DE69504645T2 - FIXED COMPOSITIONS CONTAINING BLEACH ACTIVATORS AND BLEACH CATALYSTS - Google Patents

Abstract

Bleaching and cleaning compositions comprising a bleaching compound, one or more bleach activators, and a bleach catalyst. Thus, laundry detergent compositions and automatic dishwashing compositions which comprise perborate, percarbonate and activators such as benzoyl caprolactam exhibit improved stain removal performance in the presence of the bleach catalyst.

Description

TECHNICAL AREA

The present invention relates to cleaning and bleaching compositions which employ manganese complexes to enhance performance. Bleaching, fabric washing, dishwashing and sanitizing compositions with improved oxygen bleaching activity are provided.

BACKGROUND OF THE INVENTION

It is common practice for formulators of cleaning compositions to include bleaching agents, such as sodium perborate or sodium percarbonate, in such compositions for their bleaching action. Such bleaching agents are widely known for their ability to remove various stains and soils from fabrics. Similarly, formulators of compositions for automatic dishwashers have found that various bleaching agents can help remove tea stains, proteinaceous soils, and the like from dishes. Various fabric bleaching and/or presoaking compositions also include percarbonate or perborate bleaching agents. Sanitizers for toilets, sewers, and the like may also include various bleaching agents.

Unfortunately, many bleaches do not perform optimally under all use conditions. As a general observation, perborate and percarbonate bleaches are more effective in hot water than in cold water. Nevertheless, many consumers now perform fabric washing and other cleaning operations in moderate to cold water temperatures. To improve the performance of perborate and percarbonate bleaches, many manufacturers have turned to so-called "bleach activators." Such activators typically comprise organic molecules that interact with perborate or percarbonate to release "peracid" bleach species. The combination of bleach plus activator works well over a wide range of water temperatures and use conditions.

It is also known that various transition metal cations, such as manganese, have the potential to act as bleach activators or catalysts, presumably by means of their catalytic interactions with peroxide or peracid bleach species. Unfortunately, many transition metals react so readily with per compounds that they destroy the bleach species too quickly under conventional cleaning conditions. Attempts to catalyze and improve bleaching with manganese cations have been particularly vexing because, if not done properly, the deposition of unsightly brown MnO2 stains on the surface being bleached can occur.

Various manganese bleach catalysts have been proposed. U.S. Patent 4,430,243, Bragg, teaches bleach catalysts using various chelating agents and a mixture of manganese cations and non-catalytic metal cations. Manganese gluconate catalysis is described in U.S. 4,728,455. Such prior art bleaches have not found commercial acceptance. Recently, a number of manganese bleach catalysts involving rather complex ligands have been reported (citations below).

It has now been discovered that compositions containing n-acyl lactam activators or amido derived activators in combination with bleach catalysts, particularly metal bleach catalysts, can be used to provide effective enhanced bleaching.

Accordingly, it is an object of the present invention to provide improved cleaning and bleaching compositions using bleach activators and bleach catalysts. It is a further object herein to provide a method for removing soils and stains from fabrics and dishware using the catalyzed bleaching systems of this invention. These and other objects are provided herein as will become apparent from the description below.

PROFESSIONAL BACKGROUND

The use of amido-derived bleach activators in laundry detergents is described in U.S. Patent 4,634,551. Another class of bleach activators includes benzoxazine-type activators described by Hodge et al. in U.S. Patent 4,966,723, issued October 30, 1990. The use of manganese with various complex ligands to enhance bleaching effect has been reported in the following US patents: 4,430,243, 4,728,455, 5,246,621, 5,244,594, 5,284,944, 5,194,416, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161, 5,227,084, 5,114,606, 5,114,611. See also: EP 549 271 A1, EP 544 490 A1, EP 549 272 A1 and EP 544 440 A2.

SUMMARY OF THE INVENTION

The present invention includes bleaching compositions comprising a bleaching agent, particularly a bleaching agent which is a member of the group consisting of H₂O₂, perborate, percarbonate, persulfate and peracid bleaching agents, one or more selected bleach activators and a catalytically effective amount of one or more bleach catalysts, particularly metal bleach catalysts. Preferred compositions comprise a percarbonate or perborate bleaching agent or mixtures thereof, and a bleach activator selected from N-acyl lactam type activators, amido derived activators and benzoxazine type activators and mixtures thereof. In addition, the bleaching compositions of this invention may further comprise a second bleach activator or peracid selected from tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS) and magnesium monoperoxyphthalate.

The bleach activators are chosen from the following:

a) an amido-derived bleach activator of the general formula:

or mixtures thereof, wherein R¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, R⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms, and L is a leaving group;

b) a benzoxazine-type bleach activator of the formula:

wherein R₁ is H, alkyl, alkaryl, aryl, arylalkyl and wherein R₂, R₃, R₄ and R₅ may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR₆ (wherein R₆ is H or an alkyl group) and carbonyl functions;

c) N-acyl lactam bleach activators of the formula:

wherein n is 0 to 8, preferably 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 carbon atoms, or a substituted phenyl group having 6 to 18 carbon atoms (see copending application 08/064,562 and 08/082,270), and

d) Mixtures of a), b) and c).

Preferably, the molar ratio of hydrogen peroxide obtained from the peroxygen bleach compound to the bleach activator is greater than about 1.0. Most preferably, the molar ratio of hydrogen peroxide to the bleach activator is at least about 1.5.

Preferred bleach activators of type a) are those wherein R¹ is an alkyl group having about 6 to about 12 carbon atoms, R² contains about 1 to 8 carbon atoms, and R⁵ is H or methyl. Particularly preferred bleach activators are those of the above general formulas, wherein R¹ is an alkyl group having from about 7 to about 10 carbon atoms and R² contains from about 4 to about carbon atoms.

Preferred bleach activators of type b) are those wherein R2, R3, R4 and R5 are H and R1 is a phenyl group.

The preferred acyl radicals of N-acyl lactam bleach activators of type c) have the formula R6-CO-, where R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group having from about 1 to about 12 carbon atoms, or a substituted phenyl group having from about 6 to about 18 carbon atoms. In highly preferred embodiments, R6 is a member selected from the group consisting of unsubstituted and substituted phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl, and mixtures thereof.

Highly preferred activators include benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolac tam, (6-octanamidocaproyl)oxybenzenesulfonate, (6- Nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof. Examples of highly preferred substituted benzoyl lactams include methyl benzoyl caprolactam, methyl benzoyl valerolactam, ethyl benzoyl caprolactam, ethyl benzoyl valerolactam, propyl benzoyl caprolactam, propyl benzoyl valerolactam, isopropyl benzoyl caprolactam, isopropyl benzoyl valerolactam, butyl benzoyl caprolactam, butyl benzoyl valerolactam ylbenzoylcaprolactam, tert-butylbenzoylvalerolactam, pentylbenzoylcaprolactam, pentylbenzoylvalerolactam, hexylbenzoylcaprolactam, hexylbenzoylvalerolactam, ethoxybenzoylcaprolactam, ethoxybenzoylvalerolactam, propoxybenzoylcaprolactam, propoxybenzoylvalerolactam , isopropoxybenzoyl caprolactam, Isopropoxybenzoylvalerolactam, butoxybenzoylcaprolactam, butoxybenzoylvalerolactam, tert-butoxybenzoylvalerolactam, tert-butoxybenzoylvalerolactam, pentoxybenzoylcaprolactam, pentoxybenzoylvalerolactam, hexoxybenzoylcaprolactam, hexoxybenzoylvalerolactam, 2,4,6-trichlorobenzoylcaprolactam 2 ,4,6-Trichlorobenzoylvalerolactam, Pentafluorobenzoylcaprolactam, Pentafluorobenzoylvalerolactam, Dichlorobenzoylcaprolactam, Dimethoxybenzoylcaprolactam, 4-Chlorobenzoylcaprolactam, 2,4-Dichlorobenzoylcaprolactam, Terephthaloyldicaprolactam, Pentafluorobenzoylcaprolactam, Pentafluorobenzoylvalerolactam, Dichlorobenzoylvalerolactam, Dimethoxybenzoylvalerolactam, 4-chlorobenzoylvalerolactam, 2,4-dichlorobenzoylvalerolactam, terephthaloyldivalerolactam, 4- nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam and mixtures thereof.

Particularly preferred are bleach activators consisting of benzoylcaprolactam, benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecanoylcaprolactam, undecanoylvalerolactam, 3,5,5-trimethylhexano ylcaprolactam, 3,5,5-trimethylhexanoylvalerolactam, Dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam, terephthaloyldicaprolactam, terephthaloyldivalerolactam, (6-octanamidocaproyl)oxybenzene sulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Preferred compositions herein are those wherein the bleach catalyst is a metal-based catalyst.

The invention also includes laundry compositions, particularly laundry detergents, which otherwise comprise conventional surfactants and other laundry ingredients and bleaching agents and a catalytically effective amount of a bleach catalyst. In such compositions, the bleaching agent preferably again comprises a member selected from the group consisting of percarbonate, perborate and mixtures thereof with bleach activators, particularly bleach activators selected from N-acylcaprolactams, N-acylvalerolactams, benzoxazine-type activators, amido-derived activators and mixtures thereof.

The invention also includes detergent or bleaching compositions comprising a bleaching agent, bleach activator and a catalytically effective amount of a water-soluble manganese salt.

The invention also includes a method for improving the bleaching performance of oxygen or peracid bleaching compositions comprising adding a catalytically effective amount of manganese cations in the presence of selected ligands. This results in a method for removing stains from fabrics comprising contacting the fabrics with an aqueous medium containing the compositions.

The bleach catalyst is used in a catalytically effective amount in the compositions and methods described herein. By "catalytically effective amount" is meant an amount sufficient, whatever comparative conditions are used, to effect bleaching and stain removal of soil of interest from the target substrate. Thus, in a fabric washing operation, the target substrate will typically be a fabric soiled with, for example, various food stains. For automatic dishwashing, the target substrate may be, for example, a china cup or plate with tea stains or a polyethylene plate soiled with tomato soup. Test conditions vary depending on the type of washing equipment used and the habits of the user. For example, front-loading laundry washing machines of the type used in Europe generally use less water and higher detergent concentrations than top-loading U.S.-style machines. Some machines have considerably longer wash cycles than others. Some users choose to use very hot water; others use warm or even cold water in fabric washing operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations and the level of bleach catalyst used in fully formulated detergents and bleaching compositions can be adjusted as appropriate. As a practical matter, and not by way of limitation, the compositions and processes described herein can be adjusted to contain on the order of at least one part per ten million of active bleach catalyst species in of the aqueous wash liquor, and preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of catalyst species in the laundry liquor. To further illustrate this point, on the order of 3 micromolar manganese catalyst at 40°C and pH 10 is effective under European conditions using perborate and a bleach activator (e.g., benzoyl caprolactam). Increasing the concentration by 3- to 5-fold may be successful under U.S. conditions to achieve the same results. In contrast, using a bleach activator and the manganese catalyst with perborate may enable the formulator to achieve equivalent bleaching at lower perborate usage levels than with products without a manganese catalyst.

All percentages, ratios and proportions given herein are by weight unless otherwise specified. All documents cited herein are, in their relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Bleach catalyst

The bleach catalyst material used herein may include the free acid form, the salts and the like.

One type of bleach catalyst is a catalyst system comprising a heavy metal cation with defined catalytic bleaching activity, such as copper, iron or manganese cations, an auxiliary metal cation with little or no catalytic bleaching activity, such as zinc or aluminum cations, and a sequestering agent with defined stability constancy for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are described in U.S. Patent 4,430,243.

Other types of bleach catalysts include the manganese-based complexes described in US Patent 5,246,621 and US Patent 5,244,594. Preferred examples of these catalysts include MnIV₂(u-O)₃(1,4,7-trimethyl-1,4,6-triazacyclononane)₂- (PF₆)₂, MnIII₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂, MnIV₄(u-O)₆- (1,4,7-triazacyclononane)₂(ClO₄)₄, MnIIIMnIV₄(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃, and mixtures thereof. Others are described in European Application Publication No. 549 272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful in machine dishwashing compositions and concentrated powder detergent compositions can also be selected as appropriate for the present invention. For examples of suitable bleach catalysts, see U.S. Patent 4,246,612 and U.S. Patent 5,227,084.

See also U.S. Patent 5,194,416, which teaches mononuclear manganese(IV) complexes such as MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃(PF₆).

Another type of bleach catalyst, as described in U.S. Patent 5,114,606, is a water-soluble complex of manganese (II), (III) and/or (IV) with a ligand, which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythrtol, meso-inositol, lactose and mixtures thereof.

US Patent 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a non-(macro)-cyclic ligand.

These ligands have the formula:

wherein R¹, R², R³ and R⁴ may be selected from H, substituted alkyl and aryl groups such that each R¹-N=C-R² and R³-C=N-R⁴ forms a 5- or 6-membered ring. This ring may be further substituted. B is a bridging group selected from O, S, CR⁵R⁶, NR⁷ and C=O, wherein R⁵, R⁶ and R⁴ may each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, such rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Most preferably, the ligand is 2,2'-bispyridylamine. Preferred bleach catalysts include Co-, Cu-, Mn-, Fe-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, di(isothiocyanato)bispyridylaminocobalt(II), trisdipyridylaminecobalt(II) perchlorate, Co(2,2-bispyridylamine)2O2ClO4, bis-(2,2'- bispyridylamine)copper(II) perchlorate, tris(di-2-pyridylamine)iron(II) perchlorate and mixtures thereof. Other examples include Mn-gluconate, Mn(CF3SO3)2, Co(NH3)5Cl, and binuclear Mn complexed with tetra-N-dentate and Bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+ and [Bipy2MnIII(u-O)2MnIVbipy2](ClO4)3.

The bleach catalysts of the present invention can also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and concentrating the resulting mixture by evaporation. Any conventional water-soluble salt of manganese can be used herein. Manganese (II), (III), (IV) and/or (V) is readily available on a commercial scale. In some cases, sufficient manganese may be present in the wash liquor, but it is generally preferred to add Mn cations to the compositions to ensure their presence in catalytically effective amounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of MnSO4, Mn(ClO4)2 or MnCl2 (least preferred) are dissolved in water in molar ratios of ligand:Mn salt ranging from about 1:4 to 4:1 at a neutral or slightly alkaline pH. The water can first be deoxy generation by boiling and cooled by purging with nitrogen. The resulting solution is evaporated (under N₂ if desired) and the resulting solids are used in the bleaching and detergent compositions described herein without further purification.

In an alternative mode, the water-soluble manganese source, such as MnSO4, is added to the bleach/cleaning compositions or to the aqueous bleach-cleaning bath containing the ligand. Some types of complexes are apparently formed in situ, and improved bleaching performance is ensured. In such an in situ process, it is beneficial to use a considerable molar excess of the ligand over manganese, and molar ratios of ligand:Mn are typically between 3:1 and 15:1. The additional ligand also serves to scavenge floating metal ions, such as iron and copper, thereby protecting the bleach from decomposition. One possible such system is described in European Patent Application Publication No. 549 271.

Although the structures of the bleach-catalyzing manganese complexes of the present invention have not been elucidated, it can be speculated that they include chelates or other hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Also, the oxidation state of the manganese cation during the catalytic process is not known with certainty and may be the (+II), (+III), (+IV) or (+V) valence state. Because of the possible six points of attachment of the ligand to the manganese cation, it can be reasonably speculated that multinuclear species and/or "cage" structures may be present in the aqueous bleaching media. Whatever the form of the active Mn ligand species actually present, it acts in an apparent catalytic manner, thereby providing improved bleaching performance on stubborn stains such as tea, ketchup, coffee, blood and the like.

Other bleach catalysts include: E.g. in European patent application, publication No. 408 131 (cobalt complex catalysts), European patent applications, publications Nos. 384 503 and 306 089 (metal porphyrin catalysts), US 4 728 455 (manganese/multidentate ligand catalysts), US 4 711 748 and European patent application, publication No. 224 952 (absorbed manganese on aminosilicate catalyst), US 4 601 845 (aluminosilicate support with manganese and zinc or magnesium salt), US 4 626 373 (manganese/ligand catalyst), US 4 119 557 (iron(III) complex catalyst), German patent specification 2 054,019 (cobalt chelating catalyst), Canadian Patent 866,191 (transition metal containing salts), US 4,430,243 (chelating agents containing manganese cations and non-catalytic metal cations) and US 4,728,455 (manganese gluconate catalysts).

Bleaching Compounds and Bleaching Agents - It will be appreciated that the bleach catalyst itself does not function as a bleaching agent. Rather, it is used as a catalyst to enhance the performance of conventional bleaching agents and in particular oxygen bleaching agents, such as perborate, percarbonate, persulfate and the like, particularly in the presence of bleach activators. Accordingly, the compositions described herein also contain bleaching agents or bleach mixtures containing a bleaching agent and one or more bleach activators in an amount sufficient to provide bleaching of soils or stains of interest. Bleaching agents are typically present at levels of from about 1% to about 80%, more typically from about 5% to about 20%, of the detergent composition, particularly for fabric laundering. Bleaching and presoak compositions may contain from 5% to 99% of the bleaching agent. When present, the amount of bleach activator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleach mixture comprising the bleach plus bleach activator.

The bleaching agents used herein can be any bleaching agents useful in detergent compositions for fabric cleaning, hard surface cleaning, and other cleaning purposes known or becoming known. These include oxygen bleaching agents as well as other bleaching agents. Perborate bleaching agents, e.g., sodium perborate (e.g., mono- or tetrahydrate), can be used herein.

Peroxygen bleaching agents are preferably used in the compositions. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaching agents, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleaching agents (e.g., OXONE, manufactured commercially by DuPont) may also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, with no more than about 10 weight percent of the particles being smaller than about 200 microns, and no more than about 10 weight percent of the particles being larger than about 1,250 microns. Optionally, the percarbonate can be coated with silicate, borate, or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay, and Tokai Denka.

The compositions of the present invention also include mixtures of bleach activators.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably combined with bleach activators, which leads to the in situ production in aqueous solution (during the washing process) of the peracid corresponding to the bleach activator.

Amido-derived bleach activators - The bleach activators of type a) used in the present invention are amide-substituted compounds of the general formulas:

or mixtures thereof, wherein R¹, R² and R⁵ are as defined above and L can be essentially any suitable leaving group. A leaving group is any group which is displaced from the bleach activator as a consequence of nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, leads to the formation of the peroxycarboxylic acid. In general, for a group to be a suitable leaving group it must exert an electron-withdrawing effect. It should also form a stable whole so that the rate of reverse reaction is negligible. This facilitates nucleophilic attack by the perhydroxide anion.

The L group must be sufficiently reactive for the reaction to occur within the optimal time frame (e.g., a wash cycle). However, if L is too reactive, this activator is too difficult to stabilize for use in a bleach composition. These characteristics are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this rule are known. Typically, leaving groups are those that exhibit behavior in which their conjugate acid has a pKa in the range of about 4 to about 13, preferably about 6 to about 11, and most preferably about 8 to about 11.

Preferred bleach activators are those of the above general formula wherein R¹, R² and R⁵ are as defined above and L is selected from a group consisting of:

and Mixtures thereof, wherein R¹ is an alkyl, aryl or alkaryl group having from about 1 to about 14 carbon atoms, R³ is an alkyl chain having from 1 to about 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizing group.

The preferred solubilizing groups are -SO₃⁻M⁺, -CO₂⁻M⁺, -SO₄⁻M⁺, -N⁺(R³)₄X⁺ and O → N(R³)₃, and most preferably -SO₃⁻M⁺ and -CO₂⁻M⁺, where R³ is an alkyl chain having from about 1 to about 4 carbon atoms, M is a cation which imparts solubility to the bleach activator, and X is an anion which imparts solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion. It should be noted that bleach activators having a leaving group which does not contain solubilizing groups should be well dispersed in the bleach solution to aid in their dissolution.

Preferred bleach activators are those of the above general formula, wherein L is selected from the group comprising:

wherein R³ is as defined above and Y is -SO₃⁻M⁺ or -CO₂⁻M⁺, wherein M is as defined above .

Preferred examples of bleach activators of the above formulas include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

Another important class of bleach activators, including those of type b) and c), as described herein, yield organic peracids by ring opening as a consequence of nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion. For example, in type c) activators, this ring opening reaction involves attack on the carbonyl of the lactam ring by hydrogen peroxide or its anion. Since attack of an acyl lactam by hydrogen peroxide or its anion occurs preferentially at the exocyclic carbonyl, a catalyst may be required to obtain a significant amount of ring opening. Another example of ring opening bleach activators can be found in type b) activators such as those described in U.S. Patent 4,966,723, Hodge et al., issued October 30, 1990.

Such activator compounds described by Hodge include the benzoxazine-type activators having the following formula:

including substituted benzoxazines of the type

wherein R₁ is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R₂, R₃, R₄ and R₅ may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, COOR₆- (wherein R₆ is H or an alkyl group) and carbonyl functions.

A preferred benzoxazine-type activator is:

When the activators are used, optimal surface bleaching performance is obtained with wash solutions in which the pH of such solution is between about 8.5 and 10.5, and preferably between 9.5 and 10.5, to facilitate the perhydrolysis reaction. Such a pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching systems described herein.

Another class of preferred bleach activators includes acyl lactam activators, particularly acylcaprolactams and acylvalerolactams, of the following formulas:

wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group having from 1 to about 12 carbon atoms or a substituted phenyl group having from about 6 to about 18 carbon atoms. See also copending U.S. applications 08/064,562 and 08/082,270, which describe substituted benzoyl lactams. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which is incorporated herein by reference, which describes acyl caprolactams, including benzoyl caprolactam, adsorbed in sodium perborate.

Additional Bleach Activators - Various non-limiting examples of additional activators which may optionally be included in the bleach compositions described herein include those described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al., and U.S. Patent 4,412,934. The nonanoylbenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and Mixtures thereof may also be used; see also US 4,634,551 for other typical bleaches and activators useful herein.

Bleaching Agents - Another optional, but preferred, category of bleaching agents that can be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate (INTEROX), the magnesium salt of metachlorobenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. Such bleaching agents are described in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al., filed June 3, 1985, European Patent Application 0 133 354, Banks et al., published February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Patent 4,634,551, issued January 6, 1987, to Burns et al.

The present invention may optionally further include bleaching compositions comprising an effective amount of a substantially insoluble organic peroxyacid of the general formula:

wherein R¹, R² and R⁵ have the same meanings as defined for the above-mentioned bleach activator of type a).

The excellent bleaching/cleaning effect of the present compositions is achieved with innocuousness to natural rubber machine parts and other natural rubber articles, including textiles containing natural rubber and elastic natural rubber materials. The bleaching mechanism, and particularly the surface bleaching mechanism, is not fully understood. However, it is generally believed that the bleach activator undergoes nucleophilic attack by a perhydroxide anion generated from the hydrogen peroxide evolved by the peroxygen bleach, thereby forming a peroxycarboxylic acid. This reaction is generally referred to as perhydrolysis.

The amido-derived and lactam bleach activators described herein can also be used in combination with rubber-safe, enzyme-safe, hydrophilic activators, such as TAED, typically in weight ratios of amido-derived or caprolactam activators:TAED in the range of 1:5 to 5:1, preferably about 1:1.

Auxiliary components

The compositions described herein may optionally include one or more other detergent adjuvant materials or other materials to assist or enhance cleaning performance, treatment of the substrate to be cleaned, or modification of the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.). Preferably, the adjuvant ingredients should have good stability with the bleaching agents employed herein. Preferably, the detergent compositions described herein should be boron-free and phosphate-free. In addition, dish care formulations are preferably chlorine-free. The following are illustrative examples of such adjuvant materials.

Builders - Detergent builders may optionally be incorporated into the compositions described herein to assist in controlling mineral hardness. Inorganic as well as organic builders may be used. Builders are typically used in fabric washing compositions to assist in the removal of particulate soils.

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

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range of 1.64:4 to 3.2:1, and layered silicates such as sodium layered silicates described in U.S. Patent 4,664,839, issued May 2, 1987 to H. P. Rieck. NaSKS-6 is the trade name for the crystalline layered silicate marketed by Hoechst (conventionally abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the δ-Na2SiO5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-34 17 649 and DE-A-37 42 043. SKS-6 is a highly preferred layered silicate for use herein, however other such layered silicates, such as those having the general formula NaMSixO2x+1·yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also be used herein. Various other layered silicates from Hoechst include NaSKS-5, NsSKS-7 and NaSKS-11, such as the α-, β- and γ-forms. As noted above, the δ- Na₂SiO₅ is (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful, such as magnesium silicate, which can serve as a lump-forming agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component for foam control systems.

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

Aluminosilicate builders are particularly useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed granular heavy duty detergent compositions and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those with the empirical formula:

[Mz(zAlO₂)y]·xH₂O

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

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetically derived. A process for producing aluminosilicate ion exchange materials is described in U.S. Patent 3,985,669, Krummel et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange materials have the formula:

Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] xH 2 O

wherein x is between about 20 and about 30, especially about 27. This material is known as zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 µm in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but they can also be added in the form of a neutralized salt. When employed in salt form, alkali metal, such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. An important category of polycarboxylate builders includes the ether polycarboxylates, including oxydisuccinate, as described in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and in Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972; see also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874, and 4,102,903.

Citrate builders, e.g. citric acid and soluble salts thereof (especially sodium salt), polycarboxylate builders are of particular importance for detergent formulations due to their availability from renewable sources and their biodegradability. Citrates can be used in liquids or in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are particularly useful in such compositions and combinations.

Fatty acids, e.g. C12-C18 monocarboxylic acids, may also be incorporated into the compositions alone or in combination with the aforementioned builders, particularly citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a reduction in foaming, which should be taken into account by the formulator.

In situations where phosphor-based images can be used, and in particular in formulations for bar soaps used for hand washing operations, the various alkali metal phosphates, such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate, can be used.

Chelate Builders - Although builders may be used, the detergent compositions described herein do not contain such manganese chelate builders which strip manganese from the bleach catalyst complex. In particular, phosphonates, phosphates and the aminophosphonate chelate builders such as DEQUEST are preferably not used in the compositions. However, nitrogen-based manganese chelate builders such as ethylenediamine N,N'-disuccinate (EDDS) are preferred.

Detersive Surfactants - Non-limiting examples of surfactants useful herein, typically at levels of from about 1 wt.% to about 55 wt.%, include the conventional C11-C18 alkylbenzenesulfonates ("LAS") and C10-C20 primary, branched chain and random alkyl sulfates ("AS"), the C10-C18 secondary (2,3)alkyl sulfates of the formula CH3(CH2)x(CHOSO3-M+)CH3 and CH3(CH2)y(CHOSO3-M+)CH2CH3, wherein x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, particularly sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates ("AExS"; particularly EO-1-7 ethoxy sulfates); C₁₀-C₁₈-alkyl alkoxycarboxylates (in particular the EO-1-5-ethoxycarboxylates), the C₁₀-C₁₈-glycerol ethers, the C₁₀-C₁₈-alkyl polyglycosides and their corresponding sulfated polyglycosides, and α-sulfonated C₁₂-C₁₈-fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as C12-C18 alkyl ethoxylates ("AE"), including the so-called narrow-peaked alkyl ethoxylates and C6-C12 alkylphenol alkoxylates (particularly ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, may also be incorporated into the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides may also be employed. Typical examples include the C12-C18 N-methylglucamides; see WO 9 206 154. Other sugar-derived surfactants include the N- Alkoxypolyhydroxy fatty acid amides such as C10-C18-N-(3-methoxypropyl)glucamide. The N-propyl to N-hexyl C12aC18 glucamides can be used for low sudsing. The conventional C10-C20 soaps can also be used. When high sudsing is desired, the branched chain C10-C16 soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventionally useful surfactants are listed in standard texts.

Suitable nonionic surfactants, particularly suitable for dishwashing, are the low-foaming or non-foaming ethoxylated straight-chain alcohols, such as the PlurafacTM RA series sold by Eurane Co., the LutensolTM LF series sold by BASF Co., the TritonTM DF series sold by Rohm & Haas Co., and the SynperonicTM LF series sold by ICI Co.

Clay Soil Removal/Antiredeposition Agents - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines with clay soil removal and antiredeposition agents. Granular detergent compositions containing these compounds typically contain from 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01% to about 5%.

The most preferred soil release and antiredeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds described in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which may be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984, the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art may be used in the compositions described herein. Another type of preferred antiredeposition agents includes the carboxymethyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersants - Polymeric dispersants may be advantageously used at levels of from about 0.1% to about 7% by weight in the compositions described herein, particularly in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. Although not wishing to be bound by theory, it is believed that polymeric Dispersants enhance overall wash builder performance when used in combination with other builders (including low molecular weight polycarboxylates) by inhibiting crystal growth, peptizing released particulate soil and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments containing no carboxylate residues, such as vinyl methyl ether, styrene, ethylene, etc., in the polymeric polycarboxylates described herein is suitably provided such that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful herein are the water-soluble salts of polymeric acrylic acid. The average molecular weight of such polymers in the acid form is preferably in the range of about 2,000 to 10,000, more preferably about 4,000 to 7,000, and most preferably about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal, ammonium, and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic acid/maleic acid based copolymers may also be used as a preferred component of the dispersant/antiredeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably in the range of about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers is generally in the range of about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can, for example, be used as acrylate/maleic acid copolymers. B. the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials, which are described in European Patent Application No. 66915, published December 15, 1982.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersant ability as well as act as a clay soil removal/antiredeposition agent. Typical molecular weights for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersants may also be used, particularly in conjunction with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (average) of about 10,000.

Enzymes - Enzymes can be incorporated into the formulations described herein for a wide variety of fabric washing purposes, including, for example, for removing protein-based, carbohydrate-based or triglyceride-based stains and preventing fugitive dye transfer, and for fabric restoration. The enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, and mixtures thereof. Other types of enzymes can also be incorporated. They can be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. Nevertheless, their selection is determined by several factors, such as pH activity and/or stability optima, thermostability, stability versus active detergent, builder, etc. In this respect, bacterial or fungal-derived enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases.

Enzymes are typically incorporated in amounts sufficient to provide up to about 5 mg by weight, usually about 0.01 mg to about 3 mg, of active enzyme per gram of composition. Unless otherwise specified, the compositions described herein will typically contain about 0.001% to about 5%, preferably 0.01% to 1%, by weight of a commercial enzyme preparation. Protease enzymes are typically present in such commercial preparations in amounts sufficient to provide 0.005 to 0.1 Anson Units (AU) of activity per gram of composition.

Suitable examples of proteases are the subtilisins obtained from certain strains of B. subtilis, B. lentus and B. licheniforms. Another suitable protease is obtained from a Bacillus strain with maximum activity throughout the pH range of 8 to 12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in Novo's British Patent Specification No. 1 243 784. Proteolytic enzymes suitable for the removal of protein-based stains that are commercially available include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include protease A (see European patent application 130 756, published January 9, 1985) and protease B (see European patent application, Serial No. 87 303 761.8, filed April 28, 1987, and European patent application 130 756, Bott et al., published January 9, 1985).

Amylases include, for example, α-amylases described in British Patent Specification No. 1 296 839 (Novo), RAPIDASE, International Bio-Synthetics, Inc., and TERMAMYL, Novo Industries.

In the Cellulases useful in the present invention include both bacterial and fungal cellulase. Preferably, they have a pH optimum between 1 and 9.5.

Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group such as Pseudomonas stutzeri ATCC 19.154 as described in British patent 1,372,034. See also lipases in Japanese patent application 53-20487, made available to the public on February 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and also Chromobacter viscosum lipases from U. S. Biochemical Corp., USA, and Disoynth Co., Netherlands, and lipases from Pseudomonas gladioli. The LIPOLASE enzyme, which is derived from the fungus Humicola lanuginosa and is commercially available from Novo (see also EPA 341 947) is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent dyes or pigments removed from substrates during washing operations from passing to other substances in the wash solution. Peroxidase enzymes are known in the art and include, e.g. horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described, e.g. in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.

A wide variety of enzyme materials and methods for incorporating them into synthetic detergent compositions are also described in U.S. Patent 3,553,139, issued January 5, 1971, McCarty et al. Enzymes are also described in U.S. Patent 4,101,457, Place et al., issued July 18, 1978, and U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzyme materials useful in liquid detergent formulations and their incorporation into such formulations are described in U.S. Patent 4,261,868, Hora et al., issued April 14, 1981. Enzymes for use in detergents can be stabilized using a variety of techniques. Enzyme stabilization techniques are described in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge et al., and in European Patent Application Publication No. 0 199 405, Application No. 86 200 586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.

Enzyme Stabilizers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the final compositions which make such ions available to the enzymes (Cal (CiO ions are generally somewhat more effective than magnesium ions and are preferred herein when only one type of cation is used.) Additional stability can be provided by the presence of various other stabilizers described in the art, particularly borate species: see Serverson, US 4,537,706. Typical detergents, particularly liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12 mmoles of calcium ions per liter of final composition. This may vary somewhat depending upon the amount of enzyme present and its responsiveness to the calcium or magnesium ions. The level of calcium or magnesium ions should be chosen so that a minimum amount is always available to the enzyme after complexation with builders, fatty acids, etc. in the composition has occurred. Any water-soluble calcium or magnesium salt may be used as a source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate and the corresponding magnesium salts. A small amount of calcium ions, generally about 0.05 to about 0.4 mmoles per liter, is often present in the composition due to calcium in the enzyme slurry and formulation water. In solid detergent compositions, the formulation may include a sufficient amount of a water-soluble calcium ion source to provide such amounts in the aqueous liquor. In an alternative, natural water hardness may be sufficient.

It is understood that the above amounts of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions may be added to the compositions to provide an additional level of grease removal performance. Accordingly, as a general suggestion, the compositions described herein may typically include from about 0.05% to about 2% by weight of a water-soluble source of calcium and/or magnesium ions, or both. The amount may, of course, vary with the amount and type of enzyme employed in the composition.

The compositions described herein may optionally, but preferably, contain various additional stabilizers, particularly borate-type stabilizers. Typically, such stabilizers are used in the compositions in amounts ranging from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, based on the weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on a boric acid basis). Boric acid is preferred, although other compounds such as boric oxide, borax, and other alkali metal borates (e.g., sodium ortho-, meta-, and pyroborate, and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butaneboronic acid, and p-bromophenylboronic acid) may also be used in place of boric acid.

Brighteners - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions described herein at levels typically from about 0.05% to about 1.2% by weight. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered heterocycles, and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include the following: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styrylphenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)stilbenes; 4,4'-bis(stryl)bis-phenyls and the aminocoumarins. Specific examples of these brighteners include: 4- methyl-7-diethylaminocoumarin; 1,2-bis(venzimidazol-2-yl)ethylene; 1,3-diphenylphrazoline; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styrene naphth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H- naphtho-[1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.

Suds Suppressors - Compounds to reduce or suppress the formation of suds can be incorporated into the compositions of the present invention. Suds suppressors can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.

A wide variety of materials can be used as suds suppressors, and suds suppressors are well known to those skilled in the art; see, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressors of particular interest includes monocarboxylic fatty acids and soluble salts thereof; see U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressors typically have hydrocarbyl chains containing from 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts, such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions described herein may also contain non-surfactant suds suppressors. These include, for example, the following: high molecular weight Hydrocarbons such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexaalkylmelamines or di- to tetraalkyldiaminechlorotriazines obtained as products of cyanuric chloride with two or three moles of a primary or secondary amine having 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate esters and monostearyl di-potassium metal (e.g. K, Na and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be used in liquid form. The liquid hydrocarbons are liquid at room temperature and atmospheric pressure and have a pour point in the range of about -40°C to about 50°C and a minimum boiling point of not less than about 110°C (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably having a melting point of less than about 100°C. The hydrocarbons constitute a preferred category of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons thus include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in this discussion of suds suppressors is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused to the silica. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Patent 4,265,779 issued May 5, 1981 to Gandolfo et al. and European Application No. 89 307 851.9 published February 7, 1990 by Starch, M.S.

Other silicone suds suppressors are described in U.S. Patent 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanized silica are described, for example, in German patent application DOS 2 124 526. Silicone defoamers and foam control agents in granular detergent compositions are described in US Patent 3,933,672, Bartolotta et al., and in US Patent 4,652,392, Baginski et al., issued March 24, 1987.

An exemplary silicone-based suds suppressor for use herein is a suds suppressing amount of a foam control agent consisting essentially of:

(i) polydimethylsiloxane fluid having a viscosity of about 20 cs to about 1,500 cs at 25°C;

(ii) about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin consisting of (CH₃)₃SiO1/2 units to SiO₂ units in a ratio of (CH₃)₃SiO1/2 units to SiO₂ units of about 0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) a solid silica gel.

In the preferred silicone suds suppressor used herein, the continuous phase is constructed from certain polyethylene glycols and polyethylene-polypropylene glycol copolymers and blends thereof (preferred) or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably non-linear.

To further illustrate this point, typical liquid controlled suds laundry detergent compositions optionally include from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight percent of the silicone suds suppressor which is (1) a non-aqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or silicone resin-forming silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of the mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of greater than 2% by weight; and without polypropylene glycol. Equal amounts can be used in granular compositions, gels, etc.; see also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al., at column 1, line 46, through column 4, line 35.

The silicone suds suppressor described herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all of which have an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers described herein have a solubility in water at room temperature of greater than about 2% by weight, preferably greater than about 5% by weight.

The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably from about 100 to 800, most preferably from 200 to 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of about 1:1 to 1:10, most preferably from 1:3 to 1:6, of polyethylene glycol copolymer to polyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not contain polypropylene glycol, especially with a molecular weight of 4,000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other suds suppressors useful herein include the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the silicones described in US 4,798,679,4075,118 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the trade name ISALCHEM 123. Mixed suds suppressors typically comprise mixtures of alcohol + silicone in a weight ratio of 1:5 to 5:1.

For any detergent composition used in automatic laundry washing machines, foams should not form to the extent that they overflow the washing machine. Foam suppressors, if used, are preferably present in a "foam suppressing amount." By "foam suppressing amount" it is meant that the formulator of the composition can select an amount of this foam control agent that can sufficiently control foaming, resulting in a low foaming laundry detergent for use in automatic laundry washing machines.

The compositions described herein generally include from 0% to about 5% suds suppressor. When monocarboxylic fatty acids and their salts are used as suds suppressors, they are typically present in amounts of up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% fatty acid monocarboxylate suds suppressor is used. Silicone suds suppressors are typically used in amounts of up to about 2.0% by weight of the detergent composition, although higher amounts may be used. This upper limit is inherently practical, primarily considering the minimization of cost and the effectiveness of lower amounts to effectively control sudsing. Preferably, from about 0.01% to about 1% silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentages include any silica that may be used in combination with the polyorganosiloxane, as well as any auxiliary materials that may be employed. Monostearyl phosphate suds suppressors are generally employed in amounts ranging from about 0.1% to about 2% by weight of the composition. Hydrocarbon suds suppressors are typically employed in amounts ranging from about 0.01% to about 5.0%, although higher levels may be employed. The alcohol suds suppressors are typically employed at 0.2% to 3% by weight of the finished compositions.

Fabric Softeners - Various laundry-added fabric softeners, particularly the very fine smectic clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softening clays known in the art, may optionally be used in the present compositions, typically at levels of from about 0.5% to about 10% by weight, to provide fabric softening benefits simultaneously with a dry cleaner. Clay softeners can be used in combination with amine and cationic softeners, for example as described in U.S. Patent 4,375,416, Crisp et al., March 1, 1983, and U.S. Patent 4,291,071, Harris et al., issued September 22, 1981.

Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. When used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.

More specifically, the preferred polyamine N-oxide polymers for use herein contain units of the following structural formula: R-Ax-P, wherein P is a polymerizable unit to which an N-O group may be attached, or the N-O group may form part of the polymerizable unit, or the N-O group may be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N= , x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or a combination thereof, to which the nitrogen of the N-O group may be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The NO group can be represented by the following general structures:

wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group may be bonded or form part of any of the above-mentioned groups. The amine oxide moiety of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more preferably pKa < 6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibition properties. Examples of suitable polymer backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates, and mixtures thereof. These polymers include random or block copolymers where one type of monomer is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers usually have a ratio of amine to the amine N-oxide of from 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost all degrees of polymerization. Typically, the average molecular weight is within the range of from 500 to 1,000,000, most preferably from 1,000 to 500,000, most preferably from 5,000 to 100,000.

The most preferred polyamine N-oxide useful in the detergent compositions described herein is poly(4-vinylpyridine N-oxide) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis, Volume 113, "Modern Methods of Polymer Characterization," the description of which is incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVPs are known to those skilled in the detergent art; see, e.g., EP-A-262 897 and EP-A-256 696, incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis added to the wash solutions is between about 2:1 and about 50:1, most preferably between about 3:1 and about 10:1.

The detergent compositions described herein may optionally contain about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners, which may also provide dye transfer inhibition activity. If used, the compositions described herein preferably contain about 0.01 to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt forming cation such as sodium or potassium.

In the above formula, when R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation, such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'stilbenedisulfonic acid and the disodium salt. This particular brightener species is marketed commercially under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions described herein.

In the above formula, when R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilenedisulfonic acid disodium salt. This particular brightener species is marketed commercially under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

In the above formula, when R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is marketed commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide particularly effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX, and/or Tinopal AMS-GX) provide significantly better dye transfer inhibition in aqueous wash solutions than either of these two detergent composition components when used alone. Without wishing to be bound by theory, it is believed that such brighteners act in this manner because they have a high affinity for fabrics in the wash solution and therefore deposit relatively quickly on those fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter referred to as the "depletion coefficient." The exhaustion coefficient is generally the ratio of a) the brightener material deposited on the textile to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are best suited for inhibiting dye transfer in the context of the present invention.

Of course, it will be recognized that other conventional optical brightener types of compounds may optionally be used in the present compositions to provide conventional textile "brightening" benefits rather than a true dye transfer inhibition effect. Such use is conventional and well known in detergent formulations.

Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included in the compositions described herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. When high sudsing is desired, suds boosters such as C10-C16 alkanolamides can be incorporated into the compositions, usually at levels of 1% to 10%. The C10-C14 monoethanol and diethanolamides illustrate a typical class of such suds boosters. The use of such suds boosters with high sudsing auxiliary surfactants such as amine oxides, betaines and sultaines identified above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSO4 and the like may be added at levels typically from 0.1% to 2% to provide additional foaming and enhance grease removal performance.

Various detergent ingredients employed in the present compositions can optionally be further stabilized by absorbing these ingredients onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. Preferably, the detergent ingredient is mixed with a surfactant before being absorbed into the porous substrate. In use, the detergent ingredient is released from the substrate into the aqueous wash liquor where it develops its desired detergent function.

To illustrate this technique in more detail, porous hydrophobic silica (trade name SIPERNAT D10, Degussa) is mixed with a proteolytic enzyme solution containing 3% to 5% of non-ionic surfactant from ethoxylated C13-15 alcohol (EO 7). Typically, the enzyme/surfactant solution is 2.5 times the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this method, ingredients such as the above-mentioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioning agents and hydrolysable surfactants can be "protected" for use in detergents, including liquid detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols, as exemplified by methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for solubilizing surfactant, however, polyols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups (e.g., 1,3- propanediol, ethylene glycol, glycerin and 1,2-propanediol) may also be used. The compositions may contain from 5% to 90%, usually 10% to 50%, of such carriers.

The detergent compositions described herein are preferably formulated so that during use in aqueous cleaning operations, the wash water has a pH of from about 6.5 to about 11, preferably from about 7.5 to 10.5. Automatic dishwashing product formulations preferably have a pH of from about 8 to about 11. Laundry products typically have a pH of from 9 to 11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

The following examples illustrate compositions according to the invention, but are not intended to limit the same.

EXAMPLE I

A dry laundry bleach is as follows:

Component % (wt.)

Sodium percarbonate 20.0

Benzoyl caprolactam activator 10.0

Mn catalyst (MnIV₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂ as described in U.S. Patent Nos. 5,246,621 and 5,244,594.) 0.1

Water-soluble filler (sodium carbonate/sodium silicate mixture (1 : 1)) Rest

In the above composition, sodium percarbonate can be replaced by an equivalent amount of perborate.

In the above composition, the bleach catalyst can be replaced by an equivalent amount of the following catalysts:

MnIII2 (u-O)1 (u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2 (ClO4 )2 ;

MnIV4 (u-O)6 (1,4,7-triazacyclononane)4 (ClO4 )4 ; MnIIIMnIV 4 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 ; MnIV(1,4,7-trimethyl)-1,4,7-triazacyclononane(OCH3 )3 (PF6 ); Co(2,2'-bispyridylamine)Cl2 ; Di(isothiocyanato)bispyridylamine cobalt(II); tridipyridylamine cobalt(II) perchlorate; Co(2,2-bispyridylamine) 2 O 2 ClO 4 ; bis(2,2'-bispyridylamine)copper(II) perchlorate; Tris(di-2-pyridylamine)iron(II) perchlorate; Mn-gluconate;

Mn(CF3SO3)2; Co(NH3)5Cl; binuclear Mn complexed with multidentate tetra-N and multidentate Bi-N ligands; including N4MnIII(u-O)2MnIVN4)+ and [Bipy2MnIII(u-O)2MnIVbipy2]-(ClO4)3 and mixtures thereof.

In addition, in the above composition, the bleach activator can be replaced by an equivalent amount of the following activators:

Benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, octanolycaprolactam, octanolyvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecanoylcaprolactam, undecanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam 3,5, 5-trimethylhexanoylvalerolactam, dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam, terephthaloyldicaprolactam, terephthaloyldivalerolactam, (6-Octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

The compositions of Example 1 can be used per se as a bleaching agent or they can be added to a presoak or surfactant-containing detergent composition to impart a bleaching benefit thereto.

In the laundry detergent compositions below, the abbreviated component names mean the following:

LAS - Sodium C12 alkyl benzene sulfonate

TAS - Sodium tallow alkyl sulfate

TAEn - tallow alcohol, ethoxylated with n moles of ethylene oxide per mole of alcohol.

25EY - a predominantly linear C12-C14 primary alcohol condensed with on average Y moles of ethylene oxide.

TAED - tetraacetylethylenediamine

NOBS - Nonanoyloxybenzenesulfonate

Silicate - Amorphous sodium silicate (the SiO₂:Na₂O ratio normally follows)

NaSKS-6 - Crystalline layered silicate

Carbonate - anhydrous sodium carbonate

CMC - sodium carboxymethylcellulose

Zeolite A - hydrated sodium aluminosilicate with a primary particle size in the range of 1 to 10 µm.

Polyacrylate - homopolymer of acrylic acid with a molecular weight of 4000

Citrate - trisodium citrate dihydrate

Ma/AA - copolymer of maleic acid/acrylic acid in a ratio of 1:4, average molecular weight of about 80,000.

Enzyme - Mixed proteolytic and amylolytic enzyme, distributed by Novo Industries AG.

Brightener - Disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2,2'- disulfonate .

Foam suppressor - 25% paraffin wax, melting point 50ºC, 17% hydrophobic silica, 58% paraffin oil.

Sulfate - anhydrous sodium sulfate

For use in fabric cleaning, the compositions are used in conventional manner and at conventional concentrations. Thus, in a typical mode, the compositions are introduced into an aqueous liquor in proportions which may range from about 100 ppm to about 10,000 ppm, depending on the soil load, and the soiled fabrics are agitated therewith.

EXAMPLE II

The following detergent compositions were prepared (parts by weight):

Water and various other things to refill.

* MnIV2 (u-O)3 (1,4,7-trimethyl-1,4,7-triazacyclononane)2 (PF6 )2 .

The above mentioned compositions can be modified by the addition of lipase enzymes.

The above mentioned compositions can be further modified by replacing the bleach catalyst with an equivalent amount of the bleach catalysts given in Example I.

The above compositions may also be modified by replacing the benzoylcaprolactam with an equivalent amount of the bleach activators given in Example I.

The above mentioned compositions can also be modified by replacing the TAED with an equivalent amount of NOBS or by omitting the TAED from the formulation.

The above compositions can also be replaced by replacing the perborate with an equivalent amount of percarbonate.

EXAMPLE III

A laundry bar with bleach was prepared by standard extrusion processes and comprised C12-13 LAS (20%), sodium tripolyphosphate (20%), sodium silicate (7%), sodium perborate monohydrate (10%), (6-decanamidocaproyl)oxybenzenesulfonate (10%), MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2(1.0%), MgSO4 or talc filler; and water (5%).

The above compositions can be modified by the addition of lipase enzymes.

The above compositions may be further modified by replacing the bleach catalyst with an equivalent amount of the bleach catalyst set forth in Example I.

The above compositions can also be modified by replacing the (6-decanamidocaproyl)oxybenzenesulfonate bleach activator with an equivalent amount of the bleach activators set forth in Example I.

The above compositions can also be modified by replacing the perborate with an equivalent amount of percarbonate.

EXAMPLE IV

A composition for automatic dishwashing was prepared as follows.

Component % (wt.)

Trisodium citrate 15

Sodium carbonate 20

Silicate¹ 9

Non-ionic surfactant² 3

Sodium polyacrylate (MG 4000)³ 5

Termamyl enzyme (60T) 1,1

Savinase enzyme (12T) 3.0

Sodium perborate monohydrate 10

Benzoylcaprolactam 2

Mn catalyst 4 0.03

Minor components rest

¹ BRITESIL, PQ Corporation

² Polyethylene oxide/polypropylene oxide low foamer

³ ACCUSOL, Rohm and Haas

⁴ 1:1 molar ratio of Mn cation and ligand to form MnIV₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂ in situ.

In the above composition, the perborate can be replaced by an equivalent amount of percarbonate.

In the above composition, the bleach catalyst can be replaced with an equivalent amount of preformed bleach catalyst as set forth in Example I or with metal cations and ligands to form the bleach catalyst set forth in Example I.

The above compositions may also be modified by replacing benzylcaprolactam with an equivalent amount of the bleach activators given in Example I.

In the above composition, the surfactant can be replaced by an equivalent amount of a low-foaming nonionic surfactant. Examples include low-foaming or non-foaming ethoxylated straight chain alcohols such as the PlurafacTM RA series sold by Eurane Co., the LutensolTM LF series sold by BASF Co., the TritonTM DF series sold by Rohm & Haas Co., and the SynperonicTM LF series sold by ICI Co.

Automatic dishwashing compositions may be in granular, tablet, bar or rinse aid form. Methods for making granules, tablets, bars or rinse aids are known in the art; see, for example, U.S. Patent Serial Nos. 08/106,022, 08/147,222, 08/147,224, 08/147,219, 08/052,860, 07/867,941.

All of the above granular compositions may be provided as spray dried granules or high density (over 600 g/l) granules or agglomerates. If desired, the Mn catalyst may be adsorbed onto or in water soluble granules to keep the catalyst separate from the rest of the compositions, thereby providing additional stability during storage. Such granules (which should not contain oxidizable components) may include, for example, water soluble silicates, carbonates and the like.

While the foregoing compositions are typical of those useful herein, it is most preferred that: (1) the compositions do not contain STPP builders; (2) that the ratio of nonionic surfactant to anionic surfactant is greater than 1:1, preferably at least 1.5:1; and (3) that at least 1% perborate and other chlorine scavengers be present in the compositions to minimize the formation of MnO2 during use.

Although the foregoing examples illustrate the use of the present technology in cleaning/bleaching compositions designed for use in laundry and dish care, it will be recognized by those skilled in the art that the catalyzed bleaching systems described herein can be used in any circumstance where improved oxygen bleaching is desired. Thus, for example, the technology of this invention can be used to bleach paper pulp, bleach hair, clean and sanitize prosthetic devices such as dentures, in denture compositions to clean teeth and kill oral bacteria, and in any other circumstances where bleaching is beneficial to the user.

Claims (8)

1. A detergent composition comprising a catalytically effective amount of one or more bleach catalysts, a bleach compound capable of producing hydrogen peroxide in an aqueous liquor, and one or more bleach activators, wherein the bleach activators are members selected from the group consisting of: a) an amido-derived bleach activator of the general formula: or mixtures thereof, wherein R¹ is an alkyl, aryl or alkaryl group having 1 to carbon atoms, R² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, R⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms, and L is a leaving group; b) a benzoxazine-type bleach activator of the formula: wherein R₁ is H, alkyl, alkaryl, aryl, arylalkyl and wherein R₂, R₃, R₄ and R₅ may be identical or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR₆, wherein R₆ is H or an alkyl group, and carbonyl functions; c) N-acyl lactam bleach activators of the formula: wherein n is 0 to 8, preferably 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 carbon atoms, or a substituted phenyl group having 6 to 18 carbon atoms; and d) Mixtures of a), b) and c). 2. A composition according to claim 1 comprising a percarbonate or perborate bleach compound or mixtures thereof and a bleach activator selected from the group consisting of benzoylcaprolactam, benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecanoylcaprolactam, undecanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam, 3,5,5-trimethylhexanoylvalerolactam, dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam, terephthaloyldicaprolactam, Terephthaloyldivalerolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof. 3. The composition of claim 2, wherein the bleach catalyst is selected from the group consisting of MnIV₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, MnIII₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂; MnIV₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄; MnIIIMnIV 4 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 ; MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane(OCH3 )3 (PF6 ); Co(2,2'-bispyridylamine)Cl2 ; di(isothiocyanato)bispyridylamine cobalt (II); trisdipyridylamine cobalt(II) perchlorate Co(2,2-bispyridylamine)2 O&;sub2;ClO4; bis(2,2'-bispyridylamine)copper(II) perchlorate; tris(di-2-pyridylamine)iron(II) perchlorate; Mn(CF3SO3)2; binuclear Mn; Bi-N-dentate ligands, including N4MnIII(u-O)2-MnIVN4)+ and [Bipy2MnIII(u-O)2MnIVbipy2]-(ClO4)3 and mixtures thereof. 4. Laundry detergent composition comprising conventional surfactants, other detergent ingredients and a bleach composition according to claim 1. 5. The composition of claim 4, wherein the bleaching compound is selected from the group consisting of percarbonate, perborate and mixtures gen thereof, a bleach activator selected from the group consisting of benzoylcaprolactam, benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecanoylcaprolactam, undecanoylvalerolac tam. (6-Decanamidocaproyl)oxybenzenesulfonate and mixtures thereof. 6. A method for improving the bleaching performance of bleach compositions comprising oxygen or a peracid bleach or a bleach compound capable of producing hydrogen peroxide in an aqueous liquor, and one or more bleach activators, wherein the bleach activators are members selected from the group consisting of a) an amido-derived bleach activator of the general formula: or mixtures thereof, wherein R¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, R⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms, and L is a leaving group; b) a benzoxazine-type bleach activator of the formula: wherein R₁ is H, alkyl, alkaryl, aryl, arylalkyl and wherein R₂, R₃, R₄ and R₅ may be the same or different substituents selected from H, halogen, alkyl, Al kenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR₆, where R₆ is H or an alkyl group, and carbonyl functions; c) N-acyl lactam bleach activators of the formula: wherein n is 0 to 8, preferably 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 carbon atoms, or a substituted phenyl group having 6 to 18 carbon atoms; and d) mixtures of a), b) and c); the process comprising adding a catalytically effective amount of manganese cations thereto in the presence of a ligand. 7. A method for removing stains from fabrics, hard surfaces or tableware comprising contacting the fabrics, hard surfaces or tableware with an aqueous medium comprising a bleaching composition according to claim 1. 8. A machine dishwashing composition comprising a low foaming nonionic surfactant and a bleaching composition according to claim 1.