JP2003508584A - Prescription component resistant to decomposition by aromatization, composition using the same, and washing method - Google Patents

Abstract

  (57) [Summary] Bleach booster comprising a quaternary imine cation, a zwitterion, a polyion having a net charge of about +3 to about -3 and mixtures thereof, an oxaziridinium cation, a zwitterion, a net of about +3 to about -3. Bleach enhancing compounds selected from the group consisting of bleaching species comprising charged polyions and mixtures thereof, and mixtures thereof are disclosed. The bleach-enhancing compound increases bleaching effectiveness even in low temperature solutions and provides improved stability against unwanted bleach-enhancing compound degradation. The bleach enhancing compounds are ideally suited for inclusion in bleaching compositions, including those used in conjunction with detersive surfactants and enzymes. A method for washing a fabric using the bleach-enhancing compound, and a laundry additive product using the bleach-enhancing compound are also provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION

The present invention relates to formulation components such as increased stability bleach enhancing compounds, as well as compositions and laundering methods using the increased stability bleach enhancing compounds. More particularly, the present invention relates to quaternary imine bleach boosters and / or oxaziridinium bleaching species, compositions using quaternary imine bleach boosters and / or oxaziridinium bleaching species, and washing methods.

[0002]

BACKGROUND OF THE INVENTION

Oxygen bleaches have become increasingly popular in household and personal care products in recent years in promoting stain and stain removal. Bleaching is particularly desirable from the standpoint of stain removal, cloth darkening, whitening and hygiene. Oxygen bleach is particularly accepted in laundry products such as detergents, automatic dishwashing products and hard surface cleansers. However, oxygen bleaches are somewhat limited in their effectiveness. Some common drawbacks are color damage to the fabric and damage to laundry equipment, especially the rubber hoses that these equipment comprises. In addition, oxygen bleaches are very susceptible to temperature dependence. Therefore, the cooler the solution in which they are used, the less effective the bleaching action. Temperatures above 60 ° C. are typically required for the effectiveness of oxygen bleaches in solution.

To overcome the above temperature dependence, a class of compounds known as "bleach activators" has been developed. A bleach activator, typically a perhydrolyzeable acyl compound bearing a leaving group such as oxybenzene sulfonate, reacts with an active oxygen group, typically hydrogen peroxide or its anion. Form a more effective peroxyacid oxidant. It is a peroxyacid compound, which oxidizes spotted or soiled substrate material. However, the bleach activator is also somewhat temperature dependent. The bleach activator is effective at a hot water temperature of about 40 to about 60 ° C. At water temperatures below about 40 ° C, the peroxyacid compound loses some of its bleaching effectiveness.

In order to develop a bleaching system that is effective under low temperature water conditions, US Pat.
Attempts have been made as disclosed in patents 5,360,568, 5,360,569 and 5,370,826. However, the dihydroisoquinolinium bleach boosters disclosed in these references undergo undesired degradation, including the formation of inert aromatic isoquinoliniums that, when combined with peroxygen compounds, reduce booster potency.

From the above, researchers have energetically sought effective bleach enhancers that are not subject to degradation. Thus, there remains a need for effective bleach-enhancing compounds and compositions containing bleach-enhancing compounds that provide effective bleaching even at low water temperatures, resulting in improved stability against unwanted bleach-enhancing compound degradation. ing.

[0006]

[Summary of Invention]

This need is met by the present invention in which longer lasting bleach enhancing compounds, especially bleach boosters and / or bleaching species are provided. The bleach enhancing compounds of the present invention not only prevent unwanted degradation, but also exhibit excellent bleaching effectiveness at low water temperatures.

The bleach enhancing compound is selected from the group consisting of: (a) an aryliminium cation, an aryliminium zwitterion, an aryliminium polyion with a net charge of about +3 to about -3, and mixtures thereof. Bleach Booster; (
b) Oxaziridinium cation, oxaziridinium zwitterion, about +3 to
A bleaching species selected from the group consisting of oxaziridinium polyions having a net charge of about −3 and mixtures thereof; and (c) a peroxygen source selected from the group consisting of mixtures thereof, or A bleaching composition comprising a bleach enhancing compound without it is provided in a first aspect.

According to another aspect of the invention, there is provided a cationic or zwitterionic laundry bleach enhancing compound. According to yet another aspect of the invention, there is provided a method for laundering a fabric in need of laundering, which comprises contacting the fabric with a laundry solution having a bleaching composition according to the invention as described herein. It

According to yet another aspect of the present invention, it comprises (a) an aryliminium cation, an aryliminium zwitterion, an aryliminium polyion having a net charge of about +3 to about -3, and mixtures thereof. A bleach booster selected from the group: (b) an oxaziridinium cation, an oxaziridinium zwitterion, an oxaziridinium polyion having a net charge of about +3 to about -3, and mixtures thereof. There is provided a laundry additive product comprising a bleach enhancing compound selected from the group consisting of selected bleaching species; and (c) mixtures thereof.

Accordingly, it is an object of the present invention to not only prevent undesired aromatization, but also bleach enhancing compounds that show improved performance in low temperature solutions; quaternary imine bleach boosters and / or oxaziridinium bleaching species. A bleaching composition containing; Is to provide. These and other objects, features and advantages of the invention will be understood by those of skill in the art from the following description and appended claims. All percentages, ratios and proportions herein are on a weight basis unless otherwise noted. All references cited herein are incorporated herein by reference.

[0011]

[Detailed Description of the Invention]

The present invention is a novel and highly useful bleach boost compound (“bleach booster”).
, "Bleaching species" and mixtures thereof), and compositions and methods using the novel bleach enhancing compounds. The bleach-enhancing compound of the present invention exhibits improved bleaching effectiveness even at low temperatures while preventing unwanted decomposition due to aromatization,
Results in improved performance. The bleach-enhancing compounds of the present invention act with or without a conventional peroxygen bleaching source, preferably together therewith, to provide the improved bleaching efficacy and prevention of aromatization described above.

Definitions As used herein, the term "peroxygen source" means a substance that produces a peroxygen compound, including the peroxygen compound itself. Examples include, but are not limited to, bleach activators, peracids, percarbonates, perborates, hydrogen peroxide, bleach enhancing compounds and / or bleaching species (eg, oxaziridinium). As used herein, "peroxygen compounds" include peracids and peroxides,
Examples include hydrogen peroxide and alkyl hydroperoxides. As used herein, "peracid" means peroxycarboxylic acids and / or peroxyacids such as peroxymonosulfuric acid (trade name OXONE) and salts thereof.

Bleach Booster-The bleach booster of the present invention is preferably a quaternary imine bleach booster. More preferably, the bleach booster of the present invention is
The bleach booster is selected from the group consisting of aryliminium cations, aryliminium zwitterions, and / or aryliminium polyions having a net charge of about +3 to about -3, and mixtures thereof, wherein the bleach booster has the formula I]
And [II] have:

[Chemical formula 23] In the above formula, t is 0 or 1; R ¹ -R ⁴ is H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy,
A substituted or unsubstituted group selected from the group consisting of keto, carboxyl and carboalkoxy groups; two adjacent R ¹ -R ⁴ are joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring R ⁵ may be selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. R ⁶ is a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring and a group represented by the following formula: or unsaturated _{^{group: -T o - (Z -)}} a above wherein Z ^- is being covalently bonded to _{T o,} Z ^{- _{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
_{-CH 2 (C 6 H 4)} -;

[Chemical formula 24] _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl);

[Chemical 25] (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 18 R 19 -, - CR} 18 R 19 CR 20 R 21 - , and ^{-CR 18 R 19 CR 20 R 21} CR ²² R ²³ - is selected from the group consisting ^of; R 14 ^{-R 23} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ⁷ -R ¹⁰ is H, linear or branched C ₁ -C ₁₂ alkyl A substituent independently selected from the group consisting of, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic ring. Or an unsubstituted group, provided that when t is 0, neither R ⁷ nor R ⁸ is H, and when t is 1, R ⁷ and R ⁸ are both, or R ⁹ and R ¹⁰ are both Neither is H; either R ¹ -R ¹⁰ is joined together with any other R ¹ -R ¹⁰ ,
It may form part of a covalent ring.

[0014] Preferred bleaching species, ^{(1) R 25} is H or ^{methyl, R 26} is linear or branched _C 1 _{-C 14 alkyl,} C 3 _{-C 14} cycloalkyl and _C 6 _{-C 1 4} aryl is selected from the group of substituted or unsubstituted group consisting of oxaziridinium cations of formula [III]; a (2) R ²⁵ is H or methyl, R ²⁶ has the formula: -T o _- ( Z ⁻ ) _a Oxaziridinium zwitterion of formula [IV], but is not limited thereto.

[0015]   Preferred bleach boosters include (1) R⁵Is H or methyl, and R⁶ Is a straight chain or branched C₁-C₁₄Alkyl, C_Three-C₁₄Cycloalkyl and C ₆ -C₁₄Formula [I] selected from the group of substituted or unsubstituted groups consisting of aryl.
Aryliminium cations; (2) R⁵Is H or methyl, and R⁶Is below
Have the notation:                             -T_o‐ (Z⁻)_a (Z in the above formula⁻Is T_oCovalently bound to Z⁻Is -CO_Two ⁻, -SO_Three ⁻Oh
And -OSO_Three ⁻Selected from the group consisting of: a is 1 or 2) of formula [II]
Aryliminium dipolar ion; (3) R⁶Is a straight chain or branched C₁-C₁₄Setting
Arylimini of formula [I] selected from the group consisting of substituted or unsubstituted alkyl
Um cation, or R⁶Is a group represented by the following formula:                             -T_o‐ (Z⁻)_a (Z in the above formula⁻Is -CO_Two ⁻, -SO_Three ⁻Or-OSO_Three ⁻And a is 1
Yes, T_oIs selected from the group consisting of:

[Chemical formula 26] In the above formula, p is an integer of 2 to 4 and R⁴⁵Is H and linear or branched C₁-C_{1 8} Independently selected from the group consisting of substituted or unsubstituted alkyl) of formula [II]
Reel iminium dipolar ion; and (4) R⁵Is H and Z⁻Is-CO_Two ⁻ There are aryliminium polyions with a net negative charge, which are
Not limited to.

Further preferred bleach boosters are aryl aryls of formula [I], wherein (1) R ¹ -R ⁵ is H and R ⁶ is a linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl. mini um cation; a ⁽²⁾ R 1 -R ⁵ is H, ^{R 6} has the _{^{formula: -T o - (Z -)}} a ( the formula Z ^- is being covalently bonded to _{T o,} Z ⁻ Is selected from the group consisting of —CO ₂ ^— , —SO ₃ ^— and —OSO ₃ ^— , and a is 1), but is not limited to the aryliminium zwitterion of formula [II].

Further, the aryliminium cation, the aryliminium zwitterion, and the aryliminium polyion having a net charge of about +3 to about −3, ie, all of formulas [I] and [II], are gem. -Replacement is desirable. Of the present invention
The gem-substituted bleach boosters prevent or prevent the decomposition of cations, zwitterions and polyions by aromatization. Aromatization of 6-membered ring booster (
Decomposition) reaction is not bound by theory, Hanquet et al., Tetrahedron, 1993,
49, pp. 423-438, and are well known in the art, as shown below:

[Chemical 27] Gem-substituted bleach boosters increase the turnover number of active bleach boosters by "blocking" base-induced aromatization, as described in detail above. Without being bound by theory, such substitutions may prevent or prevent the degradation of cations, zwitterions and polyions via other degradation pathways. Other pathways of degradation include, but are not limited to, attack of bleach-enhancing compounds and / or bleaching species by nucleophiles, including, but not limited to, hydroxide anions, perhydroxide anions, carboxyls present under wash conditions. There are also attacks by, but not limited to, rate anions, percarboxylate anions and other nucleophiles.

The quaternary imine bleach boosters of the present invention work in concert with a peroxygen source to provide a more effective bleaching system. Peroxygen sources are well known in the art,
The peroxygen source used in the present invention may be any of these well known sources, including peroxygen compounds and compounds which in situ form an effective amount of peroxygen under consumer use conditions. . Peroxygen source, hydrogen peroxide source,
From the reaction of the hydrogen peroxide source and the bleach activator there is a mixture of in situ formation of the peracid anion, a preformed peracid compound or a suitable peroxygen source. Of course, those skilled in the art will appreciate that other sources of peroxygen may be used without departing from the scope of the invention. The source of hydrogen peroxide may be any suitable source of hydrogen peroxide, US Pat.
At a level as detailed in 282. For example, the hydrogen peroxide source is selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof.

The bleach activator is tetraacetylethylenediamine, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium lauroyloxybenzenesulfonate, (6-octanamidecaproyl). ) Oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanenamidocaproyl) oxybenzene sulfonate and mixtures thereof. A preferred activator is tetraacetylethylenediamine (TAED),
Benzoyl caprolactam (BzCl), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyl oxybenzene sulphonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyl oxybenzene sulphonate _{(C 10} - OBS), benzoyl valerolactam (BZVL), octanoyloxybenzene sulfonate (C ₈ -OBS), perhydrolizing ester, 4- [N-
(Nonanoyl) aminohexanoyloxy] benzenesulfonate sodium salt (NACA-OBS) (an example of which is described in US Pat. No. 5,523,434), lauroyloxybenzenesulfonate or dodecanoyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzene sulfonate (unsaturated UDOBS or C ₁₁ -OBS at the 10-position) and decanoyloxybenzoic acid (DOBA) and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Is selected from the group consisting of Particularly preferred bleach activators in the pH range of about 8 to about 9.5 are selected from those having an OBS or VL leaving group.

Other preferred bleach activators are Christie et al., US 5,698,504, issued December 16, 1997, Christie et al., US 5,695,679, 1997, issued December 9, 1997. Willey et al., US 5,686,401, issued November 11, 1997, issued November 11, 1997
Hartshorn et al., US 5,686,014, W, published April 11, 1995.
Wille et al., US 5,405,412, published April 11, 1995.
y et al., US 5,405,413, Mitchel et al., US 5,130,045, issued July 14, 1992, and Chung et al., US 4,412,934, issued November 1, 1983, and co-pending. Patent application USSN 08 / 709,0
72,08 / 064,564, all of which are incorporated herein by reference.

Quaternary substituted bleach activators may also be included. The detergent composition is preferably a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP).
), And more preferably the former. The preferred QSBA structure is 1997 1
Willey et al., US 5,686,015 issued Jan. 11, Taylor et al., US 5,654,421 issued Aug. 5, 1997, Oct. 24, 1995.
US Pat. No. 5,460,747, Gosselink et al., Issued December 1, 1996.
US Pat. No. 5,584,888 to Miracle et al.
It is further described in US Pat. No. 5,578,136 issued to Taylor et al., Dated March 26, all of which are incorporated herein by reference.

Highly preferred breach activators useful herein are US 5,698,504, US 5,695,679 and US 5,686, each of which are cited above.
Amide substituted as described in 014. Preferred examples of such bleach activators include (6-octanamidocaproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate and their There is a mixture.

US Pat. No. 5,698,504, US Pat. No. 5,695,679, each cited above,
Hodge, US 5,686,014, and October 30, 1990
Other useful activators disclosed in US Pat.
There are benzoxazine-type activators such as the C ₆ H ₄ ring fused with the moiety —C (O) OC (R ¹ ) ═N— at the 1,2-position.

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

Acyl lactam activators, especially acyl caprolactams (see eg WO 94-28102A), as described in US 5,698,504, US 5,695,679 and US 5,686,014, each of which are cited above, and Acylvalerolactam (see Willey et al. US Pat. No. 5,503,639, published Apr. 2, 1996, incorporated herein by reference) is very useful herein.

The preformed peracid compound as used herein can be any convenient compound that is stable and forms an effective amount of peracid anion under the conditions of consumer use. The bleach booster of the present invention is of course used in combination with a preformed peracid compound selected from the group consisting of percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. Alternatively, an example is described in US Pat. No. 5,576,282 to Miracle et al.

[0027]   One suitable organic peroxycarboxylic acid has the general formula:

[Chemical 28] In the above formula, R is an alkylene or substituted alkylene group having 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, and Y is hydrogen, halogen,
Alkyl, aryl, -C (O) OH or -C (O) OOH.

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

[Chemical 29] In the above formula, Y is, for example, H, CH ₃ , CH ₂ Cl, C (O) OH or C (O) OO.
H and n is an integer of 0-20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted acid has the general formula:

[Chemical 30] In the above formula, Y is, for example, hydrogen, alkyl, alkylhalogen, halogen, 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 acid, such as peroxysuccinic acid (NAPSA) Others have monononylamide of peroxyadipic acid (NAPAA).

Typical diperoxy acids useful herein include alkyl and aryl diperoxy acids such as (iv) 1,12-diperoxide decanedioic acid (v) 1,9-diperoxyazelaic acid (vi ) Diperoxybrassic acid, diperoxysebacic acid and diperoxyisophthalic acid (vii) 2-decyldiperoxybutane-1,4-dioic acid (viii) 4,4'-sulfonylbisperoxybenzoic acid.

Such a bleach is commercially available from Hartman US, published Nov. 20, 1984.
U.S. Pat. No. 4,483,781, Burns et al., US Pat. No. 4,634,551, Banks et al., European patent application 0,133,354, published February 20, 1985, and November 1, 1983. No. 4,412,934 to Chung et al. Its source also includes 6-nonylamino-6-oxoperoxycaproic acid, as described in detail in Burns et al., US Pat. No. 4,634,551, issued Jan. 6, 1987. EIDu Pont de Nemours of W
Persulfate compounds such as OXONE manufactured by ilmington, DE may also be used as a suitable source of peroxymonosulfate.

The bleach activator used herein may be any compound capable of forming in situ a peracid corresponding to the bleach activator when used in combination with hydrogen peroxide. Various non-limiting examples of activators are described in US Pat. No. 5,576,282.
, US Pat. No. 4,915,854 and US Pat. No. 4,412,934. See also US 4,634,551 for other exemplary bleaches and activators useful herein.

The quaternary imine bleach booster of the present invention works in concert with a peroxygen source in increasing bleaching effectiveness. Without being bound by theory, it is believed that bleach boosters react with peroxygen sources to form the more active bleaching species, the quaternary oxaziridinium compounds. Oxaziridinium compounds have higher activity at lower temperatures than peroxygen compounds. Oxaziridinium compounds are represented by the following formulas [III] and [IV]:

[Chemical 31] In the above formula, t is 0 or 1; R ³¹ -R ³⁴ is from H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. Is a substituted or unsubstituted group selected from the group consisting of: two adjacent R ³¹ -R ³⁴ may be joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is A substituted or unsubstituted group selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups; R ²⁶ Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, substituted or unsubstituted selected from the group consisting of groups represented by heterocyclic rings and the following formula is a saturated or unsaturated ^{_{group: -T o - (Z -)}} a the formula Z ^- is being covalently bonded to _{T o,} and Z ^- represents _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
_{-CH 2 (C 6 H 4)} -;

[Chemical 32] _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl);

[Chemical 33] (Where x is 0-3; J, when present, is independently --CR³⁹R⁴⁰ ‐ 、 ‐ CR³⁹R⁴⁰CR⁴¹R⁴²-And-CR³⁹R⁴⁰CR⁴¹R⁴² CR⁴³R⁴⁴Selected from the group consisting of; R³⁵-R⁴⁴Is H, C₁-C_{1 8} Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkyle
Ring, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and
And a substituted or unsubstituted group selected from the straight-chain or branched groups consisting of an amide group.
) Selected from the group consisting of; R²⁷-R^ThirtyIs H, linear or branched C₁-C_{1 Two} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
A substituted or independently selected from the group consisting of cycloalkyl and heterocyclic ring
Is an unsubstituted group, provided that when t is 0, R is²⁷Also R²⁸Is not H, but t
When is 1, R²⁷And R²⁸Both, or R²⁹And R^ThirtyIs
Neither is H; either R²⁵-R³⁴Also any other R²⁵-R³⁴When
They may be joined together to form part of a covalent ring. Furthermore, R²⁵-R^ThirtyAnd R ³¹ -R³⁴Is the R of the bleach booster of formulas [I] and [II]⁵-R¹⁰And
And R¹-R^FourAnd each may be the same. Such an oxaziridinium compound is
It can be prepared from the quaternary imines of the invention in the following reactions:

[Chemical 34]

Bleaching Seeds -Bleaching Seeds (Oxaziridinium) may also be used directly in accordance with the present invention. The bleaching species of the present invention is preferably selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyions with a net charge of about +3 to about -3, and mixtures thereof. The above oxaziridinium compound has the following formulas [III] and [IV]:

[Chemical 35] In the above formula, t is 0 or 1; R ³¹ -R ³⁴ is from H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. Is a substituted or unsubstituted group selected from the group consisting of: two adjacent R ³¹ -R ³⁴ may be joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is A substituted or unsubstituted group selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups; R ²⁶ Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, substituted or unsubstituted selected from the group consisting of groups represented by heterocyclic rings and the following formula is a saturated or unsaturated ^{_{group: -T o - (Z -)}} a the formula Z ^- is being covalently bonded to _{T o,} and Z ^- represents _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
_{-CH 2 (C 6 H 4)} -;

[Chemical 36] _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl);

[Chemical 37] (Where x is 0-3; J, when present, is independently --CR³⁹R⁴⁰ ‐ 、 ‐ CR³⁹R⁴⁰CR⁴¹R⁴²-And-CR³⁹R⁴⁰CR⁴¹R⁴² CR⁴³R⁴⁴Selected from the group consisting of; R³⁵-R⁴⁴Is H, C₁-C_{1 8} Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkyle
Ring, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and
And a substituted or unsubstituted group selected from the straight-chain or branched groups consisting of an amide group.
) Selected from the group consisting of; R²⁷-R^ThirtyIs H, linear or branched C₁-C_{1 Two} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
A substituted or independently selected from the group consisting of cycloalkyl and heterocyclic ring
Is an unsubstituted group, provided that when t is 0, R is²⁷Also R²⁸Is not H, but t
When is 1, R²⁷And R²⁸Both, or R²⁹And R^ThirtyIs
Neither is H; either R²⁵-R³⁴Also any other R²⁵-R³⁴When
They may be joined together to form part of a covalent ring. Furthermore, R²⁵-R^ThirtyAnd R ³¹ -R³⁴Is the R of the bleach booster of formulas [I] and [II]⁵-R¹⁰And
And R¹-R^FourAnd each may be the same.

[0035] Preferred bleaching species, ^{(1) R 25} is H or ^{methyl, R 26} is linear or branched _C 1 _{-C 14 alkyl,} C 3 _{-C 14} cycloalkyl and _C 6 _{-C 1 4} aryl An oxaziridinium cation of formula [III] selected from the group of substituted or unsubstituted groups consisting of: (2) R ²⁵ is H or methyl and R ²⁶ has the formula: -T _o- ( Z ^-) _a (the formula Z ^- is being covalently bonded to _{T o,} and Z ^- represents _-CO ² -, -SO ₃ ^- and -OSO ₃ ^- is selected from the group consisting of, a is 1 or 2 there) oxaziridinium zwitterions of formula [IV]; (3) R ²⁶ is selected from the group consisting of linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl, Okisajiri of formula [III] di-cation or ^{R 2,} There is a group of the _{^{formula: -T o - (Z -)}} a ( In the formula Z ^- is -CO ₂ ^- and is, a is 1, _{T o} is selected from the group consisting of: :

[Chemical 38] The formula p is an integer from 2 to 4, Alley R ⁴⁵ are independently selected from the group consisting of H and linear or branched C ₁ -C _{1 8} substituted or unsubstituted alkyl) formula [IV] And (4) R ²⁵ is H, Z ⁻ is —CO ₂ ^— , —SO ₃ ^— or —OSO ₃ ^— , and a has a net negative charge. There are, but are not limited to, aryliminium polyions.

The bleach enhancing compounds of the present invention are used in a bleaching composition, with or without a source of peroxygen, preferably together therewith. In the bleaching composition of the present invention, the peroxygen source is from about 0.1% by weight (1 ppm) to about 60% of the composition (
600 ppm), preferably from about 1% (10 ppm) to about 40% (4% by weight of the composition.
Bleach-enhancing compound and / or bleaching species are present at a level of about 0.0001 ppm), and the bleach-enhancing compound and / or bleaching species are present at about 0.00001% (0.0001 ppm) to about 10% (100 pp) of the composition.
m), preferably about 0.0001% by weight (0.001 ppm) to about 2% of the composition.
(20 ppm), more preferably about 0.005% (0.05 ppm) to about 0.5.
% (5 ppm), and even more preferably about 0.01% (0.1 ppm) to about 0.2.
% (2 ppm). Most preferably about 0.02% (0.2 ppm) to about 0.1% (1 ppm). Preferably, the bleaching composition of the bleach composition of the present invention comprises the bleach enhancing compound and / or bleaching species in an amount such that the concentration of the bleach enhancing compound obtained in the wash liquor is from about 0.001 to about 5 ppm. Become.

Further preferably, the bleach composition of the present invention has a molar ratio of peroxygen compound to bleach enhancing compound and / or bleaching species obtained in the wash liquor which is preferably greater than 1: 1 and more preferably 10: 1. : 1, and even more preferably greater than 50: 1, with the peroxygen compound, if present, and the bleach enhancing compound and / or bleaching species. The preferred molar ratio range of peroxygen compound to bleach enhancing compound is from about 30,000: 1 to about 10.
: 1, even more preferably about 10,000: 1 to about 50: 1, even more preferably about 5000: 1 to about 100: 1, and even more preferably about 3500: 1 to about 150: 1.

Conversion values (ppm) are shown for illustrative purposes, based on an in-use product concentration of 1000 ppm. 10 of products containing 0.2% bleach enhancing compound by weight
The 00 ppm wash has a bleach enhancing compound concentration of 2 ppm. Similarly, a 3500 ppm wash of a product containing 0.2% by weight bleach enhancing compound was 6.
This results in a bleach-enhancing compound concentration of 5 ppm.

Methods for delivering the bleach-enhancing compounds of the present invention, methods for delivering bleaching compositions (products) containing such bleach-enhancing compounds particularly useful in the methods of the present invention include peroxygen sources. And a composition containing the bleach-enhancing compound and structure thereof which fits the preferred method for bleaching a substrate soiled with an aqueous medium containing the bleach-enhancing compound described herein, wherein the medium is per liter of medium. About 0.05 to about 250 ppm active oxygen from a peroxygen compound, and 0.001 to about 5 ppm, preferably about 0.01 to about 3 ppm, more preferably about 0.1 to about 2 ppm, most preferably about 0. .2 to about 1 ppm of the bleach enhancing compound. Such a preferred method for bleaching soiled substrates with an aqueous medium containing a peroxygen source and a bleach enhancing compound is of particular value in applications where color safety of soiled substrates in need of cleaning is a concern. is there. In such applications, the preferred embodiment (eg, 0.01 to about 3 ppm) is particularly important in achieving acceptable fabric color safety. Higher in-use concentrations are preferred for other applications where the color safety of dirty substrates requiring cleaning is less of a concern.

The bleaching compositions of the present invention include, but are not limited to, laundry applications including stain bleaching, dye transfer inhibition and whitening, hard surface cleaning, automatic dishwashing applications, and cosmetic applications such as dentures, teeth, hair and skin. Are used advantageously. However, because of the unique advantage of improved bleaching effectiveness in cold solutions, the bleach enhancing compounds of the present invention are ideally suited for laundry applications such as bleaching fabrics through the use of bleach-containing detergents or laundry bleach additives. . Further, the bleach enhancing compounds of the present invention are used in both granular and liquid compositions.

Accordingly, the bleaching compositions of the present invention may contain various additional ingredients desired in laundry applications. Such ingredients include detergent surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other ingredients.
Compositions containing these various additional ingredients preferably have a pH of about 6 to about 12, preferably about 8 to about 10.5 in a 1% solution of the bleaching composition. The bleaching composition preferably contains at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme, preferably 1% of the bleaching composition.
In solution, it has a pH of about 6 to about 12, preferably about 8 to about 10.5.

According to another aspect of the invention, a cationic or zwitterionic laundry bleach enhancing compound is provided. Such bleach-enhancing compounds are preferably:

[Chemical Formula 39] And in the formulas [I] and [II], t is 0 or 1; R ¹ -R ⁴ are H, alkyl, cycloalkyl, aryl, heterocyclic ring, Nitro, halo, cyano, sulfonato, alkoxy, keto,
A substituted or unsubstituted group selected from the group consisting of carboxyl and carboalkoxy groups; two adjacent R ¹ -R ⁴ are joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring R ⁵ may also be a substituent selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. Or an unsubstituted group; R ⁶ is a substituted or unsubstituted, saturated or unsubstituted selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring and a group represented by the following formula. is a saturated _{^{group: -T o - (Z -)}} a above wherein Z ^- is being covalently bonded to _{T o,} and Z ^- -C ₂ ^-, -SO ₃ ^{-, -}
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
_{-CH 2 (C 6 H 4)} -;

[Chemical 40] _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl);

[Chemical 41] (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 18 R 19 -, - CR} 18 R 19 CR 20 R 21 - , and ^{-CR 18 R 19 CR 20 R 21} CR ²² R ²³ - is selected from the group consisting ^of; R 14 ^{-R 23} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ⁷ -R ¹⁰ is H, linear or branched C ₁ -C ₁₂ alkyl A substituent independently selected from the group consisting of, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic ring. Or an unsubstituted group, provided that when t is 0, neither R ⁷ nor R ⁸ is H, and when t is 1, R ⁷ and R ⁸ are both, or R ⁹ and R ¹⁰ are both Neither is H; either R ¹ -R ¹⁰ is joined together with any other R ¹ -R ¹⁰ ,
May form part of a covalent ring; in formulas [III] and [IV], t is 0 or 1; R ³¹ -R ³⁴ is H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro , Halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups are substituted or unsubstituted groups; two adjacent R ³¹ -R ³⁴ are joined to form a fused aryl, fused carbocycle. R ²⁵ may form a formula or fused heterocyclic ring; R ²⁵ is H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. R ²⁶ is a substituted or unsubstituted group selected from the group consisting of: R ²⁶ is H, alkyl, cycloalkyl, alkaryl, aryl , Aralkyl, substituted or unsubstituted selected from the group consisting of groups represented by heterocyclic rings and the following formula is a saturated or unsaturated ^{_{group: -T o - (Z -)}} a above wherein Z ^- is T _o is covalently bonded to, Z ^- is _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
_{-CH 2 (C 6 H 4)} -;

[Chemical 42] _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl);

[Chemical 43] (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 39 R 40 -, - CR} 39 R 40 CR 41 R 42 - , and ^{-CR 39 R 40 CR 41 R 42} CR ⁴³ R ⁴⁴ - is selected from the group consisting ^of; R 35 ^{-R 44} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ²⁷ -R ³⁰ is H, linear or branched C ₁ -C _{1 2} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
A substituted or unsubstituted group independently selected from the group consisting of cycloalkyl and a heterocyclic ring, provided that when t is 0, neither R ²⁷ nor R ²⁸ is H and t
When R is 1 and R ²⁷ and R ²⁸ are not both H, or R ²⁹ and R ³⁰ are both H; then any R ²⁵ -R ³⁴ is bound together with any other R ²⁵ -R ³⁴ May form part of a covalent ring.

In another aspect of the invention, a method for laundering fabric in need of laundering is provided. In a preferred method, the fabric is contacted with the wash liquor. The fabric includes almost any fabric that can be laundered under normal consumer use conditions. The laundry liquor comprises a bleaching composition as described in detail herein. The water temperature applied in this washing method is preferably about 0 to about 50 ° C. The water to fabric ratio is preferably about 1: 1 to about 15: 1. The laundry liquor may further comprise at least one additional ingredient selected from the group consisting of detergent surfactants, chelating agents, detergent enzymes and mixtures thereof. Preferably, the wash liquor is about 6 to about 12, preferably about 8 to about 1 in a 1% solution of the bleaching composition.
It has a pH of 0.5.

According to another aspect of the invention, a laundry additive product is provided. The laundry additive product comprises a bleach enhancing compound as described in detail above. Such laundry additive products would ideally be suitable for inclusion in the wash process when additional bleaching effectiveness is desired. Such cases include, but are not limited to, cold solution laundry applications. Desirably, the laundry additive product further contains a source of peroxygen as detailed above. The laundry additive product may also contain a powder or liquid composition containing a source of hydrogen peroxide or a source of peroxygen as detailed above. Further, if the laundry additive product contains a hydrogen peroxide source, the laundry additive product may be
It may be desirable to further include a bleach activator as described in detail above.

Preferably, the laundry additive product is packaged in a dosage form suitable for addition to the laundry process when a source of peroxygen is used and high bleaching effectiveness is desired. Such unit dosage forms include pills, tablets, gelcaps, or other single dosage units such as metered powders or liquids. Fillers or carrier materials may also be included to increase the volume of the composition if desired. Suitable fillers or carrier materials are selected from, but not limited to, sulfuric acid, various salts of carbonic acid and silicic acid, talc, clay and the like. Filler or carrier materials for liquid compositions include water or low molecular weight primary and secondary alcohols such as polyols and diols. Examples are methanol, ethanol, propanol and isopropanol. Monohydric alcohols may also be used. The composition may contain from about 5 to about 90% of such materials. Acidic fillers can also be used to lower the pH. When the bleach-enhancing compound of the present invention is other than an aryliminium zwitterion or an oxaziridinium zwitterion, there are also suitable bleach-compatible, charge-balancing counterions.

Bleaching Compositions Containing Bleach-Enhancing Compounds In addition to the use of the bleach-enhancing compounds described above, the bleach-enhancing compounds of the present invention include:
In other bleaching compositions, regardless of their form, it is used with or without a source of peroxygen, preferably with it. For example, bleach enhancing compounds are used in laundry additive products. In the bleaching composition of the present invention, the peroxygen source is present at a level of from about 0.1 to about 60% by weight of the composition, preferably from about 1 to about 40% by weight of the composition. In the composition, the bleach enhancing compound is about 0.0% of the composition.
01 to about 10% by weight, more preferably about 0.005 to about 5% by weight of the composition. In the bleaching composition of the present invention, the peroxygen source is from about 0.1% by weight (1 ppm) to about 60% (600 ppm) of the composition, preferably about 1% by weight of the composition (
10 ppm) to about 40% (400 ppm) and the bleach enhancing compound is about 0.00001% (0.0001 ppm) to about 10% (10% by weight of the composition.
0 ppm), preferably about 0.0001% by weight of the composition (0.001 ppm)
About 2% (20 ppm), more preferably about 0.005% (0.05 ppm) to about 0.5% (5 ppm), even more preferably about 0.01% (0.1 ppm) to about 0.2%. Present at (2 ppm). Most preferably about 0.02% (0.2 ppm
) -About 0.1% (1 ppm).

Conversion values (ppm) are shown for illustrative purposes, based on an in-use product concentration of 1000 ppm. 10 of products containing 0.2% bleach enhancing compound by weight
The 00 ppm wash has a bleach enhancing compound concentration of 2 ppm. Similarly, a 3500 ppm wash of a product containing 0.2% by weight bleach enhancing compound was 6.
This results in a bleach-enhancing compound concentration of 5 ppm.

Although the preferred bleach enhancing compound concentration is based on a bleach enhancing compound molecular weight of about 300 g / mol, the bleach enhancing compound is preferably about 150-1000 g.
/ Mol, or higher in the case of oligomeric or polymeric bleach enhancing compounds. For example, in the bleaching composition of the present invention, the bleach enhancing compound is more preferably from about 0.005% (0.05 ppm) to about 0.5% (
When present at 5 ppm), the molar (M) concentration of the bleach enhancing compound is 1.7 x 1
0 is ^{-8 M~1.7} × ^{10 -5} M. When a high molecular weight bleach enhancing compound is used in the bleaching composition of the present invention, the preferred molarity remains unchanged,
The preferred weight concentration (ppm) increases accordingly. For example, the molecular weight is about 600 g /
More preferably, the molar bleach enhancing compound is from about 0.01% (0.1 ppm).
It is present at about 1.0% (10 ppm). In the case of oligomeric or polymeric bleach enhancing compounds, more preferred molar concentrations will be based on monomeric units with iminium or oxaziridinium active sites.

The bleaching composition of the present invention is used for laundry applications, hard surface cleaning, automatic dish washing applications,
And advantageously in cosmetic applications such as dentures, teeth, hair and skin. However, owing to the unique advantages of improved color safety and improved efficacy in low and warm aqueous solutions, probably due to increased solubility, the bleach-enhancing compounds of the present invention are suitable for bleach-containing detergent or laundry bleach addition. Ideally suited for laundry applications such as bleaching fabrics with the use of objects. Further, the bleach enhancing compounds of the present invention are used in both granular and liquid compositions. The bleach-enhancing compound and the bleaching composition containing the bleach-enhancing compound can be used as antibacterial agents and disinfectants.

Accordingly, the bleaching compositions of the present invention may contain various additional ingredients that are desirable in laundry applications. Such ingredients include detergent surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other ingredients.
Compositions containing these various additional ingredients preferably have a pH of about 6 to about 12, preferably about 8 to about 10.5 in a 1% solution of the bleaching composition. The bleaching composition preferably contains at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme, preferably 1% of the bleaching composition.
In solution, it has a pH of about 6 to about 12, preferably about 8 to about 10.5.

In another aspect of the invention, a method is provided for laundering a fabric in need of laundering. In a preferred method, the fabric is contacted with the wash liquor. The fabric includes almost any fabric that can be laundered under normal consumer use conditions. The laundry liquor comprises a bleaching composition as described in detail herein. The water temperature is preferably about 0 to about 5
0 ° C or higher. The water to fabric ratio is preferably about 1: 1 to about 15: 1. The laundry liquor may further comprise at least one additional ingredient selected from the group consisting of detergent surfactants, chelating agents, detergent enzymes and mixtures thereof. Preferably, the wash liquor is about 6 to about 12, preferably about 8 to about 1 in a 1% solution of the bleaching composition.
It has a pH of 0.5.

According to another aspect of the invention, a laundry additive product is provided. The laundry additive product comprises a bleach enhancing compound as described in detail above. Such laundry additive products would ideally be suitable for inclusion in the wash process when additional bleaching effectiveness is desired. Such cases include, but are not limited to, low and medium temperature solution laundry applications. Desirably, the laundry additive product further contains a source of peroxygen as detailed above. The laundry additive product may also contain a powder or liquid composition containing a source of hydrogen peroxide or a source of peroxygen as described in detail above. Further, if the laundry additive product contains a hydrogen peroxide source, the laundry additive product may be
It may be desirable to further include a bleach activator as described in detail above.

Preferably, the laundry additive product is packaged in a dosage form suitable for addition to the laundry process when a source of peroxygen is used and high bleaching effectiveness is desired. Such unit dosage forms include pills, tablets, gelcaps, or other single dosage units such as metered powders or liquids. Fillers or carrier materials may also be included to increase the volume of the composition if desired. Suitable fillers or carrier materials are selected from, but not limited to, sulfuric acid, various salts of carbonic acid and silicic acid, talc, clay and the like. Filler or carrier materials for liquid compositions include water or low molecular weight primary and secondary alcohols such as polyols and diols. Examples are methanol, ethanol, propanol and isopropanol. Monohydric alcohols may also be used. The composition may contain from about 5 to about 90% of such materials. Acidic fillers can also be used to lower the pH.

A preferred bleaching composition is: (a) a bleaching composition comprising a source of peroxygen, and (b) a bleach enhancing compound, the bleaching composition being provided shortly after the source of peroxygen is activated. The bleach enhancing compound becomes active in the contained aqueous solution. The peroxygen source as described above is preferably before: (i) selected from the group consisting of percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. Forming 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.

Bleaching System-In addition to the bleach enhancing compounds of the present invention, the bleaching compositions of the present invention preferably contain a bleaching system. Bleaching systems typically comprise a source of peroxygen. Peroxygen sources are well known in the art, and the peroxygen sources used in the present invention include those containing peroxygen compounds and compounds that form an effective amount of peroxygen in situ under conditions of consumer use. It may be any of the well known sources.
Peroxygen sources include hydrogen peroxide sources, in situ formation of peracid anions from the reaction of hydrogen peroxide sources and bleach activators, preformed peracid compounds or mixtures of suitable peroxygen sources. Of course, those skilled in the art will appreciate that other sources of peroxygen may be used without departing from the scope of the invention. Preferably, the peroxygen source is: (i) a preformed peracid compound selected from the group consisting of percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. 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. When present, the peroxygen source (peracid and / or hydrogen peroxide source) is typically about 1% by weight of the composition, preferably about 5% to about 30%, preferably about 20%.
% Level. When present, the amount of bleach activator is typically about 0.1% by weight of the bleaching composition containing the bleach + bleach activator, preferably from about 0.5% to about 60%, preferably It is about 40%.

A. Preformed Peracid-The preformed peracid compound as used herein can be any convenient compound that is stable and forms an effective amount of peracid anion under conditions of consumer use. The bleach-enhancing compounds of the present invention include, of course, preformed peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. Combinations may be used, examples of which are described in US Pat. No. 5,576,282 to Miracle et al.

[0057]   One suitable organic peroxycarboxylic acid has the general formula:

[Chemical 44] In the above formula, R is an alkylene or substituted alkylene group having 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, and Y is hydrogen, halogen,
Alkyl, aryl, -C (O) OH or -C (O) OOH.

Organic peroxyacids suitable for use in the present invention can have 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 45] In the above formula, Y is, for example, H, CH ₃ , CH ₂ Cl, C (O) OH or C (O) OO.
H and n is an integer of 0-20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[Chemical formula 46] In the above formula, Y is, for example, hydrogen, alkyl, alkylhalogen, halogen, 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 acid, such as peroxysuccinic acid (NAPSA) Others have monononylamide of peroxyadipic acid (NAPAA).

Typical diperoxy acids useful herein include alkyl and aryl diperoxy acids such as (iv) 1,12-diperoxide decanedioic acid (v) 1,9-diperoxyazelaic acid (vi ) Diperoxybrassic acid, diperoxysebacic acid and diperoxyisophthalic acid (vii) 2-decyldiperoxybutane-1,4-dioic acid (viii) 4,4'-sulfonylbisperoxybenzoic acid.

Such a bleach is commercially available from Hartman US, issued Nov. 20, 1984.
U.S. Pat. No. 4,483,781, Burns et al., US Pat. No. 4,634,551, Banks et al., European patent application 0,133,354, published February 20, 1985, and November 1, 1983. No. 4,412,934 to Chung et al. Its source also includes 6-nonylamino-6-oxoperoxycaproic acid, as described in detail in Burns et al., US Pat. No. 4,634,551, issued Jan. 6, 1987. EIDu Pont de Nemours of W
Persulfate compounds such as OXONE manufactured by ilmington, DE may also be used as a suitable source of peroxymonosulfate.

B. Hydrogen Peroxide Source -The hydrogen peroxide source may be any suitable source of hydrogen peroxide, U
It exists at a level as described in detail in US Pat. No. 5,576,282. For example, the hydrogen peroxide source is selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof. Hydrogen peroxide source is incorporated here Kirk Othmer's Encyclopedia of Chemical
Technology, 4th Ed. (1992, John Wiley & Sons), Vol.4, pp.271-300 "Bleaching A
gents (Survey) ", there are various forms of sodium perborate and sodium percarbonate, including various coated and modified forms.

The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, such as sodium perborate (any hydrate, but preferably mono or tetrahydrate), sodium carbonate peroxyhydrate or the corresponding percarbonate salt, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or peroxide. Sodium can be used here. Persulfate Bleach (eg DuPont
Effective oxygen sources such as OXONE) are also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Any convenient mixture of hydrogen peroxide sources may be used.

A preferred percarbonate bleach consists of dry particles having an average particle size in the range of about 500 to about 1000 μm, wherein less than about 10% by weight of the particles are less than about 200 μm and less than about 10% by weight of the particles are about 10% by weight. Larger than 1250 μm. Optionally, the percarbonate may be coated with silicates, borates or water-soluble surfactants. Percarbonates are commercially available from various sources such as FMC, Solvay and Tokai Denka.

The compositions of the present invention may also include chlorine-type bleaching agents as bleaching agents. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate ("Na
DCC "). However, chlorine-type bleaching is less preferred in enzyme-containing compositions.

C. Bleach Activator- Preferably, the source of peroxygen in the composition is formulated with an activator (peracid precursor). The activator is about 0.01% by weight of the composition, preferably about 0.5%, more preferably about 1% to about 15%.
%, Preferably about 10%, more preferably about 8%. A bleach activator as used herein, when used in combination with a hydrogen peroxide source,
It may be any compound capable of forming in situ a peracid corresponding to a bleach activator. Various non-limiting examples of activators are described in US Pat. No. 5,576,282,
Details are disclosed in US Pat. No. 4,915,854 and US Pat. No. 4,412,934. See also US 4,634,551 for other exemplary bleaches and activators useful herein.

A preferred activator is tetraacetylethylenediamine (TAED),
Benzoyl caprolactam (BzCl), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyl oxybenzene sulphonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyl oxybenzene sulphonate _{(C 10} - OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C ₈ -OBS), perhydrolysable esters and mixtures thereof, most preferably selected from the group consisting of benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of about 8 to about 9.5 are selected from those having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include nonanoyloxybenzene sulfonate (NOBS), 4- [N- (nonanoyl) aminohexanoyloxy]
Benzenesulfonate sodium salt (NACA-OBS) (example is US Patent 5
, 523, 434), lauroyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzenesulfonate (unsaturated UDOBS or C ₁₁ -OBS at the 10-position) and decanoyloxy. There is, but is not limited to, benzoic acid (DOBA).

A preferred bleach activator was issued December 16, 1997.
Christie et al., US 5,698,504, Ch, published December 9, 1997.
ristie et al., US 5,695,679, Wi, issued November 11, 1997
Lley et al., US Pat. No. 5,686,401, Hart issued Nov. 11, 1997.
Wille Shorn et al., US 5,686,014, published April 11, 1995.
y et al US 5,405,412, Willey et al US 5,405,413 issued April 11, 1995, Mitchel et al US 5,130,045 and July 1983 issued July 14,1992. Chung et al., US 4,412,934, and co-pending patent application USSN 08 / 709,07, issued January 1,
2, 08 / 064,564, all of which are incorporated herein by reference.

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

Quaternary substituted bleach activators may also be included. The bleaching composition is preferably a quaternary substituted bleach activator (QSBA) or quaternary substituted peracid (QSP).
), And more preferably the former. The preferred QSBA structure is 1997 1
Willey et al., US 5,686,015 issued Jan. 11, Taylor et al., US 5,654,421 issued Aug. 5, 1997, Oct. 24, 1995.
US Pat. No. 5,460,747, Gosselink et al., Issued December 1, 1996.
US Pat. No. 5,584,888 to Miracle et al.
It is further described in US Pat. No. 5,578,136 issued to Taylor et al., Dated March 26, all of which are incorporated herein by reference.

Highly preferred breach activators useful herein are US 5,698,504, US 5,695,679 and US 5,686, each of which are cited above.
Amide substituted as described in 014. Preferred examples of such bleach activators include (6-octanamidocaproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate and their There is a mixture.

US Pat. No. 5,698,504, US Pat. No. 5,695,679, each cited above,
Hodge, US 5,686,014, and October 30, 1990
Other useful activators disclosed in US Pat.
There are benzoxazine-type activators such as the C ₆ H ₄ ring fused with the moiety —C (O) OC (R ¹ ) ═N— at the 1,2-position.

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

Acyl lactam activators such as those described in US 5,698,504, US 5,695,679 and US 5,686,014, each of which is cited above, in particular acyl caprolactam (see for example WO 94-28102A) and Acylvalerolactam (see Willey et al. US Pat. No. 5,503,639, published Apr. 2, 1996, incorporated herein by reference) is very useful herein.

D. Organic peroxides, especially diacyl peroxides- in addition to the bleaching agents mentioned above,
The bleaching composition of the present invention may optionally contain an organic peroxide. Organic peroxides are from Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley.
and Sons, 1982, pp. 27-90, especially pp. 63-72, all incorporated herein by reference. When diacyl peroxides are used, those which minimize the adverse effects of smearing / filming are preferred.

E. The metal containing bleach catalyst -bleaching composition may optionally also contain a metal containing bleach catalyst, preferably a manganese and cobalt containing bleach catalyst. One type of metal-containing bleach catalyst is a transition metal cation of a given bleach catalytic activity, such as a copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cation, an auxiliary metal cation with little or no bleach catalytic activity, such as zinc. Or an ion sequestrant having a predetermined stability constant for aluminum cations, catalysts and auxiliary metal cations, especially ethylenediaminetetraacetic acid,
A catalyst system comprising ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such a catalyst is disclosed in Br 2 dated February 2, 1982.
It is disclosed in agg US 4,430,243.

[0078]     i.Manganese metal complex-If desired, the composition may be contacted with a manganese compound.
Can be carried. Such compounds and levels of use are well known in the art and include, for example:
Miracle et al., US 5,576,282, issued November 19, 1996,
Favre et al., US 5,246,621, 19 issued Sep. 21, 1993.
Favre et al., US 5,244,594, 1993, issued September 14, 1993.
Jureller et al., US 5,194,416, 1992, published March 16, 2013
US Patent No. 5,114,606 issued by van Vliet et al. Issued on May 19, European patent
Application Publication 549, 271A1, 549, 272A1, 544, 440A2 and 5
There are manganese-based catalysts disclosed in 44,490A1. Preference for these catalysts
An example is Mn^IV _Two(U-O)_Three(1,4,7-Trimethyl-1,4,7-tri
Azacyclononane)_Two(PF₆)_Two, Mn^III _Two(U-O)₁(U-OAc)_Two
(1,4,7-Trimethyl-1,4,7-triazacyclononane)_Two(ClO_Four )_Two, Mn^IV _Four(U-O)₆(1,4,7-Triazacyclononane)_Four(ClO _Four )_Four, Mn^IIIMn^IV _Four(U-O)₁(U-OAc)_Two(1,4,7-trime
Chill-1,4,7-triazacyclononane)_Two(ClO_Four)_Three, Mn^IV(1,4
, 7-Trimethyl-1,4,7-triazacyclononane) (OCH_Three)_Three(PF ₆ ) And mixtures thereof. Other metal-based bleach catalysts are useful
US 4,430,243 and May 19, 1992, previously incorporated herein.
Disclosed in van Kralingen US Pat. No. 5,114,611
It The use of manganese with various complexing ligands to enhance bleachability is also reported below.
In: US 4,728,455 of Rerek, issued March 1, 1988,
Madison US 5,284,944,199, issued February 8, 1994.
Van Dijk et al., US 5,246,612, 1993, published 21 September 3rd.
Kerschner et al., US 5,256,779, 199, issued October 26, 2010
Kerschner et al., US Pat. No. 5,280,117,199 issued Jan. 18, 4
Kerschner et al., US Pat. No. 5,274,147, 19 issued Dec. 28, 3
Kerschner et al., US 5,153,161, issued October 6, 1992, and
Martens et al., US 5,227,084, issued July 13, 1993.

[0079]     ii.Cobalt metal complex-Cobalt bleach catalysts useful herein are known,
For example, Perkins et al., US Pat. No. 5,597,9, issued Jan. 28, 1997.
36, US 5,595,96 to Miracle et al., Issued January 21, 1997.
7, Perkins et al., US 5,703,03, issued December 30, 1997.
0 and M.L.Tobe, "Base Hydrolysis of Transition-Metal Complexes",Adv.Ino rg.Bioinorg.Mech. , (1983), 2, pages 1-94. Most useful here
A preferred cobalt catalyst has the formula [Co (NH_Three)₅OAc] T_y("OAc" is a
Represents the set portion, "T_yIs a anion)
Min acetate, especially cobalt pentaamine acetate chloride [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 (N
H_Three)₅OAc] (BF_Four)_TwoAnd [Co (NH_Three)₅OAc] (NO_Three)_Two (Hereinafter “PAC”).   These cobalt catalysts are described, for example, in the above-cited US Pat. No. 5,597,93.
6,5,595,967,5,703,030, Tobe's paper cited above and
And US Patent 4,810,410 to Diakun et al., Issued Mar. 7, 1989; J. Chem. Ed. (1989),66(12), 1043-45 ； The Synthesis and Characterization of I
norganic Compounds, W.L.Jolly (Prentice-Hall; 1970), pp.461-3;Inorg.Chem.,1 8 , 1497-1502 (1979);Inorg.Chem.,twenty one, 2881-2885 (1982);Inorg.Chem.,18, 2023-2
025 (1979); Inorg. Synthesis, 173-176 (1960); andJournal of Physical Chem istry ,56, 22-25 (1952), easily manufactured by known operations.
Be done.

Iii. Transition Metal Complexes of Large Polycyclic Rigid Ligands-The present compositions may also suitably contain transition metal complexes of large polycyclic rigid ligands as bleach catalysts. The phrase "macropolycyclic rigid ligand" is sometimes abbreviated below as "MRL". The amount used is a catalytically effective amount, suitably about 1 ppb or higher, for example within about 99.9%, more typically about 0.001 ppm or higher, preferably about 0.05 to about 500 ppm ("ppb"). Represents parts / billion by weight and "ppm" represents parts / million by weight).

Suitable transition metals, such as Mn, are described below. "Large polycyclic" means M
It is meant that the RL is both macrocycle and polycyclic. "Polycyclic" means at least bicyclic. As used herein, the term "rigid" includes "having a superstructure" and "crosslinked.""Hard" is defined as the opposite of soft:. DHBusch, which is incorporated by reference, Chemical Re views, (1993) , 93, see 847-860. More specifically, the "hard" used here
Are identical to macrocycles (having the same ring size and type and number of atoms in the main ring) but lacking the superstructure (particularly the linking moiety, or preferably the bridging moiety) found in MRL. It means that the MRL must be stiffer than the "parent macrocycle"). In investigating the relative hardness of macrocycles with and without superstructure, the practitioner used the free form (not the metal bonded form).
Use a macro cycle. Hardness is well known to be useful in comparing macrocycles; suitable techniques for determining, measuring or comparing hardness include computer methods (eg, Zimmer, Chemical Reviews , (1995 ), 95 (38), 2629-264
8 or Hancock et al., Inorganica Chimica Acta , (1989), 164, 73-84). Preferred MRLs here are crosslinked, specific types of ultra-hard ligands. "Crosslinking" is described in non-limiting manner in Section 1.11. In 1.11, the bridge is-
CH ₂ CH ₂ - is a moiety. It bridges N ¹ and N ⁸ in the exemplary structure. For comparison, an "ipsilateral" bridge is not sufficient to build a "crosslink" and is therefore not preferred if it is introduced at N ¹ and N ¹² , eg at 1.11.

Suitable metals for hard ligand complexes include Mn (II), Mn (III), Mn (IV), Mn (V
), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni
(I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II),
Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), M
o (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (I
I), Ru (III) and Ru (IV). Preferred transition metals for the present transition metal bleach catalysts are manganese, iron and chromium.

More generally, the MRLs (and corresponding transition metal catalysts) are suitably: (a) at least one macrocycle main ring having 4 or more heteroatoms, and (b) ) Preferably, the macrocycle hardness can be increased, selected from (i) a bridging superstructure such as a linking moiety, (ii) a bridging superstructure such as a bridging linking moiety, and (iii) a combination thereof. It is composed of covalently bonded non-metallic superstructures. The term "superstructure" is also used here, as defined in the article by Busch et al. (See, for example, the article by Busch, "Chemical Reviews").

The preferred superstructures here are not only to increase the hardness of the parent macrocycle, but also to the folding of the macrocycle such that it coordinates with the metal in a crevice form. A suitable superstructure may be remarkably simple, for example connecting parts may be used as shown in FIGS. 1 and 2 below:

[Chemical 47] Where n is an integer, for example 2-8, preferably less than 6, typically 2-4; or

[Chemical 48] Where m and n are integers of about 1-8, more preferably 1-3; Z is N or CH; T is a compatible substituent such as H, alkyl, trialkylammonium, halogen, nitro. , Sulfonate and the like. The aromatic ring of 1.10 may be replaced by a saturated ring, in which case the atom of Z attached in the ring may be N, O, S or C.

[0085]   Suitable MRLs are further shown, without limitation, with the following compounds:

[Chemical 49] This is an MRL according to the invention which is a highly preferred bridged methyl substituted (all tertiary nitrogen atom) derivative of cyclam. Officially, this ligand is expanded von Ba
Using the eyer system, it is called 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane. "A Guide to IUPAC Nomenclature o
f Orgnic Compounds: Recommendations 1993 ", R. Panico, WH Powell & JCRich
er (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially Section R-2.4.2.1.

Macrocyclic hard ligand transition metal bleach catalysts suitable for use in the compositions of the present invention generally include known compounds consistent with the definitions herein, and more preferably the present laundry. Or there are a number of novel compounds specifically designed for cleaning and illustrated non-limitingly below: Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
． 6.2] Hexadecanemanganese (II) diako-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 diaco- 5,12-Dimethyl-1,5,8,12-tetraazabicyclo [6.
6.2] Hexadecanemanganese (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] hexadecane manganese (II) dichloro-5 , 12-Dibenzyl-1,5,8,12-tetraazabicyclo [
6.6.2] Hexadecane manganese (II) dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5- n-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5-n-butyl-12-methyl-1,5,8,12 -Tetraazabicyclo [6.6.2] hexadecane manganese (II)

F. Other Bleach Catalysts -The composition may include one or more other bleach catalysts. A preferred bleach catalyst is US Pat. No. 5,576,282 (especially 3- (3,4
-Dihydroisoquinolinium) propane sulphonate). Other bleach catalysts include US Pat. Nos. 5,360,569, 5,4
42,066, 5,478, 357, 5,370, 826, 5,482, 515
, 5,550,256, and cationic bleach catalysts described in WO95 / 13351, WO95 / 13352 and WO95 / 13353.

As a matter of fact, and not by way of example, the composition and cleaning process are adjusted to provide active bleach catalyst species in the aqueous cleaning medium at least as low as 0.01 ppm, and preferably in the cleaning fluid of about 0. 01 to about 25 ppm, more preferably about 0.05 to about 10 ppm, most preferably about 0.1 to about 5 ppm of bleach catalyst species is provided. To achieve such levels in the wash liquor of an automated wash process, a typical present composition is from about 0.0005 to about 0.2% by weight of the cleaning composition.
, More preferably about 0.004 to about 0.08% bleach catalyst, especially manganese or cobalt catalyst.

Preferably, the peroxygen source is selected from hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof, and bleach activators. Preferably, the bleach activator is selected from the group consisting of hydrophobic bleach activators as disclosed herein. The purpose of such bleaching compositions is to prevent undesired degradation of the bleach-enhancing compound, and to peroxidize the bleaching performance on fabrics that require cleaning, such as soiled fabrics in the wash liquor, before the bleach-enhancing compound is available. Is to bring to. The time difference between when the peracid is active in the wash liquor and when the bleach enhancing compound is active is from about 1 second to about 24 hours. On the other hand, since the bleach-enhancing compound is relatively stable in the wash liquor, the peracid may become activated in the wash liquor after the bleach-enhancing compound becomes active or available.

The purpose of the delayed-addition bleaching composition (which may or may not be used with the present invention) is to require cleaning such as soiled fabric in a wash liquor prior to the introduction of the bleach enhancing compound. Is to bring the maximum bleaching performance for the fabric to peracid. In other words, the bleaching composition contains a bleach enhancing compound that is activated in the wash liquor after the fabric requiring cleaning is added to the wash liquor. A method for the delayed (controlled) addition of bleach enhancing compounds is disclosed in the simultaneous application entitled “Controlled availability of prescription ingredients, compositions and laundry methods using same” filed Aug. 27, 1999. Pending and co-owned US provisional patent application (P & G Agent Case No. 774
9P) for further details.

On the other hand, since the bleach-enhancing compound has a high stability, a bleaching composition containing the bleach-enhancing compound which becomes active in the washing solution before the fabric requiring cleaning is added to the washing solution may also be used. The bleaching composition of the present invention preferably comprises, in addition to the one or more bleach enhancing compounds described above, one or more bleach enhancing compounds and / or enzymes which are preferably compatible with the bleach enhancing compounds and / or enzymes present in the bleaching composition. A cleaning additive is also included. As used herein, the term "compatibility" refers to the bleach-enhancing compound present in the bleaching composition to the extent that the bleach-enhancing compound and / or enzyme are not as effective as desired under normal conditions of use. It means not decreasing the bleaching activity of the compound and / or the enzymatic activity of the enzyme. As used herein, the term "cleaning additive" refers to the specific type of bleaching composition desired and product form (eg, liquid, granule, powder, bar, paste, spray, tablet, gel, foam composition). ) Means any liquid, solid or gaseous substance selected for
The material is also preferably compatible with the protease enzymes and bleaches used in the composition. Granular compositions may be in "compact" form, liquid compositions may be "concentrated"
It may be in the form.

The specific choice of cleaning adjunct material will be facilitated by considering the surface to be cleaned, the article or fabric, and the desired form of the composition depending on the cleaning conditions during use (eg, during use of the cleaning detergent). Done. Examples of suitable cleaning aids include US Pat. No. 5,705,464, 5,710,115,
5,698,504, 5,695,679, 5,686,014 and 5,64
6,101, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical brighteners,
Soil release polymer, dye transfer agent, dispersant, foam control agent, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescent agent, fabric conditioner, hydrolyzable surfactant, preservative, oxidation Inhibitors, anti-shrinkage agents, anti-wrinkle agents, fungicides, fungicides, color speckles, silver care, anti-rust and / or corrosion inhibitors, alkali sources, solubilizers, carriers, processing aids, Pigments and pH control agents include, but are not limited to. Specific bleaching composition materials are exemplified in detail below.

If the cleaning additive is not compatible with the protease variant in the bleaching composition,
Appropriate methods may also be used in which the cleaning additive and the protease variant are kept separate (not in contact with each other) until the binary combination is suitable. Suitable methods can be any method known in the art such as gel cups, encapsulation, tablets, physical isolation and the like.

Suitable bleaching compositions include, but are not limited to morphology, detergent compositions for cleaning hard surfaces (eg liquids, granules, pastes, foams, sprays, etc.);
Non-morphologically limited detergent compositions for cleaning fabrics (eg, granules, liquid and solid formulations, etc.); Dishwashing compositions (morphologically unlimited, including both granular and liquid automatic dishwashing); Morphologically A non-limiting oral bleaching composition (eg,
Dentifrice, toothpaste and mouthwash formulation); Morphologically unlimited bleaching composition (
For example, liquids, tablets).

Although the fabric bleaching composition of the present invention is mainly for use in the washing cycle of a washing machine,
However, other uses are also conceivable, such as pre-treatment products for heavily soiled fabrics, or dipping products; their use is not necessarily limited to the washing machine context, the compositions of the invention may be used alone or in compatible hand-washing compositions. You may use together with a thing.

The bleaching composition may contain from about 1 to about 99.9% by weight of the composition of a cleaning additive. As used herein, "non-fabric bleaching compositions" include hard surface bleaching compositions, dishwashing compositions, mouth bleaching compositions, denture bleaching compositions and personal cleansing compositions. When the bleaching composition of the present invention is formulated as a composition suitable for use in a washing machine washing method, the composition of the present invention preferably comprises both a surfactant and a builder compound, preferably an organic polymeric compound, It also contains one or more cleaning additives selected from bleaching agents, additional enzymes, foam control agents, dispersants, lime soap dispersants, soil suspension and anti-redeposition agents, and corrosion inhibitors. The laundry composition may also contain a softener as an additional cleaning additive. The composition of the present invention may also be used as a detergent additive product in solid or liquid form. Such additive products are present to enhance or enhance the performance of conventional detergent compositions and may be added at any stage of the cleaning process.

When formulated as a composition for hand dish washing, the composition of the present invention preferably comprises a surfactant and preferably an organic polymeric compound, a foam enhancer, a Group II metal ion, a solvent, a hydrotrope. And other cleaning additives selected from additional enzymes.

If desired, the laundry detergent composition has a density of 400 measured at 20 ° C.
~ 1200 g / L, preferably 600-950 g / L. The "compact" form of the bleaching composition is best reflected in terms of density and amount of inorganic filler salt in terms of composition; inorganic filler salt is a conventional ingredient in detergent compositions in powder form; conventional In some detergent compositions, the filler salt is present in substantial amounts, typically 17-35% by weight of the total composition. In compact compositions, the filler salt is present in an amount of not more than 15% by weight of the total composition, preferably not more than 10% of the composition, most preferably not more than 5%. The inorganic filler salt as meant in the present composition is selected from the alkali and alkaline earth metal salts of sulphates and chlorides. The preferred filler salt is sodium sulfate.

The liquid bleaching composition according to the invention may be in "concentrated form", in which case the liquid bleaching composition according to the invention contains a small amount of water compared to conventional liquid detergents. Typically, the water content of the concentrated liquid bleaching composition is preferably 40% or less by weight of the bleaching composition, more preferably 30% or less, most preferably 20% or less.

Cleaning Additives Although not essential for the purposes of the present invention, some conventional additives described below are also suitable for use in the bleaching composition, in the case of perfumes, colorants, dyes, etc. As such, it is desirable to formulate in a preferred embodiment of the present invention, for example to aid or enhance cleaning performance, to treat the substrate being cleaned, or to modify the aesthetics of the bleaching composition. The nature of these additional ingredients, and their level of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation used.
Unless stated otherwise, the bleaching compositions according to the invention are multipurpose or "heavy" detergents in the form of granules or powders, in particular laundry detergents; multipurpose detergents in the form of liquids, gels or pastes, in particular so-called heavy liquid types; liquid delicates. Fabric detergents; hand or light dishwashing agents, especially those of high forming type; mechanical dishwashing agents including various tablets, granules, liquids and rinsing aids for household and institutional use; antibacterial hand washing type, solid laundry soap, Liquid cleaning and disinfectants including mouthwash, denture cleaner, car or carpet shampoo, bathroom cleaner; hair shampoo and hair rinse; shower gel, foam bath and metal cleaner;
As well as bleach additives and cleaning aids such as "stain sticks" or pretreatment types.

Surfactant- The compositions of the present invention preferably contain a detersive surfactant.
Detergent surfactants are typically anionic, nonionic, cationic, amphoteric,
It is selected from the group consisting of bipolar and mixtures thereof. By selecting the type and amount of detergent surfactant, along with other additive components disclosed herein, the detergent composition can be formulated for use in laundry cleaning-related or other different cleaning applications, particularly dishwashing. You can. Thus, the particular surfactant used will vary depending on the particular end use application envisioned. Suitable surfactants are described below. Examples of suitable nonionic, anionic, cationic, amphoteric and zwitterionic surfactants are "Surface Active Agents and Detergents" (Vol.
II by Schwartz, Perry and Berch). A variety of such surfactants have been described in US Pat. No. 3,929 issued to Laughlin et al. On Dec. 30, 1975.
, 678, col. 23, line 58 to col. 29, line 23. The surfactant is typically about 0.1% by weight of the bleaching composition, preferably about 1%.
More preferably from about 5% to about 99.9% by weight of the bleaching composition, preferably about 80%.
, More preferably about 35%, most preferably about 30%.

Anionic Surfactants-Anionic surfactants useful in the present invention are preferably linear alkyl benzene sulfonates, α-olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulphates, alkyl alkoxy sulphates, alkyl sulphonates. , Alkylalkoxycarboxylates, alkylalkoxylated sulphates, sarcosinates, taurinates and mixtures thereof. An effective amount, typically about 0.5 to about 90% by weight, preferably about 5 to about 60%, more preferably about 10 to about 30% of anionic detersive surfactant can be used in the present invention.

[0103]   Alkyl sulfate surfactants are important anionic surfactants for use here
Another type of agent. Combined with polyhydroxy fatty acid amide (see below)
Excellent overall cleaning ability when exposed, eg full range temperature, wash concentration
And in addition to exhibiting good fat / oil cleanability over the wash time
, Dissolution of alkyl sulphates, and improved formulation in liquid detergent formulations
These surfactants have the formula ROSO_ThreeA water soluble salt or acid of M,
Where R is preferably C₁₀-C₂₄Hydrocarbyl, preferably C₁₀-C_{Two 0} Alkyl or hydroxyalkyl having an alkyl moiety, more preferably C ₁₂ -C₁₈Alkyl or hydroxyalkyl, M is H or cation
, Alkali (Group IA) metal cations (eg sodium, potassium, lithium
), Substituted or unsubstituted ammonium cations, eg methyl-, dimethyl
-And trimethylammonium, and quaternary ammonium cations such as
Tramethylammonium and dimethylpiperidinium, and ethanolami
Alkanolamines such as amine, diethanolamine, triethanolamine
Cations derived from, and mixtures thereof. Typically C_{12-1 6} Alkyl chains are preferred at low wash temperatures (eg below about 50 ° C.)_{16-1 8} Alkyl chains are preferred at high wash temperatures (eg, above about 50 ° C).

Alkylalkoxylated sulphate surfactants are another category of useful anionic surfactants. These surfactants are typically of the formula RO
(A) a water-soluble salt or acid of _m SO ₃ M, wherein R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl group having a C ₁₀ -C ₂₄ alkyl moiety, preferably C ₁₂ -C ₂₀ alkyl Or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically about 0.5 to about 6, and more preferably about. 0.5 to about 3 and M is H or a cation, such as a metal cation (eg sodium, potassium, lithium, etc.), ammonium or a substituted ammonium cation. Alkyl ethoxylated sulphates and alkyl propoxylated sulphates are considered here. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. There are cations derived from, and mixtures thereof. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylates (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylates (2).
． 25) Sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylates (3.0)
Sulfates and C ₁₂ -C ₁₈ alkyl polyethoxylates (4.0) sulphates, where M is conveniently selected from sodium and potassium.
Surfactants useful herein may be prepared from natural or synthetic alcohol sources. Chain length represents the average hydrocarbon distribution including branches.

In addition, preferably the surfactant may be a mid-chain branched alkyl sulphate, a mid-chain branched alkyl alkoxylate or a mid-chain branched alkyl alkoxylate sulphate. These surfactants are 60 / of October 14, 1997
061,971, Agent Case No. 6881P; 6 of October 14, 1997
0 / 061,975, Agent Case No. 6882, 60 / 062,086, Oct. 14, 1997, Agent Case No. 6883P; October 14, 1997
Date 60 / 061,916, Agent Case No. 6884P; 60 / 061,970, October 14, 1997, Agent Case No. 6885P; 1997, 1
60 / 062,407 dated 14th January, Agent Case No. Further described in 6886P. Other suitable mid-chain branched surfactants are described in US Patent Application 60/032,
035 (Case No. 6401P), 60 / 031,845 (Case No. 6402)
P), 60 / 031,916 (Case No. 6403P), 60 / 031,917
(Case No. 6404P), 60 / 031,761 (Case No. 6405P),
60 / 031,762 (Case No. 6406P) and 60 / 031,844 (
Case No. 6409P). Mixtures of these branched surface-active agents with conventional linear surface-active agents are also suitable for use in the composition.

Another preferred anionic surfactant is the so-called modified alkylbenzene sulphonate surfactant, MLAS. Some suitable MLAS surfactants, methods of making them and exemplary compositions are described in co-pending US patent application 60/053.
, 319 (Case No. 6766P), 60/053, 318 (Case No. 676)
7P), 60 / 053,321 (Case No. 6768P), 60 / 053,20
9 (Case No. 6769P), 60/053, 328 (Case No. 6770P)
, 60 / 053,186 (Case No. 6771P), 60 / 053,437 (Case No. 6796P), 60 / 105,017 (Case No. 7303P) and 60 / 104,962 (Case No. 7304P). Has been done. Examples of suitable anionic surfactants are "Surface Active Agents and Detergent
s "(Vol. I and II by Schwartz, Perry and Berch).

Nonionic Detergent Surfactant-A suitable nonionic detergent surfactant is described in US of Laughlin et al., Issued Dec. 30, 1975, incorporated herein by reference.
It is generally disclosed in Japanese Patent 3,929,678 at column 13, line 14 to column 16, line 6. Illustrative non-limiting species of useful nonionic surfactants are amine oxides,
Alkyl ethoxylates, alkanoyl glucose amides, alkyl betaines,
There are sulfobetaines and their mixtures.

The amine oxide is a semipolar nonionic surfactant and is selected from the group consisting of one alkyl moiety having from about 10 to about 18 carbon atoms and an alkyl group and a hydroxyalkyl group having from about 1 to about 3 carbon atoms. A water-soluble amine oxide having two moieties: an alkyl moiety of about 10 to about 18 carbon atoms and about 1 to about 3 carbon atoms.
A water-soluble phosphine oxide having two moieties selected from the group consisting of an alkyl group and a hydroxyalkyl group; and an alkyl moiety having from about 10 to about 18 carbon atoms and an alkyl having from about 1 to about 3 carbon atoms and There is a water soluble sulfoxide having a moiety selected from the group consisting of hydroxyalkyl moieties.

Semipolar nonionic detergent surfactants include amine oxide surfactants having the formula:

[Chemical 50] Wherein R ³ is an alkyl, hydroxyalkyl, alkylphenyl group having from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene having from about 2 to about 3 carbon atoms, a hydroxyalkylene group or A mixture thereof;
x is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or a polyethylene oxide group having about 1 to about 3 ethylene oxide groups. The R ⁵ groups may be joined together, for example via an oxygen or nitrogen atom, to form a ring structure.

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

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

[0112]   Condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. fat
The alkyl chain of the group alcohol is linear or branched, primary or secondary, and is usually about 8
Has about 22 carbon atoms. Have an alkyl group of about 10 to about 20 carbon atoms
Alcohol and about 2 to about 18 moles of ethylene oxide per mole of alcohol
Particularly preferred are condensation products of Examples of commercially available nonionic surfactants of this type are:
, Tergitol, both sold by Union Carbide Corporation^R15-S-9 (C ₁₁ -C₁₅Condensation product of linear secondary alcohol and 9 mol of ethylene oxide), Te
rgitol^R24-L-6 NMW (C₁₂-C₁₄Primary alcohol and ethylene oxide 6 mol
With a narrow molecular weight distribution); sold by Shell Chemical Company
Neodol^R45-9 (C₁₄-C₁₅Of linear alcohol and 9 moles of ethylene oxide
Condensation product), Neodol^R23-6.5 (C₁₂-C_ThirteenLinear alcohol and ethyleneoxy
Condensation product with 6.5 mol), Neodol^R45-7 (C₁₄-C₁₅With straight chain alcohol
Condensation product with 7 mol of ethylene oxide), Neodol^R45-4 (C₁₄-C₁₅Straight chain
Condensation product of rucor and 4 moles of ethylene oxide); The Procter & Gamble Com
Kyro for sale from pany^REOB (C_Thirteen-C₁₅Alcohol and ethyleneoxy
(Condensation product with 9 moles). Other commercially available nonionic surfactants include Shell Ch
Dobanol 91-8 for sale from emical Co.^RAnd sold by Hoechst
Genapol UD-080^RThere is. Nonionic surfactants in this category are “alkyl”
It is commonly referred to as "ethoxylate".

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x where} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and Selected from the group consisting of :, wherein the alkyl group has about 10 to about 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2, t is 0 to about 10, preferably 0; x is about 1
． 3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7.
Is. Glycosyl is preferably derived from glucose. To produce these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a glucose source to give the glucoside (1
Bond to position) is formed. Additional glycosyl units may also be attached between their 1-position and the preceding glycosyl units at the 2, 3, 4 and / or 6-positions, preferably predominantly the 2-position.

[0114]   Fatty acid amide surfactant having the formula:

[Chemical 51] In the above formula, R ⁶ is an alkyl group having about 7 to about 21 (preferably about 9 to about 17) carbon atoms, and each R ⁷ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl. and _{- (C 2 H 4 O)} x H (x is from about 1 to about 3) is selected from the group consisting of.

Preferred amides are C ₈ -C ₂₀ ammonia amides, monoethanolamides,
Diethanolamide and isopropanolamide. Preferably, the nonionic surfactant, when present in the composition, in an effective amount,
More preferably from about 0.1 to about 20% by weight, even more preferably from about 0.1 to about 15.
%, And even more preferably about 0.5 to about 10%.

Polyhydroxy Fatty Acid Amide Surfactant- The detergent composition may also contain an effective amount of a polyhydroxy fatty acid amide surfactant. By "effective amount" is meant that the composition vendor can select the amount of polyhydroxy fatty acid amide to be incorporated into the composition in order to improve the cleaning performance of the detergent composition. Generally, at conventional levels, about 1% by weight polyhydroxy fatty acid amide is incorporated to enhance cleaning performance.

The detergent composition typically contains about 1% by weight of the polyhydroxy fatty acid amide surfactant, preferably about 3 to about 30% polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component consists of compounds of the following structural formulas:

[Chemical 52] In the above formula: R¹Is H, C₁-C_FourHydrocarbyl, 2-hydroxyethyl, 2-
Hydroxypropyl or mixtures thereof, preferably C₁-C_FourAlkyl, further
Is preferably C₁Or C_TwoAlkyl, most preferably C₁Alkyl (i.e.
Chill); R^TwoIs C₅-C₃₁Hydrocarbyl, preferably linear C₇-C_{1 9} Alkyl or alkenyl, more preferably straight chain C₉-C₁₇Alkyl or
Alkenyl, most preferably straight chain C₁₁-C₁₅Alkyl or alkenyl,
Or a mixture thereof; Z is a linear hydrocarbyl chain and a direct bond to the chain.
Having at least three hydroxyl groups
, Or its alkoxylated (ethoxylated or propoxylated) derivatives
is there. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably
Z is glycityl. Suitable reducing sugars include glucose, fructose, malt
There are glucose, lactose, galactose, mannose and xylose. Raw materials and
In addition to the individual sugars mentioned above, high dextrose corn syrup and high flour
Lactose corn syrup and high maltose corn syrup are also available. This
These corn syrups produce a mix of sugar components for Z. Other suitable ingredients
It should be understood that does not mean to exclude. Z is preferably -CH_Two-
(CHOH)_n-CH_TwoOH, -CH (CH_TwoOH)-(CHOH)_n-1-CH
_TwoOH, -CH_Two-(CHOH)_Two(CHOR ') (CHOH) -CH_TwoOh oh
And their alkoxylated derivatives, wherein n is 3-5.
R'is H or a cyclic or aliphatic monosaccharide. n is 4
Lysyl, especially -CH_Two-(CHOH)_Four-CH_TwoOH is most preferred.

R ¹ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl. R ² —CO—N <includes, for example, cocamide, stearamide, oleamide, lauramide, myristoamide, capricamide, palmitoamide, tallowamide and the like. Z is 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymultityl, 1-deoxylactytyl, 1-deoxygalactyl, 1-deoxymannityl, 1-deoxymaltotriotyl, etc. There is.

Methods for making polyhydroxy fatty acid amides are known in the art. Typically,
They react alkylamines with reducing sugars in a reductive amination reaction to give the corresponding N-
The alkyl polyhydroxyamine is formed, followed by N / N in the condensation / amidation step.
-Alkyl polyhydroxyamines may be prepared by reacting with fatty aliphatic esters or triglycerides to form N-alkyl, N-polyhydroxy fatty acid amide products. A method for producing a composition containing a polyhydroxy fatty acid amide is described in, for example, Thomas Hedley & Co., Ltd. published on February 18, 1959.
GB Patent Specification 809,060, ER, issued December 20, 1960
Wilson US Patent 2,965,576, Anth, issued March 8, 1955
ony M. Schwartz, US Patent 2,703,798 and Piggott, US Patent 1,985,424, issued December 25, 1934, each of which is incorporated herein by reference.

Diamines- Preferred liquid detergent compositions useful in the method of the present invention, such as light liquids, LDL compositions, have a ratio of one or more diamines, preferably anionic surfactant to diamine present. It may further contain an amount of diamine such that it is from about 40: 1 to about 2: 1. While the above diamines maintain the proper foaming level,
Improves the removal of fat and fat-like foods.

[0121]   Suitable diamines for use in the compositions of the present invention have the formula:

[Chemical 53] Each R in the above formula²⁰Independently hydrogen, C₁-C_FourLinear or branched alkyl, the following formula
Selected from the group consisting of alkyleneoxy having:                             ‐ (R^{twenty one}O)_yR^{twenty two} R in the above formula²¹Is C_Two-C_FourIn linear or branched alkylenes and mixtures thereof
Yes; R²²Is hydrogen, C₁-C_FourAlkyl and mixtures thereof; y is 1
To about 10; X is a unit selected from:   i) C_Three-C₁₀Straight chain alkylene, C_Three-C₁₀Branched alkylene, C_Three-C_{1 0} Cyclic alkylene, C_Three-C₁₀Branched alkylene, alkyle having the formula:
Oxyalkylene:                             ‐ (R^{twenty one}O)_yR^{twenty one}- R in the above formula²¹And y are as defined above;   ii) C_Three-C₁₀Straight chain, C_Three-C₁₀Branched straight chain, C_Three-C₁₀Cyclic, C_Three-C ₁₀ Branched cyclic alkylene, C₆-C₁₀Arylene (The above unit is the above diamine
Including one or more electron-donating or electron-withdrawing moieties that adjust the pKa of about 8 or more.
); And   iii) a mixture of (i) and (ii) However, the amine has a pKa of at least about 8.

Preferred diamines of the present invention are in the range of about 8 to about 11.5, preferably about 8
． 4 to about 11, more preferably each in the range of about 8.6 to about 10.75, p
It has K ₁ and pK ₂ . For purposes of the present invention, the term "pKa" refers to the terms "pK ₁ " and "pK ₂ " separately or inclusively. As used herein, the term pKa is used throughout the specification, as used by those of skill in the art. The pKa value is obtained from standard literature, for example, "Critical Stability Constants: Volume 2, Amines" by Smith and Martel,
Easily obtained from Plenum Press, NY and London, 1975.

As applied herein, the pKa value of diamines is about 0.
Specified by measuring with an aqueous solution having an ionic strength of 1 to about 0.5M. Since the pKa used here is an equilibrium constant that depends on temperature and ionic strength, the values reported in the literature without being measured by the above method may not completely match the values and ranges according to the present invention. . To eliminate ambiguity, relevant conditions and / or references used for the pKa of the invention can be found here or in "Critical Stabilit
y Constants: Volume 2, Amines ". One typical measurement method is potentiometric titration of acid with sodium hydroxide and" The Chemist's Rea ".
dy Reference Handbook "by Shugar and Dean, McGraw Hill, NY, 1990, pKa determination by a suitable method as described and cited.

Preferred diamines from the viewpoint of performance and supply are 1,3-bis (methylamino) cyclohexane and 1,3-diaminopropane (pK ₁ = 10.5; pK ₂ =
8.8), 1,6-diaminohexane (pK ₁ = 11; pK ₂ = 10), 1,3
-Diaminopentane (Dytek EP) (pK ₁ = 10.5; pK ₂ = 8.9) 2-Methyl-1,5-diaminopentane (Dytek A) (pK ₁ = 11.2; pK ₂ = 1)
0.0). Other preferred materials are the primary / primary diamines with alkylene spacers C ₄ -C _8. In general, primary diamines are preferred over secondary and tertiary diamines.

[0125]   The following are non-limiting examples of diamines suitable for use in the present invention. 1-N, N-dimethylamino-3-aminopropane having the formula:

[Chemical 54] 1,6-diaminohexane having the formula:

[Chemical 55] 1,3-diaminopropane having the formula:

[Chemical 56] 2-Methyl-1,5-diaminopentane having the formula:

[Chemical 57] 1,3-diaminopentane having the formula below, marketed under the trade name Dytec EP:

[Chemical 58] 1,3-diaminobutane having the formula:

[Chemical 59] A diamine having an alkyleneoxy backbone, having the formula: Jeffamine EDR148:

[Chemical 60] 3-Methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophoronediamine) having the formula:

[Chemical formula 61] 1,3-bis (methylamino) cyclohexane having the formula:

[Chemical formula 62]

Additional Detergent Ingredients The following are non-limiting examples of additional detergent ingredients (additive ingredients) useful in the bleaching compositions of the present invention, particularly laundry detergent compositions, which include builders, optical brighteners, Soil release polymer, dye transfer agent, dispersant, enzyme, foam control agent, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescent agent, fabric conditioner,
Hydrolyzable surfactants, preservatives, antioxidants, chelants, stabilizers, anti-shrinkage agents,
There are anti-wrinkle agents, fungicides, fungicides, corrosion inhibitors and mixtures thereof.

Builders- The bleaching compositions of the present invention preferably contain one or more detergent builders or builder systems. When present, the composition will typically comprise at least about 1% by weight builder, preferably about 5%, more preferably about 10% to about 80%.
It preferably contains about 50%, more preferably about 30% detergent builder. The level of builders will vary widely depending on the end use of the composition and its desired physical form. When present, the composition typically contains at least 1% builder. The formulation is typically about 5 to about 50% by weight, more typically about 5 to about 30%.
Including detergent builders. Granular formulations typically contain from about 10 to about 80% by weight, and more typically from about 15 to about 50% detergent builder. However, lower or higher level builders are not excluded.

Inorganic or P-containing detergent builders include polyphosphates (exemplified by tripolyphosphate, pyrophosphate and glassy polymer metaphosphate).
, Alkali metal, ammonium and alkanol ammonium salts of phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates and aluminosilicates, but are not limited thereto. However, non-phosphate builders are also needed in some areas. It is important to note that the composition is surprising even in the presence of so-called "weak" builders such as citrate (compared to phosphates), or in so-called "underbuilt" situations that can occur with zeolites or laminated silicate builders. It works well.

Examples of silicate builders are alkali metal silicates, especially 1.6: 1-3.
Those having a SiO ₂ : Na ₂ O ratio in the 2: 1 range, and laminated silicates such as the laminated sodium silicates described in Rieck US Pat. No. 4,664,839 issued May 12, 1987. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (generally "SKS-6" here).
Abbreviated). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is a laminated silicate in the form of δ-Na ₂ SiO ₅ . It is German DE-A-3,417,649 and D
It may be prepared by the method as described in EA-3,742,043. SKS
-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi _x O _{2x +} 1.yH ₂ O (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 also be used here. Various other laminated silicates by Hoechst include NaSKS-5, NaSK as α, β and γ forms.
There are S-7 and NaSKS-11. As described above, δ-Na ₂ SiO ₅ (Na
SKS-6) is most preferred here for use. Granule prescription for crispening (cri
Other silicates are also useful, such as magnesium silicates, which can function as spening agents, stabilizers for oxygen bleaching, and as components of the foam control system.

Examples of carbonate builders are alkaline earth and alkali metal carbonates as disclosed in German patent application 2,321,001 published Nov. 15, 1973.

Aluminosilicate builders are also useful in the present invention. Aluminosilicate builders are very important in most current commercial heavy duty granular detergent compositions and are also important builder ingredients in liquid detergent formulations. Some aluminosilicate builders have the empirical formula: [M _z (zAlO ₂ ) _y ] .xH ₂ O where z and y are at least integers of 6 and the molar ratio z to y is 1 0.0 to about 0
． 5 and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure, natural aluminosilicates or synthetically derived. A process for making aluminosilicate ion exchange materials is described in Krummel et al., US Pat. No. 3,985,6 issued Oct. 12, 1976.
69. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are commercially available under the names Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na _{12 [(AlO 2) 12 (SiO 2} ) 12 ] · xH ₂ O above wherein x is from about 20 to about 30, especially It is about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) may also be used here. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, various polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having a large number of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder is usually added to the composition in acid form, but it may be added in the form of a neutralized salt. When used in salt form,
Alkali metals such as sodium, potassium and lithium, or alkanol ammonium salts are preferred.

Among the polycarboxylate builders are various categories of useful materials. One important category of polycarboxylate builders is 1
Berg, US Pat. No. 3,128,287, issued April 7, 964, January 1972.
Etherpolyesters, including oxydisuccinate, as disclosed in Lamberti et al., US 3,635,830, issued March 18, and Lamberti, US 3,936,448, issued February 3, 1976. There is a carboxylate. 19
Bush et al., US Pat. No. 4,663,071, “TMS / T,” issued May 5, 1987.
See also “DS” builder. Suitable ether polycarboxylates include Rapko US Pat. No. 3,923,679 issued Jun. 2, 1975, Jun. 1, 1979.
Crutchfield et al., US 4,158,635, dated 9th October 1978.
US Pat. Nos. 4,120,874 and 197 of Crutchfield et al.
There are also cyclic compounds, especially cycloaliphatic compounds, as described in Crutchfield et al. US Pat. No. 4,102,903, published 25 July 8th.

Other useful cleaning builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,3.
Various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as 5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid, and mellitic acid, Succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3
, 5-tricarboxylic acid, carboxymethyloxysuccinic acid and their soluble salts, such as polycarboxylates.

Citrate builders, such as citric acid and its soluble salts (particularly the sodium salt), are particularly important polycarboxylates in heavy duty liquid detergent formulations due to their availability from renewable sources and their biodegradability. A rate builder. Citrate may be used in the granular composition, especially in combination with zeolite and / or laminated silicate builders. Oxydisuccinate is also particularly useful in such compositions and combinations.

The bleaching composition of the present invention includes Bush US 4 issued Jan. 28, 1986.
Also suitable are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US Pat. Useful succinic acid builders, C ₅ -C ₂₀ alkyl and alkenyl succinic acid, and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate. Lauryl succinate is the preferred builder of this group, and European patent application 8620069 published Nov. 5, 1986.
0.5 / 0,200,263.

Other suitable polycarboxylates are Cr, published Mar. 13, 1979.
utchfield et al., US 4,144,226 and Diehl US 3,308,067, issued March 7, 1967. Diehl US Patent 3,72
See also 3,322.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be incorporated into the composition, either alone or in combination with the aforementioned builders to provide additional builder activity, especially citrate and / or succinate builders. This should be considered by the person skilled in the art as such use of fatty acids usually results in reduced foamability.

Various alkali metal phosphates, such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, may be used in the formulation of bars used in phosphorus-based builders, especially in hand laundering operations. . Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (eg US Pat.
9,581,3,213,030,3,422,021,3,400,148 and 3,422,137).

Chelating Agents -The bleaching composition may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional substituted aromatic chelating agents and mixtures thereof, all as described below. Without being bound by theory, it is believed that the effects of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash liquor by forming soluble chelates. Examples of suitable chelating agents and levels of use are described in US Pat. Nos. 5,576,282 and 5,728,671. A preferred biodegradable chelator for use herein is ethylenediamine disuccinic acid (
"EDDS"), especially the [S, S] isomers as described by Hartman and Perkins in US Pat. No. 4,704,233 dated Nov. 3, 1987. The composition may also contain a water soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a useful cherant or cobuilder in combination with insoluble builders such as zeolites, layered silicates and the like. If utilized, these chelating agents are typically about 0.1% by weight of the bleaching composition to about 15% by weight of the bleaching composition, more preferably 3.0%.

Dye Transfer Inhibitors- The bleaching compositions of the present invention are intended to prevent dye transfer from one fabric with dissolved and suspended dyes to the other that occurs during fabric laundering and conditioning operations involving colored fabrics. In addition, one or more compounds and a dye transfer inhibitor may be contained. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Not done. Examples of such dye transfer inhibitors are disclosed in US Pat. Nos. 5,707,950 and 5,707,951.

[0143] Additional suitable dye transfer inhibitors include, but are not limited to, crosslinked polymers. Crosslinked polymers are polymers in which the backbone is internally interconnected to some extent, and these links may be of chemical or physical nature, possibly with active groups on the backbone or on the side chains. Crosslinked polymer is Journal of Polymer Science, volume 22, p
It is described in ages 1035-1039. In one aspect, the cross-linked polymer is made to form a three-dimensional rigid structure and is capable of entrapping the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer swells to capture the dye. Suitable cross-linked polymers are described in co-pending European patent application 94870213.9. The addition of such polymers also enhances the performance of the enzyme within the bleaching composition.

Dye transfer inhibitors have the ability to complex with or adsorb free dye washed off from colored fabrics before the dye has the opportunity to become attached to other objects in the wash liquor. is doing. When present in the bleaching composition, the dye transfer inhibitor is present in about 0.0001% by weight of the bleaching composition, more preferably about 0.01%, most preferably about 0.05% to about 10% of the bleaching composition. %, More preferably about 2%, most preferably about 1%.

Dispersants- The bleaching compositions of the present invention may also contain dispersants. Suitable water-soluble organic salts are homo- or copolymer acids or salts thereof, polycarboxylic acids containing at least two carboxyl groups separated from each other by not more than 2 carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are MW 2000-5000 polyacrylates and their copolymers with maleic anhydride, such copolymers being 1000-10.
It has a molecular weight of 10,000. In particular, copolymers of acrylates and methyl acrylates such as 480N having a molecular weight of 4000 can be added in the detergent compositions of the invention at levels of 0.5 to 20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptizer compound having a lime soap dispersancy (LSDP) of 8 or less, preferably 7 or less, and most preferably 6 or less. . The lime soap peptizer compound is preferably 0 to
Present at a level of 20% by weight. The numerical measure of the effectiveness of lime soap peptizer is the lime soap dispersion force (LSD).
HC Borghetti and CA Bergman, J. Am. Oil. Chem. Soc., Vol.
It is investigated using the lime soap dispersion test as described in the paper ume 27, pages 88-90 (1950). This lime soap dispersion test method is widely used by those skilled in the art, for example, the following review literature: WNLinfield, Surfactant Science Series, Volum.
e 7, page 3 ； WNLinfield, Tenside surf.det., Volume 27, pages 159-163 (1990)
MKNagarajan, WFMasler, Cosmetics and Toiletries, Volume 104, pages 71-
73 (1989). LSDP is 333 ppm CaCO ₃ (Ca:
Mg = 3: 2) It is the weight% ratio of dispersant to sodium oleate necessary to disperse the lime soap precipitate formed by 0.025 g of sodium oleate in 30 ml of water of comparable hardness.

Surfactants that have good lime soap peptizer capabilities include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulphates and ethoxylated alcohols. Exemplary surfactants having an LSDP of 8 or less for the purposes of the present invention include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C ₁₈ alkyl ethoxy sulphates with an average ethoxylation degree of 1 to 5, especially C with an ethoxylation degree of 3. ₁₂ -C ₁₅ alkyl ethoxysulfate surfactant (LSDP = 4), and trade name L from BASF GmbH
Average ethoxylation degree 1 sold by utensol A012 and Lutensol A030, respectively
There are 2 (LSDP = 6) or 30 C ₁₄ -C ₁₅ ethoxylated alcohols. Polymer Lime Soap Peptizers suitable for use here are Cosmetics and To
iletries, Volume 104, pages 71-73 (1989) MK Nagarajan, WF Masler
Described in a paper by 4- (N-octanoyl-6-aminohexanoyl) benzenesulfonate,
4- (N-nonanoyl-6-aminohexanoyl) benzenesulfonate, 4-
Hydrophobic bleaching such as (N-decanoyl-6-aminohexanoyl) benzene sulphonate and mixtures thereof; Nonanoyloxybenzene sulphonate with hydrophilic / hydrophobic bleaching formulations also used as lime soap peptizer compounds sell.

The enzyme -bleaching composition may contain, in addition to the amylase of the present invention, one or more detergent enzymes that exert cleaning performance and / or fabric care benefits. Such enzymes include proteases, amylases, cellulases and lipases.
They may be incorporated into the present non-aqueous liquid bleaching compositions in the form of suspensions, "marumes" or "globules". Another suitable type of enzyme is one that takes the form of a slurry of the enzyme in a nonionic surfactant, eg, under the trade name "SL".
There are enzymes sold by vo Nordisk or microencapsulated enzymes sold by Novo Nordisk under the trade name "LDP". Suitable enzymes and use levels are described in US Pat. No. 5,576,282.

Enzymes added to the composition in the form of conventional enzyme globules are particularly preferred here for use. Such globules are typically about 100-1000 microns in size, more preferably about 200-800 microns and are suspended in the non-aqueous liquid phase of the composition.
It has been found that globules in the compositions of the present invention exhibit particularly desirable enzyme stability for retention of enzyme activity over time, as compared to other enzyme forms. As such, compositions utilizing enzyme globules need not include conventional enzyme stabilizers, which often must be used when the enzyme is incorporated into an aqueous liquid detergent.

Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanase, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases. , Malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, known amylase, mannanase,
Xyroglucanase and mixtures thereof include, but are not limited to. A preferred combination is a bleaching composition with a cocktail of conventionally applied enzymes, such as proteases, lipases, cutinases and / or cellulases, together with the amylase of the invention. Examples of such suitable enzymes are described in US Pat. No. 5,576,282, 5,728,6.
71 and 5,707,950.

A suitable protease is subtilisin (subtilisin BPN and BPN ') obtained from specific strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity in the pH range of 8-12, have been developed and sold Danish Novo Industies A / S, the following "Novo" as ESPERASE ^R. This enzyme and similar enzymes are manufactured by Novo's GB1,243,
784. Other suitable proteases include Novo's ALCALASE ^R , DUR
AZYM ^R and SAVINASE ^R , and Gist-Brocades MAXATASE ^R , MAXACAL ^R , PROPERAS
There are E ^R and Maxapem ^R (protein engineered Maxacal). Proteolytic enzymes include modified bacterial serine proteases, such as those described in European Patent Application No. 87 / 303761.8 filed April 28, 1987 (especially pages 17, 24 and 98), European Patent Application No. 199,404 of Venegas published on October 29, 1986 concerning modified bacterial serine proteolytic enzymes hereinafter referred to as "Protease B" and hereinafter referred to as "Protease A" There is one described in. A variant of the Bacillus-derived alkaline serine protease, in which lysine was replaced by arginine at position 27, tyrosine was replaced by valine at position 104, serine was replaced by asparagine at position 123, and alanine was replaced by threonine at position 274. More preferred is what is referred to as Protease C ". Protease C is WO 91/066 published on May 16, 1991.
37 corresponding to EP 9015958: 4. Also included herein are genetically modified variants of Protease C. See also the high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 93 / 18140A. Enzymatic detergents containing proteases, one or more other enzymes and a reversible protease inhibitor are described in Novo WO92 / 03529A. If desired, proteases with reduced adsorptivity and increased hydrolyzability are described in Procter &Gamble's WO
Commercially available as described in 95/07791. Recombinant trypsin-like proteases suitable for detergents here are described in WO 94/25583 from Novo.

More specifically, the protease designated "Protease D" is a carbonyl hydrolase variant with an amino acid sequence which is not found in nature, 1995.
According to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95 / 10615 of Genencor International published on 20th of March, preferably +99, +101, +103, +104, +107, +123, +
27, +105, +109, +126, +128, +135, +156, +16
6, +195, +197, +204, +206, +210, +216, +217
, +218, +222, +260, +265 and / or +274 in combination with one or more amino acid residue positions corresponding to those selected from the group consisting of a plurality of amino acid residues at the position of the carbonyl hydrolase corresponding to position +76. Derived from the precursor carbonyl hydrolase by using different amino acids instead of groups. Protease described in patent applications EP251446 and WO91 / 06637, and WO91 / 02792, protease BLAP ^R also described, are suitable for the present invention. The proteolytic enzyme is 0.0001 to 2% by weight of the composition,
It is preferably incorporated into the bleaching composition of the present invention at a pure enzyme level of 0.001-0.2%, more preferably 0.005-0.1%.

Useful proteases are described by PCT Publication: The Procter & Gamble Company 1
WO95 / 30010, published on November 9, 995; The Procter & Gamb
WO95 / 30011 published by Le Company on November 9, 1995;
The WO published by The Procter & Gamble Company on November 9, 1995
95/29979.

Other particularly useful proteases are Bacillus amyloliquefaciens subtilisin 1,3,4,8,9,10,12,13,16,17,18,19,20,21.
, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58
, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89
, 97, 98, 99, 101, 102, 104, 106, 107, 109, 11
1, 114, 116, 117, 119, 121, 123, 126, 128, 13
0, 131, 133, 134, 137, 140, 141, 142, 146, 14
7, 158, 159, 160, 166, 167, 170, 173, 174, 17
7, 181, 182, 183, 184, 185, 188, 192, 194, 19
8, 203, 204, 205, 206, 209, 210, 211, 212, 21
3, 214, 215, 216, 217, 218, 222, 224, 227, 22
8, 230, 232, 236, 237, 238, 240, 242, 243, 24
4, 245, 246, 247, 248, 249, 251, 252, 253, 25
4, 255, 256, 257, 258, 259, 260, 261, 262, 26
Position 103 of Bacillus amyloliquefaciens subtilisin along with substitution of amino acid residues with other natural amino acid residues at one or more amino acid residue positions corresponding to positions 3, 265, 268, 269, 270, 271, 272, 274 and 275. Is a polysubstituted protease variant which has been substituted with another natural amino acid residue at the amino acid residue position corresponding to
When an amino acid residue is substituted at the position corresponding to position, Bacillus amyloliqu
efaciens subtilisin 27, 99, 101, 104, 107, 109, 123
, 128, 166, 204, 206, 210, 216, 217, 218, 222
There are also amino acid residue substitutions at one or more amino acid residue positions other than the amino acid residue positions corresponding to positions 260, 265 or 274; and / or all The Pr
Oct. & Gamble Company's PCT publication application No. WO99 / 20727, WO9
Bacillus, as described in 9/20726 and WO 99/20723.
There are also polysubstituted protease variants that have been substituted with amino acid residues by another natural amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of amyloliquefaciens subtilisin.

More preferably, the protease variant has a substitution combination selected from the group consisting of:

[Chemical formula 63] Even more preferably, the protease variant has a substitution combination selected from the group consisting of:

[Chemical 64] Most preferably, the protease variant has the substitution combination: 101/103/104/1.
59/232/236/245/248/252, preferably 101G / 103
A / 104I / 159D / 232V / 236H / 245R / 248D / 252K
I am receiving

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimum pH of 5-9.5. A suitable cellulase is Barbes
disclosed in US Pat. No. 4,435,307 to goard et al., where Humicola in
A fungal cellulase produced from solens is disclosed. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,275 and DE.
-OS-2,247,832. Examples of such cellulases include Humicola insolens (Humicola grisea var.
rmoidea), in particular a cellulase produced by the Humicola strain DSM1800.

Other suitable cellulases have a molecular weight of about 50 kDa and an isoelectric point of 5.5,
A cellulase derived from Humicola insolens containing 415 amino acids; a ~ 43 kD endoglucanase derived from Humicola insolens DSM1800 showing cellulase activity. A preferred endoglucanase component is PCT patent application WO 9
It has the amino acid sequence disclosed in 1/17243. Trichoderma long described in WO 94/21801 of Genencor published on September 29, 1994
EGIII cellulase from ibrachiatum is also a suitable cellulase. A particularly suitable cellulase is a cellulase having a color care effect. An example of such a cellulase is the European patent application 91202879. filed Nov. 6, 1991.
2 (Novo Nordisk A / S). Carezyme and Celluz
yme (Novo Nordisk A / S) is especially useful. See also WO 91/17243.

Peroxidase enzymes are known in the art and include haloperoxidases such as horseradish peroxidase, ligninase, chloro and bromoperoxidase. Bleaching compositions containing peroxidase are described, for example, in US Patents 5,576,282, 5,728,671 and 5,707,9.
50, PCT International Applications WO89 / 099813, WO89 / 09813, 199
It is disclosed in European patent application EP 91202882.6 filed on November 6, 1st year and EP968700133.8 filed on February 20, 1996. The laccase enzyme is also suitable.

Preferred enhancers are substituted phenothiazines and phenoxazines, 10
-Phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-
Carboxylic acid (EPC), 10-phenoxazine propionic acid (POP), 10-
Methylphenoxazine (described in WO94 / 12621), substituted syringates (
C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate is the preferred hydrogen peroxide source. The peroxidases described above are commonly incorporated into bleaching compositions at active enzyme levels of 0.0001 to 2% by weight of the bleaching composition.

Another preferred enzyme that may be included in the bleaching composition of the present invention is lipase. Suitable lipase enzymes for detergents include Pseu disclosed in British Patent 1,372,034.
Some are produced by microorganisms of the genus Pseudomonas, such as domonas stutzeri ATCC 19.154. Suitable lipases include the microbial Pseudomonas fluorescent
Some of them show a positive immune cross-reactivity with the lipase antibody produced by IAM1057. This lipase is Ama from Nagoya, Japan under the trade name Lipase P "Amano".
It is commercially available from no Pharmaceutical Co. Ltd. and is hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Chromobacter viscosum, for example, lipase from Chromobacter viscosum var.lipolyticum NRRLB 3673 from Toyo Brewery of Takata, Japan,
Amano-CES; Chromobacter viscosum lipase from USBiochemical Corp. of USA and Disoyynth Co. of the Netherlands; lipase from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 LIPASE ^R and LIPOMAX ^R (Gist-Brocades), and LIPOLASE ^R and LIPOLASE ULTRA ^R (Novo), which are very effective when combined in the composition of the invention. I found out.

Also suitable is a special kind of lipase, namely cutinase [EC 3.1.1.50], which is considered as a lipase which does not require surface activity. The addition of cutinase to bleaching compositions is described, for example, in WO 88/09367 (Genencor). The lipase and / or cutinase is 0.0001 to 2% by weight of the bleaching composition.
Is normally incorporated into bleaching compositions at active enzyme levels of.

Known amylases (α and / or β) may also be included for the removal of carbohydrate-based soils. WO 9 of Novo Nordisk A / S, published February 3, 1994
4/02597 describes a cleaning composition incorporating a mutant amylase. Genencor's WO94 / 183, published August 18, 1994
14 and WO95 / of Novo Nordisk A / S, published April 20, 1995.
See also 10603. Other amylases known for use in bleaching compositions include both α- and β-amylases. α-Amylase is known in the art and is described in US Patent 5,003,257, EP252,666, WO91 / 00353, FR2.
676,456, EP285,123, EP525,610, EP368,34
1 and British Patent Specification No. 1,296,839 (Novo). Another suitable amylase is WO94 / published August 18, 1994.
18314, Genencor's WO96 / 052, published February 22, 1996.
95. A stability-enhancing amylase including PURAFACT OX AM ^R described in 95, and 95
It is an amylase variant of Novo Nordisk A / S disclosed in WO 95/10603 published in April, 2010.

Examples of commercial α-amylase products are TERMAMYL ^R , BAN ^R , FUNGAMYL ^R and DURAMYL ^R , all commercially available from Novo Nordisk A / S Denmark. WO95 / 263
97 is at least 25% higher than that of TERMAMYL ^R at a temperature range of 25-55 ° C and a pH value of 8-10, as measured by another suitable amylase: Phadebas ^R α-amylase activity assay. Α-amylase characterized by having Other amylolytic enzymes having improved properties in terms of activity level and combination of thermostability and high activity level are described in WO95 /
35382.

The compositions of the present invention may also include a mannanase enzyme. Preferably, the mannanase is three mannan degrading enzymes: EC3.2.1.25: β-mannosidase, EC3.2.1.78.
: Endo-1,4-β-mannosidase (hereinafter referred to as “mannanase”),
EC 3.2.1.100: selected from the group consisting of 1,4-β-mannobiosidase and mixtures thereof (IUPAC Classification-Enzyme nomenclature, 1992, I
SBN 0-12-227165-3, Academic Press).

More specifically, the treatment composition of the present invention comprises β-1,4-mannosidase (EC 3.2.1.78), referred to as mannanase when mannanase is present. The term "mannanase" or "galactomannanase" is publicly referred to as mannan endo-1,4-β-mannosidase, which has the alternative names β-mannanase and endo-1,4-mannanase, : 1,4 in mannan, galactomannan, glucomannan and galactoglucomannan
-Represents a mannanase enzyme, defined according to the art as catalyzing the random hydrolysis of -β-D-mannoside bonds.

In particular, mannanase (EC 3.2.1.78) belongs to the group of polysaccharases that degrade mannan, which is capable of cleaving polyose chains bearing mannose units,
That is, it represents an enzyme capable of cleaving the glycosidic bond of mannan, glucomannan, galactomannan and galactoglucomannan. Mannan is β-1,4-
Glucomannan is a polysaccharide having a main chain composed of linked mannose, and glucomannan is a polysaccharide having β-1,4-linked mannose and glucose alternating in the main chain or more or less regularly. Mannan is α
Mannan and glucomannan with -1,6-linked galactose side chains. These compounds may be acetylated.

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

Mannanases have been identified in several Bacillus organisms. For example, Talbot e
t al., Appl. Environ. Microbiol., Vol. 56, No. 11, pp. 3505-3510 (1990), 162.
Bacillus in dimeric form with a molecular weight of kDa and an optimum pH of 5.5-7.5.
Describes β-mannanase from us stearothermophilus. Mendoza
et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994), 38.
A β-mannanase from Bacillus subtilis having a molecular weight of kDa, optimal activity at pH 5.0 and 55 ° C. and a pl of 4.8 is described. JP
-03047076 has a molecular weight of 373 kDa as measured by gel filtration, 8 to
Β-from Bacillus sp. With an optimum pH of 10 and a pl of 5.3-5.4
A mannanase is disclosed. JP-63056289 describes the production of alkaline, thermostable β-mannanase, which hydrolyzes, for example, β-1,4-D-mannopyranoside bonds of mannan to produce manno-oligosaccharides. JP-63063774 relates to a Bacillus microorganism FERM P-8856 that produces β-mannanase and β-mannosidase at alkaline pH. JP-08051975 discloses alkaline β-mannanase from alkalophilic Bacillus sp. AM-001. A purified mannanase from Bacillus amyloliquefaciens useful for bleaching pulp and paper, and a method for its production are disclosed in WO 97/11164. WO91 / 18974 is an extreme p
Hemicellulases such as glucanases, xylanases or mannanases active at H and temperature are described. WO94 / 25576 Aspergillus showing mannanase activity useful for the degradation or modification of plant or algal cell wall material.
An enzyme from aculeatus CBS 101.43 is disclosed. WO93 / 24622
Disclose a mannanase isolated from Trichoderma reseei useful for bleaching lignocellulosic pulp. A hemicellulase capable of degrading mannan-containing hemicellulose is described in WO91 / 18974, and a purified mannanase derived from Bacillus amyloliquefaciens is WO9.
7/11164.

Preferably, the mannanase enzyme is an alkaline mannanase as described below, more preferably a mannanase derived from a bacterial source. In particular, the laundry detergent composition of the invention comprises a mannanase from Bacillus agaradhaerens strain NICMB 40482; Bacillus su
btilis strain 168, a gene yght-derived mannanase; an alkaline mannanase selected from Bacillus sp. I633-derived mannanase and / or Bacillus sp. AAI12-derived mannanase. The most preferred mannanase for inclusion in the detergent composition of the present invention is co-pending Danish Patent Application PA 1998.
The mannanase enzyme from Bacillus sp. I633 as described in 01340. The term "alkaline mannanase enzyme" refers to 7-12, preferably 7.5.
It is meant to include an enzyme having an enzyme activity of at least 10%, preferably at least 25%, and more preferably at least 40% of its maximum activity at a predetermined pH of ˜10.5.

Alkaline mannanases from Bacillus agaradhaerens NICMB 40482 have been described in co-pending US patent application 09 / 111,256. More specifically, this mannanase is: i) a polypeptide produced by Bacillus agaradhaerens NICMB 40482 ii) a SEQ ID as shown in US patent application 09 / 111,256
A polypeptide comprising an amino acid sequence as set forth at positions 32-343 of NO: 2, or iii) at least 70% homologous to the above polypeptide or substitution of one or several amino acids , A derivative of the polypeptide defined in i) or ii), which has been derived from said polypeptide by deletion or addition or which is immunoreactive with a polyclonal antibody against said polypeptide in purified form.

Further: (a) SEQ ID as shown in US patent application 09 / 111,256
A polynucleotide molecule encoding a polypeptide having mannanase activity comprising a sequence of nucleotides as set forth in NO: 1 nucleotide 97-nucleotide 1029; (b) a species homolog of (a); (c) ) SEQ ID as shown in US patent application 09 / 111,256
A polynucleotide molecule encoding a polypeptide having mannanase activity, which is at least 70% identical to the amino acid sequence of amino acid residue 32-amino acid residue 343 at NO: 2; (d) (a), (b) ) Or (c) a complementary molecule; and (e) a corresponding mannanase activity selected from the group consisting of degenerate nucleotide sequences of (a), (b), (c) or (d). It also relates to an isolated polypeptide.

Polynucleotide molecule (DNA sequence) encoding the above mannanase
The plasmid pSJ1678 containing E. coli was integrated into a strain of Escherichia coli and transformed into Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Maschero.
der Web 1b, D-38124 Braunschweig, Federal Republic of Germany, deposited by the present inventors under the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Patent Applications, on May 18, 1998 under Deposit No. DSM12180. It was

A second more preferred enzyme is the mannanase from Bacillus subtilis strain 168 described in co-pending US patent application 09 / 095,163. More particularly, this mannanase is: i) encoded by the coding portion of the DNA sequence set forth in SEQ ID NO: 5 shown in US patent application 09 / 095,163 or an analogue of that sequence, and / or Or ii) a polypeptide comprising an amino acid sequence as set forth in SEQ ID NO: 6 shown in US patent application 09 / 095,163, or iii) with at least 70% homology to the above polypeptide Has been derived from said polypeptide by the substitution, deletion or addition of one or several amino acids,
Alternatively, it is an analog of the polypeptide defined in ii), which is immunoreactive with a polyclonal antibody against the above-mentioned polypeptide in a purified form.

Further: (a) SEQ ID as shown in US patent application 09 / 095,163
A polynucleotide molecule encoding a polypeptide having mannanase activity, comprising a sequence of nucleotides as set forth in NO: 5; (b) a seed homolog of (a); (c) US Patent Application 09 / 095,163 as shown in SEQ ID
A polynucleotide molecule encoding a polypeptide having mannanase activity, which is at least 70% identical to the amino acid sequence of NO: 6; and a molecule complementary to (d) (a), (b) or (c). And (e) a corresponding isolated polypeptide having mannanase activity selected from the group consisting of the degenerate nucleotide sequence of (a), (b), (c) or (d).

A third more preferred mannanase is co-pending Danish patent application PA199.
8 01340. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. I633 ii) a SEQ as shown in Danish Application PA 1998 01340
A polypeptide comprising an amino acid sequence as set forth at positions 33-340 of ID NO: 2, or iii) one or several amino acid substitutions that are at least 65% homologous to said polypeptide, An analog of a polypeptide as defined in i) or ii), which is derived from said polypeptide by deletion or addition or is immunoreactive with a polyclonal antibody against said polypeptide in purified form.

Further: (a) SEQ as shown in Danish Application PA 1998 01340
A polynucleotide molecule encoding a polypeptide having mannanase activity, comprising a sequence of nucleotides as set forth in nucleotides 317 to 1243 of ID NO: 1; (b) a species homolog of (a); (C) SEQ as shown in Danish Application PA 1998 01340
A polynucleotide molecule encoding a polypeptide having mannanase activity, which is at least 65% identical to the amino acid sequence of amino acid residue 33-amino acid residue 340 at ID NO: 2; (d) (a), ( b) or (c) complementary molecule; and (e) a corresponding isolated polynucleotide molecule selected from the group consisting of degenerate nucleotide sequences of (a), (b), (c) or (d). Also related to.

The plasmid pBXM3, which comprises the polynucleotide molecule (DNA sequence) coding for the mannanase of the present invention, has been integrated into a strain of Escherichia coli to give Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode.
r Web 1b, D-38124 Braunschweig, Federal Republic of Germany, in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Patent Applications, May 1998.
It was deposited by the present inventors on March 29th under the deposit number DSM12197.

A fourth more preferred mannanase is co-pending Danish Patent Application PA199.
No. 8 01341. More particularly, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI12 ii) a SEQ as shown in Danish Application PA 1998 01341
A polypeptide comprising an amino acid sequence as set forth at positions 25-362 of ID NO: 2, or iii) one or several amino acid substitutions that are at least 65% homologous to the above polypeptide, An analog of a polypeptide as defined in i) or ii), which is derived from said polypeptide by deletion or addition or is immunoreactive with a polyclonal antibody against said polypeptide in purified form.

Further: (a) SEQ as shown in Danish Application PA 1998 01341
A polynucleotide molecule encoding a polypeptide having mannanase activity, comprising a sequence of nucleotides as set forth in nucleotides 225 to 1236 of ID NO: 1; (b) a species homolog of (a); (C) SEQ as shown in Danish Application PA 1998 01341
A polynucleotide molecule encoding a polypeptide having mannanase activity, which is at least 65% identical to the amino acid sequence of amino acid residue 25-amino acid residue 362 at ID NO: 2; (d) (a), ( b) or (c) complementary molecule; and (e) a corresponding isolated polynucleotide molecule selected from the group consisting of degenerate nucleotide sequences of (a), (b), (c) or (d). Also related to.

The plasmid pBXM1 comprising the polynucleotide molecule (DNA sequence) coding for the mannanase of the present invention was integrated into a strain of Escherichia coli and transformed into Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode.
r Web 1b, D-38124 Braunschweig, Federal Republic of Germany in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Patent Applications, 1998
It was deposited by the present inventors under the deposit number DSM 12433 on 7th October.

The mannanase, when present, is preferably 0.0001-2% by weight of the composition, more preferably 0.0005-0.1%, most preferably 0.001-0.
． A pure enzyme level of 02% is incorporated into the treatment composition of the present invention.

The compositions of the present invention may also include a xyloglucanase enzyme. The xyloglucanase suitable for the purposes of the present invention is preferably a xyloglucan-specific endonuclease at a level of about 0.001 to about 1% by weight of the composition, more preferably about 0.01 to about 0.5%. It is an enzyme that exhibits glucanase activity. The term "endoglucanase activity" as used herein refers to 1,4-β-present in cellulosic materials such as cellulose, cellulose derivatives, lichenin, β-D-glucan or xyloglucan.
By the ability of an enzyme to hydrolyze D-glycosidic bonds. Endoglucanase activity was determined according to methods known in the art, examples of which are described in WO 94/14953 and below. 1 unit of endoglucanase activity (eg CMC
U, AVIU, XGU or BGU) is defined as the production of 1 μmol reducing sugar / min from a glucan substrate, such as CMC (CMCU), acid swelling Avicel.
l (AVIU), xyloglucan (XGU) or cereal β-glucan (BGU)
Is. Reducing sugars are examined as described in WO 94/14953 and below. The specific activity of endoglucanase on the substrate is defined as units / mg protein.

Enzymes exhibiting XGU endoglucanase activity as maximal activity (hereinafter “xyloglucan specific”) are suitable, the enzymes being: i) comprising at least one of the following partial sequences: Or the DNA sequence contained therein:

[Chemical 65] Alternatively, Aspergillus aculeatu encoded by a sequence homologous to a xyloglucan-specific polypeptide having endoglucanase activity and encoded by a DNA sequence defined in ii) i).
It is immunoreactive with an antibody to the highly purified endoglucanase from s CBS 101.43 and is specific to xyloglucan.

More specifically, the term “xyloglucan-specific” as used herein means that the endoglucanase enzyme exhibits its maximal endoglucanase activity on a xyloglucan substrate, other cellulose-containing substrates such as Carboxymethyl cellulose, cellulose or other glucans are meant to exhibit preferably less than 75% activity, more preferably less than 50% activity, most preferably less than about 25% activity. Preferably, the specificity of endoglucanase for xyloglucan is
It is further defined as the relative activity obtained as a result of incubation of the enzyme with the xyloglucan and other substrates tested and as the release of reducing sugars under optimal conditions. For example, its specificity is xyloglucan to β-glucan activity (XGU / BGU), xyloglucan to carboxymethylcellulose activity (XG / BGU).
U / CMCU), or xyloglucan vs. acid swollen Avicell activity (XGU / AVI)
U), which is preferably about 50 or more, eg 75, 90 or 1
00.

As used herein, the term "derived from" refers to an endoglucanase produced by strain CBS101.43 as well as a DNA sequence isolated from strain CBS101.43, It also relates to an endoglucanase produced in the transformed host organism. As used herein, the term “homologue” (eg, presoaked in 5 × SSC, 5 × SSC, 5 × Denhardt's solution and 50 μg of denatured sonicated calf thymus DNA at −40 ° C. Prehybridize over time, then hybridize in the same solution supplemented with 50 μCi ³² P-dCTP labeled probe for 18 hours at −40 ° C., then in 2 × SSC, 0.2% SDS at 40 ° C. for 30 minutes. Wash 3 times)
Figure 2 shows a polypeptide encoded by a DNA that hybridizes with a probe similar to the DNA encoding for an endoglucanase enzyme specific for xyloglucan under certain conditions. More specifically, the term includes any of the above sequences encoding for an endoglucanase specific for xyloglucan and at least 75%, at least 80%, at least 85%, at least 90% or more of said sequence. Relates to DNA sequences which are at least 70% homologous, including at least 95%. The term refers to a host into which a DNA construct containing any of the above DNA sequences has been introduced without modification of any of the above DNA sequences, for example, without producing an amino acid sequence different from the polypeptide encoded by that sequence. Nucleotide substitutions corresponding to the codon usage of the organism, or different amino acid sequences, and thus possibly different amino acid sequences which may give rise to endoglucanase variants with different properties than the natural enzyme, and thus possibly different protein structures. The meaning includes substitution. Other examples of possible modifications include insertion of one or more nucleotides into the sequence, addition of one or more nucleotides to the end of the sequence, or 1 at or at the end of the sequence.
It is the deletion of the above nucleotides.

Xyloglucan-specific endoglucanases useful in the present invention include 50 or more, such as 75, 90 or 100 XGU / BGU, XGU (as described above).
/ CMU and / or XGU / AVIU ratio. Furthermore, the xyloglucan-specific endoglucanase is preferably substantially devoid of activity against β-glucan when the activity against xyloglucan is 100%, and / or carboxymethylcellulose and / or
It exhibits an activity against Avicells of at most 25%, eg at most 10% or about 5%.
In addition, the xyloglucan-specific endoglucanases of the invention are preferably substantially devoid of transferase activity, ie the activity observed with most endoglucanases specific to plant-sourced xyloglucan.

Xyloglucan-specific endoglucanases are also obtained from the fungal species A. aculeatus, as described in WO94 / 14953. Microbial endoglucanases specific for xyloglucan have also been described in WO94 / 14953.
An endoglucanase specific for xyloglucan from plants has also been described,
These enzymes have transferase activity and should therefore be regarded as inferior to xyloglucan-specific microbial endoglucanases whenever exhaustive degradation of xyloglucan is desired. An additional advantage of microbial enzymes is that they are generally produced in microbial hosts in higher amounts than enzymes of other origin.

Xyloglucanase, when present, preferably comprises 0.0001 of the composition.
˜2% by weight, more preferably 0.0005 to 0.1%, most preferably 0.00
Pure enzyme levels of 1-0.02% are incorporated into the treatment compositions of the present invention.

The above enzymes can be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. Purified or unpurified forms of these enzymes can be used. Variants of natural enzymes are also included in the definition. Variants are, for example, proteins of natural enzymes and / or
Alternatively, it is obtained by genetic engineering, chemical and / or physical modification. Expression of the enzyme by the host organism into which the genetic material responsible for producing the enzyme has been cloned is also conventional. The above enzymes are usually incorporated into bleaching compositions at active enzyme levels of 0.0001 to 2% by weight of the bleaching composition. Enzymes can be added as individual single components (globules containing one enzyme, granules, stabilizing liquids, etc.) or as a mixture of two or more enzymes (eg cogranulates). Other suitable detergent ingredients that may be added are enzyme oxidation scavengers. An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine.

Various enzyme materials and their means of incorporation into synthetic bleaching compositions are also described by Genencor I.
nternational WO 93/07263 and WO 93/07260, Novo WO
89/08694 and McCarty et al., US 5,553, dated January 5, 1971.
139. The enzyme is described in US 4, US Pat.
101,457 and Hughes, US 4,507,219 dated 26 March 1985.
But it is further disclosed. Enzymatic substances useful in liquid detergent formulations and their incorporation in such formulations is described in Hora et al., US 4,261, April 14, 1981.
868.

Enzyme Stabilizers- Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization technology is described in US Pat. No. 3,600,319, G. Gedge et al., August 17, 1971.
edge et al EP 199,405 and Venegas EP 2 dated 29 October 1986.
00,586. The enzyme stabilization system is also, for example, US 3,5.
19, 570. A useful Bacillus sp. AC13 producing protease, xylanase and cellulase is described in WO9401532 from Novo. The enzyme used herein can be stabilized in the final composition by the presence of a water-soluble source of calcium and / or magnesium ions, which provides such ions to the enzyme. Suitable enzyme stabilizers and levels of use are described in US Pat.
6, 282.

Other Detergent Ingredients -The bleaching composition may be one or more of the following: polymer dispersants, soil stain removal / redeposition inhibitors, brighteners, suds suppressors, dyes, perfumes, structural elasticizers. , Fabric softeners, carriers, hydrotropes, processing aids and / or pigments may optionally be included. Suitable examples and use levels for such other detergent ingredients are found in US Pat.
, 576, 282.

Methods of Cleaning-In addition to the methods described herein for cleaning body parts by personal cleansing of fabrics, dishes and other hard surfaces, the present invention provides for soiled or spotted fabrics. And the above-mentioned stains and / or stains are directly contacted with the bleaching composition in a highly concentrated form as described above before washing such fabrics with a conventional washing aqueous solution. Consists of Preferably, the bleaching composition is left in contact with the stain / stain for about 30 seconds to 24 hours before routinely washing the pretreated stain / stain substrate. More preferably, the pretreatment time is about 1-180 minutes.

The following examples are meant to illustrate the compositions of the invention and are not necessarily meant to limit or limit the scope of the invention. In the examples below, some abbreviations known to those of skill in the art are used in accordance with the disclosure provided herein.

[0195] Production of Synthesis Example Example I 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate (7): Step 1: Dimethyl benzyl cyanide (2) Production: two dropping Dimethyl sulfoxide (200 ml) into a 1 L 3-neck round bottom flask equipped with a funnel, side arm adapter, ammonium hydroxide trap, reflux condenser, mechanical stirrer, thermometer and adapter, and fritted diffuser.
And cool in an ice bath. Diffuse methyl chloride gas into dimethyl sulfoxide with stirring. After 15 minutes, sodium hydroxide (50% aqueous solution, 32.9
g) and benzyl cyanide ( 1 , 11.7 g, 1 eq) are added simultaneously as separate solutions from two dropping funnels at a rate that does not raise the temperature above 35 ° C. After the addition of sodium hydroxide and benzyl cyanide is complete, the reaction is stirred at room temperature so that methyl chloride continues to diffuse into the solution. After 1 hour, the methyl chloride flow was stopped (total 38.8 g, 3.8 eq) and the reaction was extracted with toluene (3 x 100 ml) and ether (100 ml). The combined organic layers are washed with saturated sodium bicarbonate solution (2 × 100 ml), brine (100 ml), dried over sodium sulphate and concentrated to give 2 . The manufacturing method is represented by the following reaction:

[Chemical formula 66]

Step 2 : Preparation of 1-amino-2,2-dimethyl-2-phenylethane ( 3 ): anhydrous to a 250 ml three neck round bottom flask equipped with pressure equalizing dropping funnel, argon gas inlet and reflux condenser. Add diethyl ether (100 ml) and cool in an ice bath. Lithium aluminum hydride (3.68 g, 2 eq) is slowly added to the reaction mixture. After the dropping was completed, dimethylbenzyl cyanide ( 2 , 7.00 g, 1 equivalent)
Is added dropwise over 15 minutes. The reaction is allowed to warm slowly to room temperature overnight with stirring. Water (7.0 ml) is added over 15 minutes, followed by sodium hydroxide (15% aqueous solution, 7.0 ml). The mixture was stirred for about 1 hour and then water (21.
0 ml) is added. The reaction is diluted with diethyl ether (100 ml) and vacuum filtered. Wash the filter cake with diethyl ether (8 x 50 ml),
The combined organic layers are dried over magnesium sulfate and concentrated under vacuum to give 3 . The manufacturing method is represented by the following reaction:

[Chemical formula 67]

Step 3 : Preparation of 4,4-dimethyl-3,4-dihydroisoquinoline ( 4 ): 1-amino-2,2-dimethyl-2-phenylethane (4.15 g, 1 eq)
And a formic acid (6.65 g, 3.5 eq.) In a 50 ml round bottom flask equipped with a magnetic stir bar and distillation apparatus were stirred at 100 ° C. for 1 hour and then further formic acid (2
ml, 0.9 eq) is added. After stirring for another hour, the mixture is heated to 200 ° C. and vacuum is applied. After removing unreacted formic acid and water, the resulting oily N-formyl-β, β-dimethyl-β-phenethylamine is cooled to room temperature. 10 with side arm adapter, dropping funnel and mechanical stirrer
To a 0 ml round bottom flask, polysulfuric acid (29.7 g) and phosphorus pentoxide (4.74 g).
). The mixture is stirred and heated at 180 ° C. for about 1 hour to give about 1
Cool to 50 ° C. N-formyl-β, β-dimethyl-β-phenethylamine (5.31 g, 1 eq) is melted and added as a stream to the acid mixture. Heat the reaction to 180 ° C. and stir overnight. The reaction mixture is cooled to about 60 ° C. and slowly mixed with ice water (250 ml). The diluted reaction mixture is washed with diethyl ether (2 x 100 ml). The aqueous solution is stirred while adding a saturated aqueous solution of potassium hydroxide and cooled in an acetone / dry ice bath. When the pH of the mixture reaches 9, the mixture is extracted with diethyl ether (4 x 100 ml). The organic layer is washed with pH 10 buffer (200 ml), dried over magnesium sulphate and concentrated under vacuum to give 4 . The manufacturing method is represented by the following reaction:

[Chemical 68]

Step 4 : Preparation of 1,2-decanediol cyclic sulphate ( 6 ): To a 500 ml three neck round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel and reflux condenser, 1,2-decanediol ( 5). , 8.72 g, 50.0 mmol) and 50 ml of carbon tetrachloride. After dissolution of 1,2-decanediol, thionyl chloride (5.5 ml, 75 mmol) is added dropwise at room temperature, and the reaction solution is heated to 60 ° C.
After 2 hours, cool the reaction with an ice bath. Water (50 ml) and acetonitrile (
75 ml) is added. Hydrated ruthenium chloride (0.131 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) are added and the reaction mixture is stirred at room temperature for 1 hour. The mixture was extracted with diethyl ether (4 x 175 ml) and the organic layer was washed with water (5 x 100 ml), saturated sodium bicarbonate (3 x 100 ml), brine (2 x 100 ml) and filtered through Celite / silica gel. , Dried over magnesium sulfate. The clear liquid is concentrated to give 6 as a clear oil. The manufacturing method is represented by the following reaction:

[Chemical 69]

Step 5 : Preparation of 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate ( 7 ): 4,4-dimethyl-into a 100 ml round bottom flask equipped with a magnetic stir bar. 3,4-Dihydroisoquinoline (2.45 g, 15.4 mmol) and acetonitrile (15
． 2 ml). To this solution is added 1,2-decanediol cyclic sulphate ( 4 , 3.78 g, 16.0 mmol) in one portion. The reaction mixture became viscous within 5 minutes and additional acetonitrile (60 ml) was added. The reaction is stirred overnight. The precipitate is collected, washed with acetone and air dried to give 7 . The manufacturing method is represented by the following reaction:

[Chemical 70]

Example II Preparation of 1- (3,3-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate ( 11 ): Step 1 : N-formyl-α, α-dimethyl-β-phenethylamine ( 9) ) Production of glacial acetic acid (8
(3.0 ml) and cool in an ice bath. Sodium cyanide (16.3 g, 1
Equivalent) and a solution of concentrated sulfuric acid in acetic acid (160g / 83.0ml) at a temperature of 20 ° C.
Add at a rate slow enough to keep below (Caution: Great care must be taken to avoid contact with poisonous gases). 2-Methyl-1-phenyl-2-propanol ( 8 , 50.0 g, 1 eq) is slowly added to the reaction mixture and stirred at room temperature overnight. Argonize the solution for 3 hours and pour into ice water (300 ml). An oil layer forms, which is separated and stored. The aqueous layer is neutralized to pH 7 with sodium carbonate and extracted with diethyl ether (3 x 200 ml). The organic layer is combined with the oil layer already separated, dried over magnesium sulphate and concentrated to give 9 . The manufacturing method is represented by the following reaction:

[Chemical 71]

Step 2 : Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline ( 10 ): 1 L equipped with side arm adapter, dropping funnel and mechanical stirrer
Into a 3-neck round bottom flask are charged polysulfuric acid (378 g) and phosphorus pentoxide (60.4 g). The mixture is stirred and heated at 180 ° C. for about 1 hour to about 150 ° C.
Cool down. N-formyl-α, α-dimethyl-β-phenethylamine is melted and added as a stream to the acid mixture. Heat the reaction to 180 ° C,
Stir overnight. The reaction mixture is cooled to about 100 ° C. and slowly mixed with ice water (2 L). Then filtered diluted reaction mixture with Celite ^R. The filtrate is washed with diethyl ether (2 x 100 ml). The aqueous solution is stirred while adding a saturated aqueous solution of potassium hydroxide and cooled in an acetone / dry ice bath. When the pH of the mixture reaches 9, the mixture is extracted with diethyl ether (4 x 100 ml). The organic layer is washed with pH 10 buffer (200 ml), dried over magnesium sulphate and concentrated under vacuum to give 4 . The manufacturing method is represented by the following reaction:

[Chemical 72]

Step 3 : Preparation of 3,3-Dimethyl-3,4-dihydroisoquinoline tetrafluoroborate ( 11 ): To a round bottom flask equipped with a magnetic stir bar at 0 ° C. trimethyloxonium tetrafluoroborate (Meerwein salt, 1.13 g, 7.7 mmol) and methylene chloride (1
5 ml). To the stirred solution in methylene chloride (40 ml) 3,3-dimethyl-
A solution of 3,4-dihydroisoquinoline (1.11 g, 7.0 mmol) is added over 5 minutes. Warm the heterogeneous solution to room temperature and stir overnight. The solution is concentrated and ethanol is added to the resulting oil to give crystals, which gives 11 . The manufacturing method is represented by the following reaction:

[Chemical formula 73]

Example III Preparation of 1,1-diphenyl-3-julylpseudoisoindolinium tetrafluoroborate ( 15 ): Step 1 : Preparation of 1,1-diphenyl-3-julylpseudoisoindole ( 12 ) , Fuson, RC et al. J. Org. Chem. 1951, 16, 648, as described in the art.

Step 2 : Preparation of 1,2-hexanediol cyclic sulphate ( 14 ): To a 500 ml three neck round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel and reflux condenser, 1,2-hexanediol ( 13) , 5.91 g, 50.0 mmol
) And 50 ml of carbon tetrachloride. After dissolution of 1,2-hexanediol, thionyl chloride (5.5 ml, 75 mmol) was added dropwise at room temperature, and the reaction solution was heated to 60 ° C. After 2 hours, cool the reaction with an ice bath. Water (50 ml) and acetonitrile (75 ml) are added. Hydrated ruthenium chloride (0.131g, 0.50mmol
) And sodium periodate (21.4 g, 100 mmol) are added and the reaction mixture is stirred at room temperature for 1 hour. The mixture was extracted with diethyl ether (4 x 175 ml) and the organic layer was water (5 x 100 ml), saturated sodium bicarbonate (3 x 100 ml).
Wash with brine (2 × 100 ml), filter through Celite / silica gel and dry over magnesium sulfate. The clear liquid is concentrated to give 7 as a clear oil. The manufacturing method is represented by the following reaction:

[Chemical 74]

Step 3 : Preparation of 1,1-diphenyl-3-julylpseudoisoindolinium tetrafluoroborate ( 15 ): Into a 200 ml round bottom flask equipped with a magnetic stir bar, 1,1-diphenyl-3-jurylp. Soidisoindole ( 12 , 5.55 g, 20.0 mmol) and acetonitrile (30 ml) are added. To this solution is added 1,2-hexanediol cyclic sulphate ( 14 , 2.60 g, 22.0 mmol) in one portion. The reaction mixture is 5
It became viscous within minutes and additional acetonitrile (60 ml) was added. The reaction is stirred overnight. The precipitate is collected, washed with acetone and air dried to give 15 . The manufacturing method is represented by the following reaction:

[Chemical 75]

[0206] Bleaching detergent compositions having the form of Formulation Examples Example IV granular laundry detergents are exemplified by the following formulations. A B C D E Bleach enhancing compound ^* 0.05 0.01 0.13 0.04 0.07 Conventional Activator (NOBS) 0.00 2.00 1.20 0.70 0.00 Conventional Activator (TAED) 3.00 0.00 2.00 0.00 0.00 Conventional Activator (NACA-OBS) 3.00 0.00 0.00 0.00 2.20 Sodium percarbonate 5.30 0.00 0.00 4.00 0.00 Sodium perborate monohydrate 0.00 5.30 3.60 0.00 4.30 Linear alkylbenzene sulfonate 12.00 0.00 12.00 0.00 21.00 C45AE0.6S 0.00 15.00 0.00 15.00 0.00 C2 Dimethylamine N-oxide 0.00 2.00 0.00 2.00 0.00 C12 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 dimethyl hydroxy 1.50 0.00 1.50 0.00 0.00 Ethyl 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 Tripolyphosphate Sodium 25.00 25.00 15.00 15.00 25.00 Zeolite 0.00 0.00 0.00 0.00 0.00 Acrylic acid / maleic acid copolymer 0.00 0.00 0.00 0.00 1.00 Polyacrylic acid, partial neutralization 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 Sodium silicate 3.00 3.00 3.00 3.00 6.00 Sodium bicarbonate 5.00 5.00 5.00 5.00 5.00 Savinase (4T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 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) Whitening agent 0.20 0.20 0.20 0.05 0.20 Sulfonated zinc phthalocyanine 0.50 0.00 0.25 0.00 0.00 Photobleach MgSO ₄ 2.20 2.20 2.20 2.20 0.64 Na ₂ SO ₄ Remainder Remainder Remainder ^* 1- (4,4-dimethyl-3,4-dihydroisoquinoline prepared according to Example I ) Decane-2-sulfate Any of the above compositions is used to wash the fabric at a concentration of 3500 ppm in water, 25 ° C and a 15: 1 water: garment ratio. A typical pH is about 9.5 but may be adjusted by varying the acid to Na salt form ratio of the alkylbenzene sulfonate.

Example V A bleaching detergent composition having the form of a granular laundry detergent is exemplified in the following formulation. A B C D E Bleach enhancing compound ^* 0.26 0.38 0.04 0.03 0.01 Conventional Activator (NOBS) 0.00 0.00 0.00 0.50 0.00 Conventional Activator (TAED) 1.80 1.00 2.50 3.00 1.00 Conventional Activator (NACA-OBS) 3.00 0.00 0.00 2.50 0.00 Sodium Percarbonate 5.30 0.00 0.00 0.00 0.00 Sodium Perborate Monohydrate 0.00 9.00 17.60 9.00 9.00 Linear Alkylbenzenesulfonate 21.00 12.00 0.00 12.00 12.00 C45AE0.6S 0.00 0.00 15.00 0.00 0.00 C2 Dimethylamine N-oxide 0.00 0.00 2.00 0.00 0.00 C12 cocoamidopropyl betaine 0.00 1.50 0.00 1.50 1.50 Palm N-methylglucamide 0.00 1.70 2.00 1.70 1.70 C12 dimethyl hydroxy 1.00 1.50 0.00 1.50 1.50 Ethyl 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 Tripolyphosphate Sodium 25.00 15.00 25.00 15.00 15.00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Acrylic / maleic acid copolymer 0.00 0.00 0.00 0.00 0.00 Polyacrylic acid, partial neutralization 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 (Methylenephosphonic acid) Whitening agent 0.20 0.30 0.20 0.30 0.30 Sulfonated zinc phthalocyanine 0.25 0.00 0.00 0.00 0.00 Photobleach MgSO ₄ 0.64 0.00 2.20 0.00 0.00 Na ₂ SO ₄ Remainder Remainder Remainder It prepared according remainder ^* example I 1-(4,4-dimethyl-3,4-dihydro isoquinolinium ) Decan-2-sulfate any of the above compositions are also concentration in water 3500 ppm, 25 ° C. and 15: 1 water: used for washing fabrics in garment ratio. A typical pH is about 9.5 but may be adjusted by varying the acid to Na salt form ratio of the alkylbenzene sulfonate.

[0208] EXAMPLE VI Bleaching detergent powder comprises the following ingredients: Ingredient wt% bleach enhancing compound ^* 0.07 TAED 2.0 perborate tetrasodium anhydride 10 C ₁₂ linear alkyl benzene sulfonate 8 Phosphate (tripolyphosphate sodium as) 9 sodium carbonate 20 talc 15 brightener, prepared according perfume 0.3 sodium chloride 25 water and to other 100% balance ^* example I 1-(4,4-dimethyl-3,4-dihydroisoquinoline) Decane-2-sulfate

[0209] While the solid laundry detergent that is suitable in terms of hand washing Example VII soiled fabrics prepared by standard extrusion processes, which comprises the following: Ingredient wt% bleach enhancing compound ¹ 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 to 10 microns) 5 carboxymethylcellulose 0.2 polyacrylates (m.w.1400) 0.2 brighteners, prepared according perfume 0.2 protease 0.3 CaSO ₄ 1 MgSO ₄ 1 water 4 filler ² balance to 100% ¹ example I 1- (4,4-dimethyl-3,4-dihydroisoquinoline ) Decane-2-sulfate ² can be selected from convenient substances such as CaCO ₃ , talc, clay, silicates and the like. Acidic fillers may also be used to reduce pH.

[0210] prepared by standard processes laundry detergent composition suitable for Examples VIII machinery, which is the following composition: Ingredient wt% bleach enhancing compound ^* 0.82 TAED 7.20 Sodium perborate tetrahydrate 9.2 Sodium carbonate 23.74 Anionic surfactant 14.80 Aluminosilicate 21.30 Silicate 1.85 Diethylenetriaminepentaacetic acid 0.43 Polyacrylic acid 2.72 Whitening agent 0.23 Solid polyethylene glycol 1.05 Sulfate 8.21 Perfume 0.25 Water 7.72 Processing aid 0.10 Other 0.43 ^* 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according to Example I The composition has a temperature of 20-40 ° C. and a water: fabric ratio of about 20: 1 and about 1 in solution.
Used to wash fabrics at a concentration of 000 ppm.

Example IX Component wt% Bleach Enhancement Compound ^* 1.0 TAED 10.0 Sodium Perborate Tetrahydrate 8.0 Sodium Carbonate 21.0 Anionic Surfactant 12.0 Aluminosilicate 18.0 Diethylenetriamine V Acetic acid 0.3 Nonionic surfactant 0.5 Polyacrylic acid 2.0 Whitening agent 0.3 Sulfate 17.0 Perfume 0.25 Water 6.7 Others 2.95 ^* 1- (prepared according to Example I 4,4-Dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate The composition is about 8 in solution at a temperature of 20-40 ° C. and a water: fabric ratio of about 20: 1.
Used to wash the fabric at a concentration of 50 ppm.

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 come within the scope of the invention are considered to be covered by the appended claims.

The compositions of the present invention may be conveniently prepared by any process selected by the practitioner, non-limiting examples of which are US Pat. No. 5,691,297,5,574,005,5.
569,645, 5,565,422, 5,516,448, 5,489,39
2 and 5,486,303. In addition to the above examples, the bleaching system of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are US Pat. No. 5,679,630, 5,565,14.
5, 5, 478, 489, 5, 470, 507, 5, 466, 802, 5, 46
0,752, 5,458,810, 5,458,809 and 5,288,43
1 is described. Although the present invention has been described in detail with reference to the preferred embodiments and examples, various changes and modifications can be made without departing from the scope of the present invention and the present invention is not limited to those described herein. Will be apparent to those skilled in the art.

[Sequence list]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Robert, Richard, Dijkstra             Cleves, Ohio, USA             Mitchell, park, drive, 7715 (72) Inventor Gregory, Scott, Miracle             Hamilton, Ohio, USA             Old, Oxford, Road,             3065 F-term (reference) 4H003 AA01 AB01 AB19 AB27 AC03                       AC18 AD03 BA17 DA01 EA09                       EA12 EA28 EB24 EB30 EB42                       EC01 EE01 EE05 FA07 FA09                       FA43

Claims (23)

[Claims] 1. A bleaching composition comprising a bleach enhancing compound with or without a peroxygen source, said bleach enhancing compound comprising: (a) an aryliminium cation, an aryliminium zwitterion. , About +
A bleach booster selected from the group consisting of aryliminium polyions having a net charge of 3 to about -3 and mixtures thereof; the bleach booster has the formulas [I] and [II]: 1] In the above formula, t is 0 or 1; R ¹ -R ⁴ is H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy,
A substituted or unsubstituted group selected from the group consisting of keto, carboxyl and carboalkoxy groups; two adjacent R ¹ -R ⁴ are joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring R ⁵ may be selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. R ⁶ is a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring and a group represented by the following formula: or unsaturated _{^{group: -T o - (Z -)}} a above wherein Z ^- is being covalently bonded to _{T o,} Z ^{- _{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
-CH ₂ (C ₆ H ₄ )-; _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl); (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 18 R 19 -, - CR} 18 R 19 CR 20 R 21 - , and ^{-CR 18 R 19 CR 20 R 21} CR ²² R ²³ - is selected from the group consisting ^of; R 14 ^{-R 23} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ⁷ -R ¹⁰ is H, linear or branched C ₁ -C ₁₂ alkyl A substituent independently selected from the group consisting of, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic ring. Or an unsubstituted group, provided that when t is 0, neither R ⁷ nor R ⁸ is H, and when t is 1, R ⁷ and R ⁸ are both, or R ⁹ and R ¹⁰ are both Neither is H; either R ¹ -R ¹⁰ is joined together with any other R ¹ -R ¹⁰ ,
May form part of a covalent ring; (b) Oxaziridinium cation, oxaziridinium zwitterion, about +
A bleaching species selected from the group consisting of oxaziridinium polyions having a net charge of 3 to about -3 and mixtures thereof;
Represented by III] and [IV]: In the above formula, t is 0 or 1; R ³¹ -R ³⁴ is from H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. Is a substituted or unsubstituted group selected from the group consisting of: two adjacent R ³¹ -R ³⁴ may be joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is A substituted or unsubstituted group selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups; R ²⁶ Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, substituted or unsubstituted selected from the group consisting of groups represented by heterocyclic rings and the following formula is a saturated or unsaturated ^{_{group: -T o - (Z -)}} a the formula Z ^- is being covalently bonded to _{T o,} and Z ^- represents _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
-CH ₂ (C ₆ H ₄ )-; _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl); (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 39 R 40 -, - CR} 39 R 40 CR 41 R 42 - , and ^{-CR 39 R 40 CR 41 R 42} CR ⁴³ R ⁴⁴ - is selected from the group consisting ^of; R 35 ^{-R 44} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ²⁷ -R ³⁰ is H, linear or branched C ₁ -C _{1 2} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
A substituted or unsubstituted group independently selected from the group consisting of cycloalkyl and a heterocyclic ring, provided that when t is 0, neither R ²⁷ nor R ²⁸ is H and t
When R 1 is 1, R ²⁷ and R ²⁸ are not both H, or R ²⁹ and R ³⁰ are both H; no R ²⁵ -R ³⁴ is bound together with any other R ²⁵ -R ³⁴ May form part of a covalent ring; and (c) a bleaching composition selected from the group consisting of mixtures thereof. 2. The bleach enhancing compound is about 0.001 to about 10% by weight of the composition and the peroxygen source, when present, is about 0.01 to about 60% by weight of the composition. The bleaching composition according to Item 1. 3. A peroxygen source, when present, is selected from the group consisting of (a) percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. A preformed peracid compound; (b) a hydrogen peroxide source selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof; and selected from the group consisting of bleach activators or none The bleaching composition according to claim 1. 4. R ⁶ is represented by the following formula: —T _o- (Z ⁻ ) _{a In the} above formula, Z ⁻ is covalently bonded to T _o , and Z ⁻ is —CO ₂ ^— , —SO ₃ ^—. and -OSO ₃ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is: embedded image The formula x is a 0 to 2; J, when present, independently ^-CR 18 ^{R 19} -
^{, -CR 18 R 19 CR 20 R} 21 - , and ^{-CR 18 R 19 CR 20 R 21} C
R ²² R ²³ - is selected from the group consisting ^of; R 14 ^{-R 23} is selected _H, C 1 _{-C 18} alkyl, cycloalkyl, alkaryl, aryl, from linear or branched group consisting of aralkyl and alkylene The bleaching composition according to claim 1, which is a substituted or unsubstituted group. 5. The bleaching composition according to claim 4, wherein the bleach booster is an aryliminium zwitterion, wherein R ⁵ is H or methyl and a is 1. 6. The bleaching composition according to claim 4, wherein the bleach booster is an aryliminium polyion having a net negative charge, wherein R ⁵ is H or methyl and a is 2. 7. The bleach booster is an aryliminium cation, wherein R ⁵ is H.
The bleaching composition according to claim 1, wherein the bleaching composition is methyl or R ⁶ is H or linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl and cycloalkyl. 8. The bleach booster is an aryliminium cation, wherein R ⁶ is selected from the group consisting of linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl and cycloalkyl, or said bleach. booster an aryliminium zwitterions, wherein ^{R 6} is a group represented by the following _{^{formula: -T o - (Z -)}} a above wherein Z ^- is _-CO ² -, -SO ₃ ^- or -OSO ₃ ^- a; a is a 1; _{T o} is selected from the group consisting of: embedded image The formula p is an integer from 2 to 4, R ⁴⁵ is independently selected from the group consisting of H and linear or branched C ₁ -C _{1 8} substituted or unsubstituted alkyl and cycloalkyl, claim 1 The bleaching composition described in. 9. The bleaching species is an oxaziridinium cation, wherein R ²⁶ is selected from the group consisting of linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl or cycloalkyl, or The bleaching species is an oxaziridinium zwitterion,
Wherein ^{R 26} is a group represented by the following _{^{formula: -T o - (Z -)}} a above wherein Z ^- is _-CO ² -, -SO ₃ ^- or -OSO ₃ ^- a; a is 1 _Yes ; To is selected from the group consisting of: The formula p is an integer from 2 to 4, R ⁴⁵ are independently selected from the group consisting of H and linear or branched C ₁ -C _{1 8} substituted or unsubstituted alkyl or cycloalkyl, claim 1 The bleaching composition described in. 10. The bleaching species is an oxaziridinium polyion having a net negative charge, wherein R ²⁵ is H or methyl and Z ⁻ is —CO ₂ ^— , —SO ₃ ^— or —OS.
The bleaching composition according to claim 1, which is O ₃ ⁻ and a is 2. 11. The bleaching species is an oxaziridinium polyion having a net negative charge, wherein R ²⁵ is H or methyl and R ²⁶ is selected from the group consisting of groups of the formula: _{^{: -T o - (Z -)}} a above wherein Z ^- is _-CO ² -, -SO ₃ ^- or -OSO ₃ ^- a; a is a 1; _{T o} is selected from the group consisting of: : [Chemical formula 10] The formula p is an integer from 2 to 4, R ⁴⁵ are independently selected from the group consisting of H and linear or branched C ₁ -C _{1 8} substituted or unsubstituted alkyl and cycloalkyl, claim 1 The bleaching composition described in. 12. The method according to claim 12,   The bleaching composition of claim 1, wherein the bleaching composition further comprises a surfactant. 13.   The bleaching composition according to claim 12, wherein the surfactant is an anionic surfactant. 14.   The bleaching composition according to claim 1, wherein the bleaching composition further comprises an enzyme. 15. The bleaching composition of claim 1, wherein the bleaching composition further comprises a chelating agent. 16. embedded image And a cationic or zwitterionic laundry bleach enhancing compound selected from the group consisting of and mixtures thereof: In formulas [I] and [II], t is 0 or 1; R ¹ -R ⁴ is H, alkyl, Is a substituted or unsubstituted group selected from the group consisting of cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups; two adjacent R ¹ -R ^{4 May} be joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ⁵ is H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo. Substituted or non-substituted selected from the group consisting of cyano, sulphonato, alkoxy, keto, carboxyl and carboalkoxy groups. Is substituent; R ⁶ is H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring and substituted or unsubstituted selected from the group consisting of groups represented by the following formula, a saturated or unsaturated group it _{^{is: -T o - (Z -)}} a above wherein Z ^- is being covalently bonded to _{T o,} and Z ^- represents _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
-CH ₂ (C ₆ H ₄ )-; _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl); (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 18 R 19 -, - CR} 18 R 19 CR 20 R 21 - , and ^{-CR 18 R 19 CR 20 R 21} CR ²² R ²³ - is selected from the group consisting ^of; R 14 ^{-R 23} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ⁷ -R ¹⁰ is H, linear or branched C ₁ -C ₁₂ alkyl A substituent independently selected from the group consisting of, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic ring. Or an unsubstituted group, provided that when t is 0, neither R ⁷ nor R ⁸ is H, and when t is 1, R ⁷ and R ⁸ are both, or R ⁹ and R ¹⁰ are both Neither is H; either R ¹ -R ¹⁰ is joined together with any other R ¹ -R ¹⁰ ,
May form part of a covalent ring; in formulas [III] and [IV], t is 0 or 1; R ³¹ -R ³⁴ is H
, An alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy group; substituted or unsubstituted group; two adjacent R ³¹ R ³⁴ may be joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo A cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy group, which is a substituted or unsubstituted group;
R ²⁶ is a substituted or unsubstituted, saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring and a group represented by the following formula: _o - ^(Z _{-) a} above wherein Z ^- is being covalently bonded to _{T o,} and Z ^- represents _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
-CH ₂ (C ₆ H ₄ )-; _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl); (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 39 R 40 -, - CR} 39 R 40 CR 41 R 42 - , and ^{-CR 39 R 40 CR 41 R 42} CR ⁴³ R ⁴⁴ - is selected from the group consisting ^of; R 35 ^{-R 44} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ²⁷ -R ³⁰ is H, linear or branched C ₁ -C _{1 2} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
A substituted or unsubstituted group independently selected from the group consisting of cycloalkyl and a heterocyclic ring, provided that when t is 0, neither R ²⁷ nor R ²⁸ is H and t
When There is a ^1, both ^{R 27} and ^{R 28,} or ^{R 29} and ^{R 30} are not H both; either ^R 25 ^{-R 34} is also coupled with any other ^R 25 ^{-R 34} The cationic or zwitterionic laundry bleach enhancing compound as described above, which may form part of a covalent ring. 17. A method for laundering a fabric in need of washing, which comprises contacting the fabric with a wash liquor having the bleaching composition of claim 1. 18. (a) Aryliminium cation, aryliminium zwitterion, about +
A bleach booster selected from the group consisting of aryliminium polyions having a net charge of 3 to about -3 and mixtures thereof; the bleach booster has the formulas [I] and [II]: 16] In the above formula, t is 0 or 1; R ¹ -R ⁴ is H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy,
A substituted or unsubstituted group selected from the group consisting of keto, carboxyl and carboalkoxy groups; two adjacent R ¹ -R ⁴ are joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring R ⁵ may be selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. R ⁶ is a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring and a group represented by the following formula: or unsaturated _{^{group: -T o - (Z -)}} a above wherein Z ^- is being covalently bonded to _{T o,} Z ^{- _{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
-CH ₂ (C ₆ H ₄ )-; _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl); (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 18 R 19 -, - CR} 18 R 19 CR 20 R 21 - , and ^{-CR 18 R 19 CR 20 R 21} CR ²² R ²³ - is selected from the group consisting ^of; R 14 ^{-R 23} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ⁷ -R ¹⁰ is H, linear or branched C ₁ -C ₁₂ alkyl A substituent independently selected from the group consisting of, alkylene, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic ring. Or an unsubstituted group, provided that when t is 0, neither R ⁷ nor R ⁸ is H, and when t is 1, R ⁷ and R ⁸ are both, or R ⁹ and R ¹⁰ are both Neither is H; either R ¹ -R ¹⁰ is joined together with any other R ¹ -R ¹⁰ ,
May form part of a covalent ring; (b) Oxaziridinium cation, oxaziridinium zwitterion, about +
A bleaching species selected from the group consisting of oxaziridinium polyions having a net charge of 3 to about -3 and mixtures thereof;
Represented by III] and [IV]: In the above formula, t is 0 or 1; R ³¹ -R ³⁴ is from H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups. Is a substituted or unsubstituted group selected from the group consisting of: two adjacent R ³¹ -R ³⁴ may be joined to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R ²⁵ is A substituted or unsubstituted group selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl and carboalkoxy groups; R ²⁶ Is H, alkyl,
Cycloalkyl, alkaryl, aryl, aralkyl, substituted or unsubstituted selected from the group consisting of groups represented by heterocyclic rings and the following formula is a saturated or unsaturated ^{_{group: -T o - (Z -)}} a the formula Z ^- is being covalently bonded to _{T o,} and Z ^- represents _{^{-CO 2 -, -SO 3 -,}} -
OSO ₃ ^-, -SO ₂ ^- and -OSO ₂ ^- is selected from the group consisting of, a is is 1 or 2; _{T o} is ^{(1) - (CH (R} 12)) - or - ^{(C (R 12} ) ₂ )-(R ¹² is independently selected from H or C ₁ -C ₈ alkyl); (2)
-CH ₂ (C ₆ H ₄ )-; _{(5) - (CH 2)} d (E) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O-); (6 ^{) -C (O) NR 13 -} (R 13 is H
Or C ₁ -C ₄ alkyl); (Above wherein x is a 0 to 3; J, when present, independently ^{-CR 39 R 40 -, - CR} 39 R 40 CR 41 R 42 - , and ^{-CR 39 R 40 CR 41 R 42} CR ⁴³ R ⁴⁴ - is selected from the group consisting ^of; R 35 ^{-R 44} is _H, C _{1 -C} 1 ₈ alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, Is a substituted or unsubstituted group selected from the linear or branched group consisting of carboxyalkyl and amido groups; R ²⁷ -R ³⁰ is H, linear or branched C ₁ -C _{1 2} Alkyl, alkylene, alkoxy, aryl, alkaryl, aralkyl,
A substituted or unsubstituted group independently selected from the group consisting of cycloalkyl and a heterocyclic ring, provided that when t is 0, neither R ²⁷ nor R ²⁸ is H and t
When R 1 is 1, R ²⁷ and R ²⁸ are not both H, or R ²⁹ and R ³⁰ are both H; no R ²⁵ -R ³⁴ is bound together with any other R ²⁵ -R ³⁴ May form part of a covalent ring; and (c) a laundry additive product comprising a bleach enhancing compound selected from the group consisting of mixtures thereof. 19. R ⁶ is selected from the group consisting of linear or branched C ₁ -C ₁₄ substituted or unsubstituted alkyl and cycloalkyl, or R ⁶ is a group of the formula: —T _o - ^(Z _{-) a} above wherein Z ^- is _-CO ² -, -SO ₃ ^- or -OSO ₃ ^- a; a is 1 or 2; _{T o} is selected from the group consisting of: [ 22 The formula p is an integer from 2 to 4, R ⁴⁵ are independently selected from the group consisting of H and linear or branched C ₁ -C _{1 8} substituted or unsubstituted alkyl and cycloalkyl, claim 18 The laundry additive product described in. 20. R ¹ -R ⁴ are independently selected from the group consisting of H, alkyl and alkoxy, R ⁵ is selected from H or methyl, R ⁶ is linear or branched C ₁ -C ₁₄ substituted or or is selected from unsubstituted alkyl and the group consisting of cycloalkyl, or ^{R 6} is a group represented by the following _{^{formula: -T o - (Z -)}} a above wherein Z ^- is -SO ₃ ^- or -OSO ₃ ^-, a is 1, claim 1
The laundry additive product according to item 9. 21. The laundry additive product of claim 18, wherein the laundry additive product is a dosage form selected from the group consisting of pills, tablets, caplets, gelcaps or other single dosage forms. 22. The laundry additive product of claim 18, wherein the laundry additive product further comprises a suitable carrier. 23. The bleach activator is tetraacetylethylenediamine (TAED),
Benzoyl caprolactam (BzCl), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyl oxybenzene sulphonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyl oxybenzene sulphonate _{(C 10} - OBS), benzoyl valerolactam (BZVL), octanoyloxybenzene sulfonate (C ₈ -OBS), perhydrolizing ester, 4- [N-
(Nonanoyl) aminohexanoyloxy] benzenesulfonate sodium salt (NACA-OBS), lauroyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzenesulfonate (UD)
A bleaching composition according to claim 3, which is selected from the group consisting of OBS), decanoyloxybenzoic acid (DOBA) and mixtures thereof.