liquor.

Particularly suitable polymeric dye transfer inhibitors are polyamine N-oxide polymers, N-
It is a copolymer of vinylpyrrolidone and N-vinylimidazole, a polyvinylpyrrolidone polymer, polyvinyloxazolidone and polyvinylimidazole, or a mixture thereof. 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 may be chemical or physical and optionally contain active groups on the backbone or on the branched chains. Crosslinked polymers are described in Journal of Polymer Science, Volume 22, 1035-
It is described on page 1039.

In one embodiment, the crosslinked polymer is prepared so that it forms a sterically rigid structure and the dye can be entrapped in the pores formed by the steric structure. In another embodiment, the crosslinked polymer swells to capture the dye. Such crosslinked polymers are described in pending European patent application No. 94870213.9. The addition of such polymers also enhances the performance of the enzymes of the invention.

PH and Buffer Species Many of the detergent and laundry compositions described herein are buffered, ie, relatively resistant to pH reduction in the presence of acidic soil. However, other compositions of the invention have a significantly lower buffering capacity or are substantially unbuffered. Techniques for adjusting or changing pH to recommended levels are not limited to buffers,
It is well known to those skilled in the art, including the use of additional alkalis, acids, pH jump systems, two compartment containers, etc.

Preferred ADD compositions of the present invention are described in US Pat. Nos. 5,705,464 and 5,710,115.
And a pH adjusting component selected from water-soluble alkaline salts and water-soluble organic or inorganic builders, as described in US Pat.

Material Protecting Agents Preferred ADD compositions are described in US Pat. Nos. 5,705,464, 5,710,115 and
One or more material protectants effective as corrosion inhibitors and / or antifog aids, such as those described in 646,101, may be included.

If present, such protective material may be, for example, from about 0.01 to about 5 of the ADD composition.
Formulated at low levels, weight percent.

Other Materials Detergent or adjunct ingredients optionally included in the composition are designed to assist or enhance laundry performance, treatment of the substrate to be washed, or to improve the aesthetics of the composition. One or more materials can also be included. For the compositions of the present invention, the usual usage levels established in the field (generally, the auxiliary components total from about 30 to about 30% of the composition).
Auxiliary ingredients that can be included at about 99.9% by weight, preferably about 70 to about 95% by weight, include: US Pat. Nos. 5,705,464, 5,710,115, 5,698,50.
Other active ingredients such as non-phosphate builders, color speckles, silver protectants, antifog agents and / or corrosion inhibitors as described in Nos. 4, 5,695,679, 5,686,014 and 5,646,101. Agents, dyes, fillers, bactericides, alkalinity sources, hydrotropic agents, antioxidants, fragrances, solubilizers, carriers, processing aids, pigments, and pH adjusters, but are not limited thereto. Not a thing.

Laundry Method In addition to the methods of cleaning fabrics, dishes and other hard surfaces, and body parts by personal cleansing described herein, the present invention also treats soiled or dyed fabrics prior to laundering. A method of contacting the dye and / or soil directly with a highly concentrated form of the bleaching composition as described above, before washing such a fabric using a conventional wash solution. Include. Preferably, the bleaching composition is soiled /
Contact with the dye for about 30 seconds to 24 hours before washing the pretreated soiled / dyed fabric in the usual manner. More preferably, the pretreatment time is about 1-180 minutes.

Organocatalytic Products The organocatalytic compounds and / or bleaching compositions of the present invention can be used in a variety of products used in laundry processes.

In a preferred embodiment, there is provided a product comprising an organocatalytic compound of the invention and / or a bleaching composition. The product further includes instructions for using the organocatalyst compound and / or the bleaching composition to wash fabrics in need of cleaning, preferably stained fabrics. Instructions for use include multiple steps, preferably a series of (i) contacting the fabric with a wash solution, preferably containing a peracid, and (ii) an organocatalyst compound and / or a bleaching composition by means of dosing. The step of adding to the washing solution is included.

The dosing step of step (ii) can be accomplished by the various dosing means described herein.

According to these instructions, the fabric is added to the wash solution followed by the organocatalyst compound and / or the bleaching composition.

It is also effective to add a long-lasting organocatalyst compound and / or bleaching composition to the wash solution after adding the fabric to the wash solution, but because of the high stability of the long-lasting organic catalyst, The order of addition is not very important.

Measurement of Long Lasting Organocatalysts Test Method I is described below to help determine which organocatalyst is within the scope of the present invention.

Test Method I: General Principles / Parameters: Keep all solutions at 20 ° C. The pH is adjusted using sodium carbonate or sulfuric acid as needed. All solutions are continuously stirred at 500 rpm except for a small amount (1-5 mL) of dye bleach solution (DBS) aliquot taken to measure absorption. The absorption value is based on the standard dye solution (R
DS) λ _max . Peracetic acid, a 32 wt% solution in dilute acetic acid, is purchased from Aldrich (# 26,933-6). OC is an organic catalyst.

OCS was adjusted to 0.0% immediately before the addition of OCS to the base solution (within 1 minute).
10 mmol (typically about 2-3 mg, depending on molecular weight) of organic catalyst (OC)
Is a solution containing an organic catalyst prepared by dissolving 5 mL of deionized water at 20 ° C. If the organic catalyst does not dissolve in 5 mL of deionized water, add 5 mL of organic solvent to 5 mL of deionized water to help dissolve the organic catalyst. The organic solvent used is methanol, ethanol, dimethylformamide, or acetonitrile. If the organic catalyst does not dissolve in a 1: 1 mixture of deionized water and organic solvent, add 10 parts of organic catalyst.
Dissolve in 0% organic solvent. If the organocatalyst is found to be insoluble in the above solvent medium, it is added to the base solution in pure form.

BS is the base solution to which OCS is added. Base solution is deionized water 1.0
10 mg (10 ppm) of L as a chelating agent (capable of sequestering transition metal ions to avoid decomposition of peracetic acid and / or bleach), and peracetic acid (
When 76 mg (76 ppm, 1.0 mmol) was added (as 100% active),
Prepared by mixing with sufficient sodium carbonate such that the pH of the solution is 10.0 (between 9.9 and 10.1). Preparation of BS is completed by stirring for 1 minute.

OCBS is a base solution containing an organic catalyst, and OC1 was added to freshly prepared BS1L.
Prepare by adding S. The preparation of OCBS is completed by adding OCS to BS. At this time, the pH of OCBS is 10.0 (between 9.9 and 10.1).
Should be. If the pH is not within this range, the OCBS pH will be 10.0 (
Sodium carbonate or sulfuric acid is added, and the OC
It is necessary to repeat the preparation of OCBS by adding S to BS.

CDS is a concentrated dye solution defined as a 90 ppm deionized aqueous solution of Tropaeolin O dye (Aldrich 19,968-0).

DBS is a dye bleaching solution formed by adding a 100 mL aliquot of OCBS to 10 mL CDS. DBS should have an initial pH of 10.0. If (unexpectedly) the pH of DBS drops below 9.6 at time = t _D (defined below), the pH will remain between 9.8 and 10.1 for t _D. Must be adjusted to.

W _OC is a parameter representing the weight of 100% pure organic catalyst (OC) used to form the organic catalyst solution (OCS) in the final test method. The deficient value for this parameter is 0.010 mmol added to 1.0 L BS.

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.}

D _dec is a parameter representing the time elapsed between the formation of OCBS and the formation of a dye bleaching solution (DBS) by adding OCBS to CDS in the test method. This value is the degradation duration of the organocatalyst in OCBS before adding it to CDS. Lack of parameter d _dec (eg d _dec = 45 minutes) (defau
lt) value is defined in the claim. The value of the parameter d _dec is the parameter _dr
It is specified to be equal to the value of _ef .

D _ref is a parameter in the test method that represents the time elapsed between the completion of BS preparation and the formation of the dye bleaching solution (DBS) by adding BS to CDS. This value is the baseline duration of peracid in BS before addition to CDS. The default value of the parameter d _ref (eg d _ref = 45 minutes) is defined in the claims. The value of the parameter d _ref is defined to be equal to the value of the parameter d _dec .

D _bleach is a parameter representing the time elapsed between the formation of the dye bleaching solution (DBS) and the data acquisition in the test method. This value is BS or OC
Bleach duration of DBS formed from adding BS to CDS.

Test Method (Part I): The first step is the preparation of BS as described above. Set the time of BS preparation completion to t = 0. A 100 mL aliquot of BS was taken at d _ref , and CDS10.
Add to 0 mL. A 1 to 5 mL aliquot R of the obtained DBS is collected immediately before absorption measurement (data acquisition). At the end of d _bleach , the absorption of R is measured at λ _max .

The time point at which the aliquot R was measured for absorption (data acquisition) is defined as t _R.
Therefore, it is necessary that t _R = d _ref + d _bleach . The absorption values measured at t _R is defined as _{A t (R).} The symbol δAt _(R) is defined as _{Amax-At ( R)} .

Test Method (Part II): The first step is the preparation of OCBS as described above. Time to complete OCBS preparation is t
Set to = 0. Take a 100 mL aliquot of OCBS at d _dec and add to 10.0 mL of CDS in one go. A 1 to 5 mL aliquot D of the obtained DBS is collected immediately before absorption measurement (data acquisition). At the end of d _bleach , the absorption of D is measured at λ _max .

The time point at which the aliquot D was measured for absorption (data acquisition) is defined as t _D.
Therefore, it is necessary that t _D = d _dec + d _bleach . The absorption values measured at t _D is defined as _{A t (D).} The symbol δAt _(D) is defined as _{Amax-At ( D)} .

The Organocatalyst Life (OCL) is defined as the value of d _dec (or the time it takes for OC to be exhausted in OCBS ₎ , so δA _{t (D)} = 3 × δA _{t (R)} .

There are two cases depending on the value of δA _{t (D)} compared to the value of δA _{t (R)} .

Case A: When the value of δA _{t (D)} is ≧ m _f xδA _{t (R)} (m _f is 3), a long-lasting organocatalyst is shown, whose OC is of the present invention. Enter the range.

Case B: The value of δA _{t (D)} is <m _f xδA _{t (R)} (m _f (final multiplier) is 3)
), No long lasting organocatalyst is shown and its OC is not within the scope of the present invention.

Finally, the value of the final multiplier (m _f ) relating the value of δA _{t (D)} to δA _{t (R)} remains constant over 30 minutes and the measurement of m _f at d _dec = 2 minutes. If the value is greater than 1.5 times the value of m _f , which remains constant over 30 minutes,
OCL is defined as d _dec where the value of m _f is initially constant.

The following examples illustrate the compositions of the present invention, but do not necessarily limit the scope of the invention. Since some of the organic catalyst compounds synthesized in the following examples (for example, structure 6 ) have stereogenic centers, two or more kinds of isomer catalyst compounds may be selected depending on the selection of the isomer starting materials. Can be synthesized. As will be apparent to those skilled in the art, organocatalytic compounds having different isomeric configurations can have a variety of properties, including organocatalyst life.

[0274]

EXAMPLES Production of Synthesis Examples Example I N-(1-cyclohexylethyl) -3,4-dihydro-isoquinolinium tetra- phenyl borate (1)

[Chemical Formula 92] Typical synthetic methods of dihydroisoquinolinium salts are described in the art, for example in Pa.
ge, P.CB. et al. J. Org. Chem. 1998, 63, 2774. The parent amine used in this reaction is 1-cyclohexylethylamine.

[0275] Production Example II N-tert-butyl-3,4-dihydro isoquinolinium tetraphenylborate (2)

[Chemical formula 93] Typical synthetic methods of dihydroisoquinolinium salts are described in the art, for example in Pa.
ge, P.CB. et al. J. Org. Chem. 1998, 63, 2774. The parent amine used in this reaction is 1-cyclohexylethylamine.

Example III Preparation of 3- (3,4-dihydroisoquinolinium) -butane-2-sulfate (6 ) Step 1: Preparation of 3,4-dihydroisoquinoline ( 2 ) is described in US Pat. No. 5,576.
, 282.

Step 2: Preparation of 2,3-butanediol sulfate ( 5 ):

[Chemical 94]

2,3-Butanediol ( 4 , 4, 4 .51 g, 50.0 mmol) and carbon tetrachloride 50 mL
Put in. When the 2,3-butanediol was dissolved, thionyl chloride (5.5 mL,
75 mmol) is added dropwise at room temperature and the reaction mixture is heated to about 60 ° C. After 2 hours, the reaction mixture is gradually cooled to about 0 ° C. Add deionized water (50 mL) and acetonitrile (75 mL). Ruthenium chloride hydrate (0.13 g, 0.
50 mmol) and sodium iodide (21.4 g, 100 mmol) are added and the reaction mixture is stirred at room temperature for 1 hour. Mix the mixture with diethyl ether (4x1
75 mL), the organic phase is washed with deionized water (5x100 mL), saturated sodium bicarbonate solution (3x100 mL), and brine (2x100 mL), then filtered through celite / silica gel. The filtrate is dehumidified over magnesium sulphate, filtered and concentrated by rotary evaporation to give a clear oil.

Step 3: Preparation of 3- (3,4-dihydroisoquinolinium) -butane-2-sulfate ( 6 )

[Chemical 95] In a 100 mL round bottom flask equipped with a magnetic stirrer, 3,4-dihydroisoquinoline (2.02 g, 15.4 mmol) and acetonitrile (15.2 mL).
). 2,3-butanediol cyclic sulfate (2.43 g, 1
6.0 mmol) are added at once. Once the reaction mixture is concentrated, additional acetonitrile (60 mL) is added and the reaction mixture is stirred overnight. The precipitate is collected, washed 5 times with acetone and air dried.

Example IV Preparation of 3- (3,4-dihydroisoquinolinium) -propane-1-sulfate ( 8)

[Chemical 96] In a 100 mL round bottom flask equipped with a magnetic stirrer, 3,4-dihydroisoquinoline (2.02 g, 15.4 mmol) and acetonitrile (15.2 mL).
). 2,3-propanediol cyclic sulfate (2.21 g,
16.0 mmol) is added at once. Once the reaction mixture is concentrated, additional acetonitrile (60 mL) is added and the reaction mixture is stirred overnight. The precipitate is collected, washed 5 times with acetone and air dried.

The following examples illustrate the compositions of the present invention, but do not necessarily limit the scope of the invention.

The following examples use some abbreviations known to those of skill in the art and consistent with the disclosure provided herein.

The organic catalyst in the examples below may be any of the organic catalysts mentioned above, including examples I to IV, but preferably the organic catalyst is represented by the structure below (having the above substituents).

[Chemical 97]

[Chemical 98]

[0284] Preferably, the organic catalyst is an iminium-based organic catalyst represented by the following structure (having the above-mentioned substituent).

[Chemical 99]

[Chemical 100]

[0285] EXAMPLE V Granular automatic dishwashing composition ingredients A B C Citric Acid 15.0 - - Citrate 4.0 29.0 15.0 Acrylate / methacrylate 6.0 - 6.0 copolymer - acrylate maleic acid copolymer - 3.7 - Dry additives carbonate Salt 9.0-20.0 Alkali metal silicate 8.5 17.0 9.0 Paraffin-0.5-Benzotriazole-0.3-Amylase 1.6 1.6 1.6 Protease 0.2 0.1 0.06 Percarbonate (AvO) 1.5--Perborate monohydrate-0.3 1.5 Per Borate tetrahydrate-0.9-NOBS--2.40 TAED 3.8 4.4-Organocatalyst 0.2 1 0.005 Diethylenetriamine penta 0.13 0.13 0.13 Methylphosphonic acid (Mg salt) Alkyl ethoxy sulphate 3.0--3-fold ethoxylated alkyl ethoxy propoxy-1.5- Nonionic surfactant Foaming inhibitor 2.0--Olin SLF 18 Nonionic surfactant--2.0 Sulfate (100% remaining)

Example VI Compact high density (0.96 Kg / l) dishwashing compositions AF of the present invention. Ingredients ABCDEF STPP-51.4 51.4--44.3 Citrate 17.05--49.6 40.2-Carbonate 17.50 14.0 20.0-8.0 33.6 Bicarbonate---26.0--Silicate 14.81 15.0 8.0-25.0 3.6 Metasilicate Acid 2.50 4.5 4.5---PB1 9.74 7.79 7.79---PB4---9.6--Percarbonate----11.8 4.8 Nonionic substances 2.00 1.50 1.50 2.6 1.9 5.9 TAED 2.39--3.8-1.4 HEDP 1.00- ----DETPMP 0.65-----MnTACN----0.008-NOBS-2.40----PAAC--0.008---Organocatalyst 0.0001 0.01 0.6 3 1 2 Paraffin 0.50 0.38 0.38 0.6--Protease 0.1 0.06 0.05 0.03 0.07 0.01 Amylase 1.5 1.5 1.5 2.6 2.1 0.8 BTA 0.30 0.22 0.22 0.3 0.3 0.3 Polycarboxylate 6.0---4.2 0.9 Perfume 0.2 0.12 0.12 0.2 0.2 0.2 Sulfate / water 20.57 1.97 2.97 3.6 4.5 3.9 pH (1% solution) 11.0 11.0 11.3 9.6 10.8 10.9

Example VII Granular dishwashing compositions AF of the present invention having a bulk density of 1.02 Kg / l. Ingredients ABCDEF STPP 30.00 33.5 27.9 29.62 33.8 22.0 Carbonate 30.50 30.50 30.5 23.00 34.5 45.0 Silicate 7.40 7.50 12.6 13.3 3.2 6.2 Metasilicate-4.5 Percarbonate---4.0-PB1 4.4 4.5 4.3--NaDCC --2.00-0.9 Non-ionic substances 1.0 0.75 1.0 1.90 0.7 0.5 TAED 1.00---NOBS----2.0-PAAC-0.004---Organocatalyst 0.05 0.00001 10 7 5 0.8 Paraffin 0.25 0.25--Protease 0.05 0.06 0.025 0.1 0.02 0.07 Amylase 0.38 0.64 0.46-0.6 BTA 0.15 0.15-0.2 Perfume 0.2 0.2 0.05 0.1 0.2 Sulfate / water 23.45 16.87 22.26 30.08 21.7 25.4 pH (1% solution) 10.80 11.3 11.0 10.70 11.5 10.9

Example VIII Tablet detergent compositions AH of the present invention are prepared by compressing a granular dishwashing detergent composition at a pressure of 13 KN / cm ² using a standard 12 head rotary press.

[0289]

[Table 1]

[0290] EXAMPLE IX Granular fabric cleaning composition ingredients Example No. A B Linear alkyl benzene sulphonate 11.4 10.70 Tallow alkyl sulphate 1.80 2.40 C _14-15 alkyl sulphate 3.00 3.10 C _{14- 15} alcohol, 7-fold ethoxylated 4.00 4.00 Tallow alcohol, 11-fold ethoxylated 1.80 1.80 Dispersant 0.07 0.1 Silicone liquid 0.80 0.80 Trisodium citrate 14.00 15 0.0000 Citric acid 3.00 2.50 Zeolite 32.50 32.10 Maleic acid acrylic acid copolymer 5.00 5.00 Diethylenetriamine pentamethylene 1.00 0.20 Phosphonate protease 0.1 0.01 Lipase 0 .36 0.40 amylase 0.30 0.30 sodium silicate 2.00 2.50 Sodium sulphate 3.50 5.20 Polyvinylpyrrolidone 0.30 0.50 Perborate 0.51 TAED 1.0-NOBS-1.0 Organocatalyst 0.11 Phenolsulfonate 0. 1-Peroxidase 0.1 0.1 Minor components up to 100 Up to 100

Example X Granular Fabric Cleaning Composition Ingredients Example Number A B Sodium Linear C ₁₂ Alkyl 6.5 8.0 Sodium Benzene Sulfonate Sulfate 15.0 18.0 Zeolite A 26.0 22.0 Sodium Nitrilotriacetic Acid 5 0.0 5.0 Polyvinylpyrrolidone 0.5 0.7 TAED 3.0-NOBS-2.4 Organic catalyst 1 0.5 Boric acid 4.0-Perborate 0.51 Phenol sulfonate 0.1-Protease 0.02 0.05 Filler (eg silicate, carbonate, up to 100 perfume, water)

Example XI Compact Granular Fabric Cleaning Composition Ingredients % by Weight Alkyl Sulfate 8.0 Alkyl Ethoxy Sulfate 2.0 C25 and C45 Alcohol 6.0 (3- and 7-fold Ethoxylated) Mixture Polyhydroxy Fatty Acid Amide 2.5 Zeolite 17.0 Layered silicate / citrate 16.0 Carbonate 7.0 Maleic acid acrylic acid copolymer 5.0 Soil free polymer 0.4 Carboxymethylcellulose 0.4 Poly (4-vinylpyridine)- N-oxide 0.1 Copolymer of vinylimidazole and vinylpyrrolidone 0.1 PEG2000 0.2 Protease 0.03 Lipase 0.2 Cellulase 0.2 TAED 6.0 Percarbonate 22.0 Organic catalyst 0.1 Ethylenediamine Disuccinic acid 0.3 Foaming inhibitor 3.5 Disodium-4, '-Bis (2-morpholino-0.25 4-anilino-s-triazin-6-ylamino) stilbene-2,2' disulfonate disodium-4,4'-bis (2-sulfostyryl) 0.05 biphenyl Water, fragrance and small ingredients up to 100

Example XII Granular Fabric Cleaning Composition Components Weight% Linear alkyl benzene sulfonate 7.6 C _{16 to} C ₁₈ alkyl sulphate 1.3 C _14-15 alcohol, 7-fold ethoxylated 4.0 coco-alkyl-dimethyl hydroxy Ethyl 1.4 Ammonium chloride dispersant 0.07 Silicone liquid 0.8 Trisodium citrate 5.0 Zeolite 4A 15.0 Maleic acid acrylic acid copolymer 4.0 Diethylenetriamine pentamethylenephosphonic acid 0.4 Perborate 15.0 TAED 5.0 Organocatalyst 2 Smectite clay 10.0 Poly (oxyethylene) (MW300,000) 0.3 Protease 0.02 Lipase 0.2 Amylase 0.3 Cellulase 0.2 Sodium silicate 3.0 Sodium carbonate 10.0 Carbo Xymethylcellulose 0.2 Brightener 0.2 Water, fragrance and minor ingredients up to 100

Example XIII Granular Fabric Cleaning Composition Components Weight% Linear Alkylbenzene Sulfonate 6.92 Tallow Alkylsulfate 2.05 C _14-15 Alcohol, _7x Ethoxylated 4.4 C _12-15 Alkylethoxysulfate, 3x Ethoxylated 0.16 Zeolite 20.2 Citrate 5.5 Carbonate 15.4 Silicate 3.0 Maleic acid acrylic acid copolymer 4.0 Carboxymethyl cellulose 0.31 Soil free polymer 0.30 Protease 0 .1 Lipase 0.36 Cellulase 0.13 Perborate tetrahydrate 11.64 Perborate monohydrate 8.7 TAED 5.0 Organocatalyst 0.05 Diethylenetriamine pentamethylphosphonic acid 0.38 Magnesium sulfate 0.40 Brightener 0.19 Fragrance, silicone, foam control Agent 0.85 to minor components 100

[0295] EXAMPLE XIV Granular fabric cleaning composition ingredients A B C based granular component LAS / AS / AES (65/35) 9.95 - - LAS / AS / AES (70/30) - 12.05 7.70 aluminosilicate 14.06 15.74 17.10 Sodium carbonate 11.86 12.74 13.07 Sodium silicate 0.58 0.58 0.58 NaPAA solid 2.26 2.26 1.47 PEG solid 1.01 1.12 0.66 Brightener 0.17 0.17 0.11 DTPA--0.70 Sulfate 5.46 6.64 4.25 DC-1400 Degassing agent 0.02 0.02 0.02 Moisture 3.73 3.98 4.33 Small amount Ingredient 0.31 0.49 0.31 BOT Spray nonionic surfactant 0.50 0.50 0.50 Aggregate ingredient LAS / AS (25/75) 11.70 9.60 10.47 Aluminosilicate 13.73 11.26 12.28 Carbonate 8.11 6.66 7.26 PEG4000 0.59 0.48 0.52 Moisture / Small ingredient 4.88 4.00 4.36 Functional additive Sodium carbonate 7.37 6.98 7.45 Perborate 1.03 1.03 2.56 AC base coating-1.00-NOBS--2.40 Organic catalyst 1 0.001 0.01 Soil release Coalescence 0.26 0.41 0.31 Cellulase 0.33 0.33 0.24 Protease 0.1 0.05 0.15 AE-Flake 0.40 0.40 0.29 Liquid Spray perfume 0.42 0.42 0.42 Non-ionic material spray 1.00 1.00 0.50 minor component 100

Example XV Granular Fabric Cleaning Composition A B Surfactant -NaLAS 6.40 - -KLAS - 9.90 -AS / AE3S 6.40 4.39 -TAS 0.08 0.11 -C24AE5 3.48 - -Genagen - 1.88 -N- cocoyl N- methyl 1.14 2.82 glucamine _{(lin) -C 8-10} dimethyl hydroxyethyl 1.00 1.40 chloride Builder - zeolite 20.59 13.39 -SKS-6 10.84 10.78 - Citric Acid 2.00- Buffer-Carbonate 9.60 12.07-Bicarbonate 2.00-Sulfate 2.64- Silicate 0.61 0.16 Polymer- Acrylic acid / Maleic acid 1.17 1.12 Copolymer (Na) -CMC 0.45 0.24-Polymer 0.34 0.18-Hexamethylenediamine tetra-1. 00 1.00 E24 ethoxylate, diquaternized with methyl chloride Enzyme-Protease (% pure enzyme) 0.03 0.03-Cellulase 0.26 0.26-Amylase 0.65 0.73 -Lipase 0. 27 0.15 Bleach-TAED (100%) 3.85 3.50-N-nonanoyl-6-amino-2.75 Phenol sulfonate ester of caproic acid-Percarbonate 16.20 18.30-Organic catalyst 0 .00053-HEDP 0.48 0.48-EDDS 0.30 0.30 Others-Malic particles 2.20 + bicarb-Brightener 15/49 0.077 / 0.014 0.07 / 0.014-Zinc phthalocyanine sulfonate 0.0026 0.0026-poly Dimethylsiloxane, 0.25 0.24 with trimethylsilyl endblock units-Soap- 1.00 -fragrance 0.45 0.55 total 100 100

Example XVI Granular Fabric Cleaning Composition A B Surfactant - - NaLAS 6.8 0.4 KLAS - 10.9 FAS 0.9 0.1 AS 0.6 1.5 C25AE3S 0.1 - AE5 4.2 - N- cocoyl N- methyl - 1.8 glucamine Genagen - 1.2 C _8-10 dimethyl hydroxyethyl - 1.0 ammonium chloride Builder SKS-6 3.3 9.0 zeolite 17.2 18.9 citric acid 1.5 - buffer carbonate 21 1 15.0 Sodium bicarbonate-2.6 Sulfate 15.2 5.5 Malic acid-2.9 Silicate 0.1 -Polymer Acrylic acid / Maleic acid 2.2 0.9 Copolymer ( Na) Hexamethylenediamine tetra-0.5 0.7 E24 ethoxylate, diquaternized with methyl chloride Polymer 0.1 0.1 CMC 0.2 0.1 Enzyme--Protease (% Pure enzyme) 0.02 0.05 lipase 0.18 0.14 amylase 0.64 0.73 cellulase 0.13 0.26 bleach TAED (100%) 2.2 2.5 N-nonanoyl-6 -Amino-1.96 Phenol sulfonate ester of caproic acid Sodium percarbonate-13.1 PB4 15.6-Organic catalyst 1 0.5 EDDS 0.17 0.21 MgSO4 0.35 0.47 HEDP 0.15 0. 34 Brightener 0.06 0.04 Zinc phthalocyanine sulfonate 0.0015 0.0020 Polydimethylsiloxane, 0.04 0.14 Trimethylsilyl End-blocked soap 0.5 0.5 0.7 Perfume 0.35 0.45 Speckle 0.5 0.6

Example XVII The granular laundry detergent compositions XVII AC of the present invention are particularly useful under European machine laundering conditions. Ingredients ABC LAS 7.0 5.61 4.76 TAS--1.57 C45AS 6.0 2.24 3.89 C25E3S 1.0 0.76 1.18 C45E7--2.0 C25E3 4.0 5.5-QAS 0.8 2.0 2.0 STPP---Zeolite A 25.0 19.5 19.5 Citric acid 2.0 2.0 2.0 NaSKS-6 8.0 10.6 10.6 Carbonate I 8.0 10.0 8.6 MA / AA 1.0 2.6 1.6 CMC 0.5 0.4 0.4 PB4-12.7-Percarbonate--19.7 TAED-3.1 5.0 Organic catalyst 10 0.04 3 Citrate 7.0--DTPMP 0.25 0.2 0.2 HEDP 0.3 0.3 0.3 QEA1 0.9 1.2 1.0 Protease 0.02 0.05 0.035 Lipase 0.15 0.25 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.4 0.7 0.3 PVPI / PVNO 0.4-0.1 Photoactivated bleach (ppm) 15ppm 27ppm 27ppm Brightener 1 0.08 0.19 0.19 Brightener 2-0.04 0.04 perfume 0.3 0.3 0.3 intumescent granules (40% malic acid, 15 15 quintuple 40% sodium carbonate, sodium carbonate 20%) silica Over emissions antifoam 0.5 2.4 2.4 minor ingredients / inactive ingredients total 100%

Example XVIII The following formulations are examples of compositions of the invention which may be in granular or tablet form. Ingredients 14 C45AS / TAS 3.0 LAS 8.0 C25AE3S 1.0 NaSKS-6 9.0 C25AE5 / AE3 5.0 Zeolite A 10.0 SKS-6 (I) (dry addition) 2.0 MA / AA 2 0.0 Citric acid 1.5 EDDS 0.5 HEDP 0.2 PB1 10.0 NACA OBS 2.0 TAED 2.0 Organocatalyst 1 Carbonate 8.0 Sulfate 2.0 Amylase 0.3 Lipase 0.2 Protease ¹ 0.02 Minor component (Brightener / SRP1 / 0.5 CMC / photobleach / MgSO4 / PVPVI / foam suppressor / PEG) Fragrance 0.5

[0300] Examples of sodium XIX Liquid fabric cleaning composition Example No. Component A B C _12-14 alkenyl succinic acid 3.0 8.0 Citric acid monohydrate 10.0 15.0 Sodium _{C 12-15} alkyl sulphate 8.0 8.0 C _12-15 alcohol - 3.0 Sulfate, 2-fold ethoxylated C _12-15 alcohol, 7-fold ethoxylated-8.0 C _12-15 alcohol, 5-fold ethoxylated 8.0-diethylenetriamine penta (methylenephosphonic acid) 0.2-oleic acid 1.8-ethanol 4.0 4.0 propanediol 2.0 2.0 Protease 0.01 0.02 Foaming inhibitor 0.15 0.15 NaOH pH up to 7.5 Perborate 0.5 1 Organic catalyst 0.01 0.5 Phenol sulfonate 0.1 0.2 Peroxidase 0.4 0.1 Water and minor components up to 100%

Example XX Liquid Fabric Cleaning Composition Example No. Component 17 NaLAS (100% am) 16 Neodol 21.5 EDDS 1.2 Dispersant 1.3 Perborate 12 Organocatalyst 0.1 N-nonanoyl-6- Aminocaproic acid 6 Phenolsulfonate ester protease (% pure enzyme) 0.03 Cellulase 0.03 Solvent (BPP) 18.5 Polymer 0.1 Carbonate 10 FWA15 0.2 TiO ₂ 0.5 PEG8000 0.4 Perfume 1 0.0-1.2 Foam suppressor 0.06 Water and minor components up to 100%

Example XXI Two-layer Effervescent Denture Cleansing Tablets Component ABCD Acidic Layer Protease 1.0 1.5 0.01 0.05 Tartaric Acid 24.0 24.0 24.00 24.00 Sodium Carbonate 4.0 4.0 4.00 4.00 Sulfamic Acid 10.0 10.0 10.00 10.00 PEG 20,000 4.0 4.0 4.00 4.00 Heavy Sodium carbonate 24.5 24.5 24.50 24.50 Potassium persulfate 15.0 15.0 15.00 15.00 Sodium acid pyrophosphate 7.0 7.0 7.00 7.00 Dry silica 2.0 2.0 2.00 2.00 Tetraacetylethylenediamine 7.0 7.0 7.00 7.00 Perfume 1.0 1.0 1.00 1.00 Alkaline layer Sodium perborate monohydrate 32.0 32.0 32.00 32.00 Organic catalyst 1 0.05 0.5 2 Sodium bicarbonate 19.0 19.0 19.00 19.00 EDTA 3.0 3.0 3.00 3.00 Sodium tripolyphosphate 12.0 12.0 12.00 12.00 PEG 20,000 2.0 2.0 2.00 2.00 Sodium carbonate 2.0 2.0 2.00 2.00 Dry silica 2.0 2.0 2.00 2.00 Dye / fragrance 2.0 2.0 2.00 2.00

Example XXII Granular Detergent Compositions XXII A through E are particularly useful under Japanese machine washing conditions,
Manufactured according to the present invention. Ingredients ABCDE LAS 23.57 23.57 21.67 21.68 21.68 FAS 4.16 4.16 3.83 3.83 3.83 Nonionic surfactant 3.30 3.30 2.94 3.27 3.27 Bis (hydroxyethyl) 0.47 0.47 1.20 1.20 1.20 Methylammonium chloride SKS-6 7.50 7.50 5.17 5.76 5.06 Polyacrylate copolymer 7.03 7.03 14.36 14.36 14.36 (MW11000) (maleic acid / acrylate ratio 4: 6) Zeolite 11.90 11.40 10.69 11.34 11.34 Carbonate 14.90 14.82 11.71 11.18 11.18 Silicate 12.00 12.00 12.37 12.38 12.38 Protease 0.016 0.016 0.046 0.046 0.046 Lipase--0.28--Amylase--0.62--Cellulase--0.48-0.70 NOBS 3.75 3.75 2.70 2.70 2.70 PB1 3.53-2.60--Sodium percarbonate-4.21-3.16 3.16 Organic catalyst 0.1 0.01 2 5 0.5 SRP 0.52 0.52 0.70 0.70 0.70 Brightener 0.31 0.31 0.28 0.28 0.50 AE-Coflakes 0.17 0.20 0.17 0.17 0.17 Polydimethylsiloxa - - 0.68 0.68 0.68 Perfume 0.06 0.06 0.08 - - Perfume - - - 0.23 0.23 Hydrophobic precipitated silica 0.30 0.30 0.30 0.30 0.30 PEG4000 0.19 0.19 0.17 0.17 0.17 minor components / inactive ingredients total 100%

Example XXIII A bleaching detergent composition in the form of a granular laundry detergent is illustrated by the following formulation. A B C D E Organic Catalyst 0.05 0.01 0.13 0.04 0.07 Conventional active agents (NOBS) 0.00 2.00 1.20 0.70 0.00 Conventional activator (TAED) 3.00 0.00 2.00 0.00 0.00 Conventional active agents (NACA-OBS) 3.00 0.00 0.00 0.00 2.20 Sodium percarbonate 5.30 0.00 0.00 4.00 0.00 Sodium perborate monohydrate 0.00 5.30 3.60 0.00 4.30 Linear alkylbenzene 12.00 0.00 12.00 0.00 21.00 Sulfonate C45AE0.6S 0.00 15.00 0.00 15.00 0.00 C2 Dimethylamine N-oxide 0.00 2.00 0.00 2.00 0.00 C12 Cocoamidopropyl betaine 1.50 0.00 1.50 0.00 0.00 Palm N-methylglucamide 1.70 2.00 1.70 2.00 0.00 C12 Dimethylhydroxyethyl 1.50 0.00 1.50 0.00 0.00 Ammonium chloride AE23-6.5T 2.50 3.50 2.50 3.50 1.00 C25E3S 4.00 0.00 4.00 0.00 0.00 Sodium tripolyphosphate 25.00 25.00 15.00 15.00 25.00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Phosphoric acid / maleic acid copolymer 0.00 0.00 0.00 0.00 1.00 Polyacrylic acid, partially neutralized 3.00 3.00 3.00 3.00 0.00 Soil release agent 0.00 0.00 0.50 0.40 0.00 Carboxymethyl cellulose 0.40 0.40 0.40 0.40 0.40 Sodium carbonate 2.00 2.00 2.00 0.00 8.00 Silicon Sodium acid salt 3.00 3.00 3.00 3.00 6.00 Sodium bicarbonate 5.00 5.00 5.00 5.00 5.00 5.00 Savinase (4T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriamine penta 1.60 1.60 1.60 1.60 0.40 (Methylenephosphonic acid) Brightener 0.20 0.20 0.20 0.05 0.20 Sulfonated zinc phthalocyanine 0.50 0.00 0.25 0.00 0.00 Photobleaching agent MgSO ₄ 2.20 2.20 2.20 2.20 0.64 Na ₂ SO ₄ Remaining Remaining Remaining Above All the compositions were used to wash fabrics at a water concentration of 3500 ppm at 25 ° C and a water: fabric ratio of 15: 1. Used. A typical pH is about 9.5 but can be adjusted by changing the ratio of acid to Na salt form of alkylbenzene sulfonate.

Example XXIV A bleaching detergent composition in the form of a granular laundry detergent is illustrated by the formulation below. A B C D E Organic Catalyst 0.06 0.34 0.14 0.14 0.20 Sodium percarbonate 5.30 0.00 0.00 0.00 0.00 sodium perborate monohydrate 0.00 9.00 17.60 9.00 9.00 linear alkylbenzene 21.00 12.00 0.00 12.00 12.00 sulfonate C45AE0.6S 0.00 0.00 15.00 0.00 0.00 C2 dimethylamine N-oxide 0.00 0.00 2.00 0.00 0.00 C12 cocoamidopropyl betaine 0.00 1.50 0.00 1.50 1.50 Palm N-methylglucamide 0.00 1.70 2.00 1.70 1.70 C12 dimethylhydroxyethyl 1.00 1.50 0.00 1.50 1.50 Ammonium chloride AE23-6.5T 0.00 2.50 3.50 2.50 2.50 C25E3S 0.00 4.00 0.00 4.00 4.00 Conventional activator (NOBS) 0.00 0.00 0.00 1.00 0.00 Conventional activator (TAED) 1.80 1.00 2.50 3.00 1.00 Sodium tripolyphosphate 25.00 15.00 25.00 15.00 15.00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Acrylic acid / Maleic acid copolymer 0.00 0.00 0.00 0.00 0.00 Polyacrylic acid, partially neutralized 0.00 3.00 3.00 3.00 3.00 Soil release agent 0.30 0.50 0.00 0.50 0.50 Carboxymethyl cellulose 0.00 0.40 0.40 0.40 0.40 Sodium carbonate 0.00 2.00 2.00 2.00 2.00 Sodium silicate 6.00 3.00 3.00 3.00 3.00 Sodium bicarbonate 2.00 5.00 5.00 5.00 5.00 Savinase (4T) 0.60 1.00 1.00 1.00 1.00 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriamine penta 0.40 0.00 1.60 0.00 0.00 (Methylene Phosphonic acid) Brightener 0.20 0.30 0.20 0.30 0.30 Sulfonated zinc phthalocyanine 0.25 0.00 0.00 0.00 0.00 Photobleaching agent MgSO ₄ 0.64 0.00 2.20 0.00 0.00 Na ₂ SO ₄ Remaining Remaining Remaining Remaining All of the above compositions are in water for washing fabrics. Used at a concentration of 3500 ppm at 25 ° C and a water: fabric ratio of 15: 1. A typical pH is about 9.5 but can be adjusted by changing the ratio of acid to Na salt form of alkylbenzene sulfonate.

Example XXV Bleaching detergent powder comprises the following ingredients: Ingredient wt% Organic catalyst 0.07 TAED 2.0 Sodium perborate tetrahydrate 10 C ₁₂ Linear alkylbenzene sulfonate 8 Phosphate (as sodium tripolyphosphate) 9 Sodium carbonate 20 Talc 15 Brightener, Fragrance 0.3 Sodium chloride 25 Water and minor components 100% in total

Example XXVI A laundry bar comprising the following ingredients, suitable for hand laundering soiled fabrics, is prepared by standard extrusion processes. Ingredient wt% Organic catalyst 0.2 TAED 1.7 NOBS 0.2 Sodium perborate tetrahydrate 12 C ₁₂ Linear alkylbenzene sulfonate 30 Phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 Sodium pyrophosphate 7 Coconut Monoethanolamide 2 Zeolite A (0.1-10 micron) 5 Carboxymethylcellulose 0.2 Polyacrylate (mw 1400) 0.2 Brightener, fragrance 0.2 Protease 0.3 CaSO ₄ 1 MgSO ₄ 1 Water 4 Filler ¹ total 100% ¹ Can be selected from convenient materials such as CaCO ₃ , talc, clay, silicates and the like. Acidic fillers can be used to lower the pH.

Example XXVII A laundry detergent composition suitable for machine use, comprising the following ingredients, is prepared by standard procedures. Ingredient % by Weight Organic Catalyst 0.82 TAED 7.20 Sodium Perborate Tetrahydrate 9.2 Sodium Carbonate 23.74 Anionic Surfactant 14.80 Aluminosilicate 21.30 Silicate 1.85 Diethylenetriamine Pentaacetic acid 0.43 Polyacrylic acid 2.72 Brightener 0.23 Polyethylene glycol solid 1.05 Sulfate 8.21 Fragrance 0.25 Water 7.72 Processing aid 0.10 Other 0.43 This composition is a fabric Concentration in solution about 1000ppm, temperature 20-40 ℃
, And water to fabric ratio of about 20: 1.

Example XXVIII Component Weight% Organocatalyst 1.0 TAED 10.0 Sodium perborate tetrahydrate 8.0 Sodium carbonate 21.0 Anionic surfactant 12.0 Aluminosilicate 18.0 Diethylenetriamine penta Acetic acid 0.3 Nonionic surfactant 0.5 Polyacrylic acid 2.0 Brightener 0.3 Sulfate 17.0 Perfume 0.25 Water 6.7 Others 2.95

Example XXIX A bleaching composition suitable for use in the highly effervescent phosphate area has the following composition: Ingredient A (wt%) B (wt%) Organic catalyst 0.02 0.018 NOBS 1.90 2.00 Sodium perborate tetrahydrate 2.25 3.00 Sodium carbonate 13.00 13.00 Anion Type surfactant 19.00 19.00 Type cationic surfactant 0.60 0.60 Nonionic type surfactant-0.40 Sodium tripolyphosphate 22.50 22.50 Diethylenetriamine pentaacetic acid 0.90 0.90 Acrylic acid / maleic acid copolymer 0.90 0.90 Carboxymethyl cellulose 0.40 0.40 Protease 0.70 0.70 Amylase 0.36 0.36 Cellulase 0.35 0.35 Brightener 0.16 0. 18 Magnesium sulfate 0.70 0.70 Water 3.0 1.0 Sodium sulfate Remaining Remaining

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

The composition is used as a laundry aid for laundry, with a concentration in solution of about 850 ppm, a temperature of 5 to 50 ° C. and a water to fabric ratio of about 20: 1.

The compositions of the present invention can be effectively produced by any of the methods chosen by the formulator, examples of which are US Pat. Nos. 5,691,297, 5,574,005, 5,569,645, 5,5
No. 65,422, No. 5,516,448, No. 5,489,392, and No. 5,486,303, but not limited thereto.

In addition to the above examples, the bleaching compositions of the present invention can be formulated into any suitable laundry detergent composition, examples of which are described in US Pat. Nos. 5,679,630, 5,565,145, 5,478,489, 5,470,507, 5,466,802, 5,460,752, 5,458,81
0, 5,458,809, and 5,288,431.

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 to 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 Penny, S. Weed             Oran, Kentucky, United States             Gar, Perimeter, Drive, 604 F-term (reference) 4H003 AA01 AB31 AC23 BA17 DA19                       EA15 EB08 EB19 EB24 EB30                       EB32 EC01 EC02 ED01 EE01                       EE03 EE05 FA06 FA07 FA12                       FA22 FA26 FA29 FA43 FA44

Claims (26)

[Claims] 1. A bleaching composition comprising an organic catalyst compound with or without a peroxygen source, wherein the organic catalyst compound exhibits an organic catalyst life of 30 minutes or more. A bleaching composition, characterized in that it is selected from the group consisting of catalyst compounds. 2. The bleaching composition according to claim 1, wherein the organocatalyst compound is selected from the group consisting of organocatalyst compounds exhibiting an organocatalyst life of 45 minutes or more. 3. The bleaching composition according to claim 1, wherein the organocatalyst compound is selected from the group consisting of organocatalyst compounds exhibiting an organocatalyst life of 60 minutes or more. 4. The bleaching composition according to claim 1, wherein the organocatalyst compound is selected from the group consisting of organocatalyst compounds exhibiting an organocatalyst life of 90 minutes or more. 5. The bleaching composition according to claim 1, wherein the organocatalyst compound is selected from the group consisting of organocatalyst compounds exhibiting an organocatalyst life of 2 hours or more. 6.   The organic catalyst compound is selected from the group consisting of the following (a) to (g):
The bleaching composition described:   (A) Ally having a net charge of about +3 to about -3 represented by the following formula [I]:
Ruiminium cations and aryliminium polyions: [Chemical 1] (In the formula, R^Two~ R^ThreeAre independently H, alkyl, cycloalkyl, aryl,
Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfona
Group consisting of alkoxide, alkoxy, keto, carboxyl, and carboalkoxy groups
A saturated or unsaturated group selected from, substituted or unsubstituted,
Selected from R¹And R^FourIs saturated, either substituted or unsubstituted.
Or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, ara
Alkyl, heterocycle, silyl, nitro, halo, cyano, alkoxy, keto and cal.
A group selected from the group consisting of voalkoxy groups, provided that R¹Or R^Four R is isopropyl, R^TwoOr R^ThreeIs ArCOCH_ThreeNot X⁻Is
A suitable charge-balancing counterion, v is an integer from 1 to 3),   (B) Ally having a net charge of about +3 to about -3, represented by formula [II] below.
Ruiminium twin ion: [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) Oki represented by the following formula [III] and having a net charge of about +3 to about -3.
Saziridinium cation and polyion: [Chemical 4] (In the formula, R^{2 '}~ R^{3 '}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, a substituted or an unsubstituted group, R ^{1 '} And R^{4 '}Is substituted or unsubstituted, saturated or unsaturated
H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, compounds
Ring, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy
A group selected from the group consisting of^{1 '}Or R^{4 '}Is isop
R if Ropil^{2 '}Or R^{3 '}Is ArCOCH_ThreeNot X⁻Is suitable
Is a counter ion that balances charge, and v is an integer of 1 to 3),   (D) an oxa having a net charge of about +3 to about -3 represented by the following formula [IV]:
Zyridinium Zwitterion: [Chemical 5] (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 6] 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),   (E) with a net charge of about -3 to about +3, represented by the following formulas [V] and [VI]:
A modified amine: [Chemical 7] (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
Substitutions selected from the group consisting of groups having ionic and / or cationic charges
Selected from the substituted or unsubstituted groups, R⁸And R¹¹Is replaced
Saturated or unsaturated, substituted or unsubstituted, H, alkyl, cycloalkyl
Rualkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halo
, Cyano, alkoxy, keto and carboalkoxy groups and anions and /
Or a group selected from the group consisting of groups having a cationic charge, R¹²Away
It is degrouped and its protonated form is pK_aValue (H_TwoO standard) is 37> pK _a It falls within the range of> -2, but R⁸~ R¹²Are all paired, if present
Can be combined to form a fused aryl, fused carbocycle or fused heterocycle,
The formula below [Chemical 8] In the group represented by_p ⁻Is T₀Covalently bound to Z_p ⁻Is -CO_Two ⁻,-
SO_Three ⁻, -OSO_Three ⁻, -SO_Two ⁻And -OSO_Two ⁻Selected from the group consisting of
Where p is 1, 2 or 3 and T₀Is replaced or not replaced
, Saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, a
Aralkyl, and selected from the group consisting of heterocycles),   (F) The net charge represented by the following formulas [VII] to [X] is about −3 to about +3.
Modified amine oxide: [Chemical 9] (In the formula, R⁸~ R¹⁰Are independently H, alkyl, cycloalkyl, aryl
, Alkaryl, aralkyl, heterocycle, silyl, nitro, halo, cyano, sulfo
Nato, alkoxy, keto, carboxyl, and carboalkoxy groups and anions
Substitutions selected from the group consisting of groups having ionic and / or cationic charges
Selected from the substituted or unsubstituted groups, 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 groups having anionic and / or cationic charges
Group, R¹²Is a leaving group and its protonated form is pK_aValue (H_Two O standard) is 37> pK_aIt falls within the range of> -2, but R⁸~ R¹²Is present
Combine to form a fused aryl, fused carbocycle or fused heterocycle.
In this formula, a group represented by the following formula also exists, [Chemical 10] 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), and   (G) a mixture thereof. 7.   The organic catalyst compound is selected from the group consisting of the following (a) to (g):
The bleaching composition according to:   (A) Ally having a net charge of about +3 to about -3 represented by the following formula [XI]:
Ruiminium cations and aryliminium polyions: [Chemical 11] (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 provided that R^{19 '}But-
CH (CH_Three)_TwoThen R^{20 '}Is COCH_ThreeNot R¹⁸Is H,
Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, cyclo
Ryl, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxyl
, And carboalkoxy groups selected from the group consisting of, substituted or substituted
R may be a non-substituted group, R¹⁹Tired, substituted or not,
Sum or unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl,
A group selected from the group consisting of aralkyl and heterocycle, G being (1) -O
-, (2) -N (R²³)-, And (3) -N (R²³R²⁴) -A group consisting of
Selected from R²¹~ R²⁴Are independently H, oxygen, straight chain or branched chain
C₁~ C₁₂Alkyl, alkylene, alkoxy, aryl, alkaryl,
A substituted, selected from the group consisting of aralkyl, cycloalkyl, and heterocycle.
A substituted or unsubstituted group, provided that R¹⁸, R¹⁹, R²⁰, R ²¹ ~ R²⁴Is all R¹⁸, R¹⁹, R²⁰, R²¹~ R²⁴With either
Can be combined to form part of a common ring, all gem-R²¹~ R²²Is
Can be combined to form a carbonyl, all vic-R²¹~ R^Two
FourCan combine to form unsaturation, the substituent R²¹~ R²⁴Any group of
May form a fused unsaturated moiety that is entangled and substituted or unsubstituted.
Can be done, X⁻Is a counter ion that has a suitable charge balance, and v is an integer of 1 to 3.
Is),   (B) An ant having a net charge of about +3 to about -3 represented by the following formula [XII].
Luminium Zwitterion: [Chemical 12] [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 13] 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 14] 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, provided that all R²⁹Based on Germany
Instead of being selected to stand up to H, 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
Unfused fused unsaturated moieties can be formed, provided that [Chemical 15] The group represented by is CH_TwoCH (OSO_Three ⁻) R⁴¹(R⁴¹Is gem-dimethyl
From the group consisting of substituted alkyl, unsubstituted alkyl and phenyl.
Selected), not],   (C) Oki represented by the following formula [XIII] and having a net charge of about +3 to about -3.
Saziridinium cation and polyion: [Chemical 16] (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.
),   (D) Oki represented by the following formula [XIV] and having a net charge of about +3 to about -3.
Saziridinium Zwitterion: [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, 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
Group represented by the following formula [Chemical 18] Then 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 19] 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.
Selected from all the groups that are substituted or unsubstituted, provided that all R^{29 '}Basis
Are not independently selected to be H, and G is (1) -O-, (2)-
N (R^{30 '})-, And (3) -N (R^{30 '}R^{31 '})-
Selected, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Independently, H, oxygen
, Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkyle
Amine, heterocycle, alkoxy, arylcarbonyl group, carboxyalkyl group and
With a substituted or unsubstituted group selected from the group consisting of amido groups
Yes, R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Lotus
All R^{25 '}, R^{26 '}, R^{27 '}, R^{28 '}, R^{30 '}And R^{31 '}Noi
Can be combined with a gap 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 above groups in combination with a substituted or unsubstituted
A saturated part can be formed, provided that the following formula [Chemical 20] The group represented by is CH_TwoCH (OSO_Three ⁻) R⁴¹(R⁴¹Is gem-dimethyl
From the group consisting of substituted alkyl, unsubstituted alkyl and phenyl.
Not selected)],   (E) The net charge represented by the following formulas [XV] and [XVI] is about -3 to about +3.
Modified amines that are: [Chemical 21] 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 R³⁵Are 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-R³⁵Substituents may be combined to form fused aryl, condensed
R carbocycles or fused heterocycles can be formed and R³²Is 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 good³³Is H, alkyl, cycloalkyl, alkaryl, aryl
Selected from the group consisting of aralkyl, aralkyl and heterocycle, substituted or substituted
It may be a saturated or unsaturated group, which is not represented by the formula below.
There is also a group, [Chemical formula 22] 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 23] 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, provided that all R³⁸Based on Germany
Instead of being selected to stand up to H, 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),   (F) with a net charge of about -3 to about +3, represented by formulas [XVII]-[XX] below:
Some modified amine oxides: [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 R³⁵Are 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 selected³⁵The substituents are combined to form a fused aryl,
Fused carbocycles or fused heterocycles can be formed, R³²Is 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-group³³Is H, alkyl, cycloalkyl, alkaryl, ant
Selected from the group consisting of aryl, aralkyl and heterocycle, substituted or substituted
It may be a saturated or unsaturated group, which is not represented by this formula.
There is also a group [Chemical 25] 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 26] 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, provided that all R³⁸Based on Germany
It is not selected to stand and become H, and 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), and   (G) a mixture thereof. 8.   The organic catalyst compound is selected from the group consisting of the following (a) to (f):
The bleaching composition according to:   (A) Arylimi represented by the formula [XI] and having a net charge of about +3 to about -3.
Cations and aryliminium polyions (wherein R of formula [XI]¹⁸ Is H or methyl, R¹⁹Is substituted or unsubstituted, saturated
Or unsaturated C₁~ C₁₄Alkyl or cycloalkyl, R²⁰Is H
Is),   (B) an aryl group having a net charge of about +3 to about -3 represented by formula [XII].
Minium zwitterion (where R in formula [XII]²⁵Is H or methyl, and
Ceremony [Chemical 27] With respect to the groups represented by_p ⁻Is -CO_Two ⁻, -SO_Three ⁻Or -OSO _Three ⁻ And p is 1 or 2),   (C) Oxazily represented by the formula [XIII] and having a net charge of about +3 to about -3.
Dinium cations and oxaziridinium polyions (wherein R of formula [XIII] ^{18 '} Is H or methyl, R^{19 '}Is or has not been replaced
C, saturated or unsaturated₁~ C₁₄Alkyl or cycloalkyl, R ^{20 '} Is H),   (D) an aryl group represented by the formula [XIV] having a net charge of about +3 to about -3.
Minium zwitterion (where R in formula [XIV]^{25 '}Is H or methyl,
And expression [Chemical 28] With respect to the group represented by_p ⁻Is -CO_Two ⁻, -SO_Three ⁻, -OSO_Three ⁻ And p is 1 or 2),   (E) represented by the formulas [XV] and [XVI], the net charge is about +1 to about -1,
R³²Is H and / or Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻Or -O
SO_Three ⁻A modified amine that is   (F) represented by formulas [XVII] and [XX], having a net charge of about +1 to about −1,
R³²Is H and / or Z_p ⁻Is -CO_Two ⁻, -SO_Three ⁻Or -O
SO_Three ⁻Is a modified amine. 9. The organocatalytic compound comprises from about 0.0001 to about 10% by weight of the bleaching composition, and said peroxygen source, if present, from about 0.01 to about 60% by weight of the bleaching composition. A bleaching composition according to claim 1 which constitutes%. 10. The bleaching composition of claim 9 wherein the organocatalytic compound comprises from about 0.01 to about 0.5% by weight of the bleaching composition. 11. 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, A bleaching composition according to claim 1 selected from the group consisting of and bleach activators. 12. The peroxygen source is a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and a bleach activator. The bleaching composition according to claim 11, wherein: 13. The bleaching activator is tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS).
), Nonanoyloxybenzene sulfonate (NOBS), phenyl benzoate (
PhBz), decanoyl oxybenzene sulphonate _(C 10 -OBS), benzoyl valerolactam (BZVL), octanoyl oxybenzenesulfonate _(C 8 -OBS), perhydrolyzable resistance (perhydrolyzable) ester, 4- [N- (nonanoyl ) Aminohexanoyloxy] -benzenesulfonate sodium salt (
NACA-OBS), lauroyloxybenzene sulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzene sulfonate (UDO).
A bleaching composition according to claim 11, which is selected from the group consisting of BS), decanoyloxybenzoic acid (DOBA) and mixtures thereof. 14. A surfactant, a solvent, a buffer, an enzyme, a soil release agent, a clay soil remover, a dispersant,
Selected from the group consisting of brighteners, suds suppressors, fabric softeners, suds boosters, enzyme stabilizers, builders, chelating agents, other bleaches, dyes, dye transfer inhibitors, perfumes and mixtures thereof. The bleaching composition of claim 1, further comprising one or more of the following detergent ingredients. 15.   The bleaching composition according to claim 1, which is a laundry detergent. 16.   The bleaching composition according to claim 1, which is a laundry additive. 17. The bleaching composition of claim 16, wherein the laundry additive further comprises a suitable carrier. 18. A method of laundering a fabric in need of laundering, comprising contacting the fabric with a laundry solution comprising the bleaching composition of claim 1. 19. The method of claim 18, wherein the in-use concentration of the organocatalytic compound is from about 0.01 ppm to about 10 ppm. 20. The method of claim 19, wherein the in-use concentration of the organocatalytic compound is about 0.04 ppm to 2.5 ppm. 21. The in-use concentration of the organocatalytic compound is from about 0.1 ppm to 1 ppm.
The method described in 0. 22. A product comprising the bleaching composition of claim 1, further comprising instructions for using the composition to wash fabrics in need thereof. A product, the instructions for use of which include the step of contacting the fabric with a cleaning solution comprising the product. 23.   Selected from the group consisting of organocatalytic compounds exhibiting an organocatalytic lifetime of 30 minutes or more
An organic catalyst compound,   An organic catalyst compound selected from the group consisting of the following (a) to (i):   (A) Ally having a net charge of about +3 to about -3 represented by the following formula [XI]:
Ruiminium cations and aryliminium polyions: [Chemical 29] (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 provided that R²⁰Is fe
R, not Nil^{19 '}R is isopropyl, R²⁰Is COCH_ThreeThen
R¹⁸Is H, alkyl, cycloalkyl, alkaryl, aryl, ara
Alkyl, heterocycle, silyl, nitro, halo, cyano, sulfonate, alkoxy,
A group selected from the group consisting of keto, carboxyl, and carboalkoxy groups,
It may be a substituted or unsubstituted group, R¹⁹Is H, alkyl, cyclo
A non-linear group selected from the group consisting of alkyl and alkaryl, G
Is (1) -O-, (2) -N (R²³)-, And (3) -N (R²³R²⁴ ) -Selected from the group consisting of²¹~ R²⁴Are independently H, oxygen, linear
Or branched chain C₁~ C₁₂Alkyl, alkylene, alkoxy, aryl,
Selected from the group consisting of alkaryl, aralkyl, cycloalkyl, and heterocycle
A substituted, substituted or unsubstituted group with the proviso that R¹⁸, R^{1 9} , R²⁰, R²¹~ R²⁴Is all R¹⁸, R¹⁹, R²⁰, R²¹~ R^{Two Four} Can be combined with any of the above to form part of a common ring, and all gem-R
²¹~ R²²Can combine to form carbonyls, and all vic
-R²¹~ R²⁴Can combine to form unsaturation, the substituent R²¹~ R^{Two Four} Substituted or unsubstituted fused unsaturated moieties in combination with any of the groups
Can form a minute, X⁻Is a suitable charge-balancing counterion, v
Is an integer from 1 to 3),   (B) An ant having a net charge of about +3 to about -3 represented by the following formula [XII].
Luminium Zwitterion: [Chemical 30] [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 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 [Chemical 32] 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, provided that all R²⁹Based on Germany
Instead of being selected to stand up to H, 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
Unfused fused unsaturated moieties can be formed, provided that [Chemical 33] The group represented by is CH_TwoCH (OSO_Three ⁻) R⁴¹(R⁴¹Is gem-dimethyl
From the group consisting of substituted alkyl, unsubstituted alkyl and phenyl.
Selected), not],   (C) Modified amine represented by the following formulas [XV] and [XVI]: [Chemical 34] (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 and Persulphona
Is a group selected from the group³⁵Are independently H, alkyl, cyclo
Alkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo, sia
No, sulfonate, alkoxy, keto, carboxyl, and carboalkoxy
Selected from the group consisting of groups, selected from substituted or unsubstituted groups
And all 2 vic-Rs³⁵Substituents are combined to form fused aryl, fused
Carbocycles or fused heterocycles can be formed and R³²Is H, alkyl, shik
Roalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro,
Halo, cyano, sulfonate, alkoxy, keto, carboxyl, and carbo
Selected from the group consisting of alkoxy groups, substituted or unsubstituted
R is good³³Is H, alkyl, cycloalkyl, alkaryl, aryl
Selected from the group consisting of, aralkyl, heterocycle, substituted, or substituted
May be a saturated or unsaturated group, which is represented by the formula:
Groups also exist, [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 [Chemical 36] 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, provided that all R³⁸Based on Germany
Instead of being selected to stand up to H, 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 37] In the formula, when G is present, m is 1 to 3, and when G is not present, m is 1 to 4
Where n is an integer from 0 to 4 and R³⁴Is or has been replaced
None, saturated or unsaturated hydroxy, perhydroxy, alkoxy, peral
Koxy, carboxyl, percarboxyl, sulfonates and persulfonates
R is a group selected from³⁵Are independently H, alkyl, cycloalkyl
Alkyl, aryl, fused aryl, heterocycle, fused heterocycle, nitro, halo, cyano
, Sulfonate, alkoxy, keto, carboxyl, and carboalkoxy groups
Selected from the group consisting of, substituted or unsubstituted groups selected from
And all 2 vic-Rs³⁵Substituents are combined to form condensed aryl, condensed carbon
Can form a ring or fused heterocycle, R³²Is H, alkyl, cyclo
Alkyl, alkaryl, aryl, 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
Good, R³³Is H, alkyl, cycloalkyl, alkaryl, aryl,
Aralkyl, selected from the group consisting of heterocycles, substituted, or substituted
It may be a saturated or unsaturated group, and this formula includes a group represented by the following formula.
Also exists, [Chemical 38] 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 39] 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, provided that all R³⁸Based on Germany
It is not selected to stand and become H, and 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),   (F) Oki represented by the following formula [XIII] and having a net charge of about +3 to about -3.
Saziridinium cation and polyion: [Chemical 40] (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) Oki represented by the following formula [XIV] and having a net charge of about +3 to about -3.
Saziridinium Zwitterion: [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 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
Group represented by the following formula [Chemical 42] Then 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 43] 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.
Selected from all the groups that are substituted or unsubstituted, provided that all R^{29 '}But
It is not independently selected to be H, and 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), and   (I) a mixture thereof. 24. The organocatalyst compound of claim 23, wherein the organocatalyst exhibits an organocatalyst life of greater than 30 minutes. 25. The organocatalyst compound of claim 23, wherein the organocatalyst exhibits an organocatalyst life of greater than 1 hour. 26. The organocatalyst compound of claim 23, wherein the organocatalyst exhibits an organocatalyst life of greater than 2 hours.