MXPA96005655A - Peroxig whitening composition - Google Patents

Abstract

The present invention relates to: Bleaching compositions comprising an inorganic peroxygen compound and bicyclic and tricyclic diketone as an activator for the peroxygen compound. The composition preferably comprises about 1 to about 75% peroxygen bleach compound and about 1 to about 75% of a bicyclic or tricyclic diketone bleached compound activator. Conventional additives such as surfactants, antifoaming agents, fabric softeners, stabilizers, inorganic reinforcing salts, buffers, enzymes and the like may be present as indicated. The compositions can be formulated as dry concentrated aqueous solutions, aqueous solutions containing non-aqueous solvents, and so on. The compositions are safe for the environment, are effective bleaching agents below room temperature to higher temperatures, are biodegradable and are otherwise highly desirable.

Description

BLEACHING COMPOSITION DB PEROXIGEMQ The present invention relates to bleaching compositions containing a peroxygen bleaching compound and a bicyclic or tricyclic diketone. In the aqueous solution and at room temperature or at higher temperatures, the peroxygen bleach compound is activated to form a dioxirane. More particularly, this invention relates to bleaching compositions comprising a mixture of a monopersulfate peroxygen bleach compound and a bicyclic or tricyclic diketone bleach activator which react together in the aqueous solution to form a dioxirane bleach composition.

BACKGROUND OF THE INVENTION Bleaching compositions are used at home and in industrial applications to bleach stains on hard surfaces and soiled fabrics. Hypochlorite bleaches are effective in removing stains, when used in relatively high concentrations, but hypochlorite, along with other chlorine bleaches, cause severe damage to fabric colors as well as damage to textile fibers. . Additionally, liquid hypochlorite bleaches present packaging handling problems. Damage to fabric and color can be minimized by using milder oxygen bleaches such as sodium perborate or potassium monopersulfate. The stain removal characteristics of these peroxygen bleaches, however, are much less desirable than those of the harsher halogen bleaching agents. As a result of this, commercial bleach compositions which contain peroxygen bleach commonly use activators, e.g., compounds that improve the performance of the peroxygen bleach. Bleaching compositions employing different types of bleach activators have been described, for example, in the Poplin patent of the United States of America No. 1,940,768 of December 26, 1933; in the Baevsky patent, United States of America No. 3,061,550 of October 30, 1962; in the MacKellar and others patent of the United States of America No. 3,338,839 of August 29, 1967; and the Woods patent of the United States of America No, 3,556,711 of January 19, 1971.

The continued attempt to find effective activators, other than those already present and employed in the art, include US Pat. No. 3,822,114 which discloses a bleaching composition comprising a peroxygen bleaching compound and a bleach activator. aldehyde or ketone. U.S. Patent No. 3,822,114 fails to provide a bleach composition acceptable to the user and effective already that the bleaching process can not be carried out at room temperature, requiring instead that the washing to remove stains from the fabrics be carried out at temperatures in excess of 100 ° F.

Robert W. Murray in his article entitled "Dioxiranos", Chem Rev. 1989. pages 1187-1201, describes the formation of dioxiranes of ketones and monopersulfates but fails to teach the bleach activators of cycloalkenidone ketal described in the co-pending application Series No. 7 / 870,632 of the bicyclic or tricyclic diketone activators of the present invention, which makes it possible to carry out the bleaching at room temperature of the stained fabrics and the hard surfaces. aldermar Adam et al., in Acc. Chem Res. 1989, pages 22, 205-211 shows the formation of oxiranes of monopersulfates and ketones but as in the case of Murray, the publication fails to describe the criticality of the bleach activator selection. if satisfactory bleaching results are to be performed at room temperature.

In the co-pending patent application Series No. 7 / 870,632 assigned to the same assignee of the present application, bleach activators are described representing an improvement over those previously described for use in cleaning of fabrics and hard surfaces. The described activators are capable of activating the peroxygen compound at room temperature while causing less damage to the fabric that is being cleaned. The bleach activators described in the aforementioned application are the ketal cyclohexanediones and when mixed with the peroxygen compound allow the user to effectively remove stains and dirt from fabrics and / or hard surfaces at room temperature.

It is an object of this invention to provide improved bleaching compositions for use at room temperature by bleaching and / or removing stains from fabrics and hard surfaces.

It is a further object of the invention to provide new and improved activating agents for peroxygen bleaches.

It is still another object of the invention to provide improved concentrated bleaching compositions for use alone or in combination with other conventional lavage aids to improve the removal of stains on fabrics or hard surfaces.

It has now been found that by combining a peroxygen bleaching agent with a bicyclic ketone or As a tricyclic activator for the bleaching agent, improved compositions are obtained which achieve the above objects and are unexpectedly superior in their bleaching effectiveness with respect to the prior art compositions.

The peroxygen bleach compositions of the invention can be used directly in an aqueous solution for bleaching a fabric or a hard surface or in the alternative the bleaching compositions can be incorporated as an additive to a cleaning composition such as a laundry detergent, a non-aqueous laundry detergent, a scouring powder, a hard surface cleaning composition, an automatic powder dishwashing composition, a non-aqueous automatic dishwashing composition, a bleaching composition for hair, a wound cleaning composition, a dental cleaning composition, a paper bleaching composition, a pre-stain remover and the like.

SYNTHESIS OF THE INVENTION The present invention provides new and improved peroxygen bleaching compositions which are comprised of a peroxygen bleach compound and a bicyclic bleach or tricyclic diketone bleach activator corresponding to the general formula: wherein R Rj, R3 and R4 are each hydrogen, Cl-8 alkyl, C6-12 aryl, C7-12 alkylaryl, halogen (fluoro, chloro or bromo), or nitrogen, m is O, 1, 2 or 3 and n is 0, 1, 2, or 3. The compositions described can be used to whiten or clean fabric articles and hard surfaces at room temperature with virtually no damage resulting to the fabric or surface being cleaned. The invention also provides cleaning compositions incorporating the aforementioned compositions in their formulas, provides a process for the activation of the peroxygen compounds and methods for using the bleaching compositions.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to peroxygen bleaching compositions, and to the processes of stain removal and / or bleaching, carried out in an aqueous solution using the peroxygen bleaching compositions of the invention. The peroxygen bleach activator combination, for example, the bleaching composition of the invention is useful in a plurality of practical areas both in the home and in the industry. For example, the bleach compound activator compositions can be used alone or in combination with other conventional ingredients to carry out (1) the direct bleaching of the blemishes on the fabrics; (2) the removal by bleaching of the spots found on hard surfaces; and (3) the inhibition of the transfer to fabric articles of solubilized or suspended dyes found in the solutions for washing the fabrics.

The bleaching compositions of the present invention comprise a mixture of a peroxygen bleaching compound preferably a monoperoxysulfate and more preferably a potassium monoperoxysulfate and bicyclic or tricyclic diketone, more specifically a decalindione or a derivative thereof, having the formula as mentioned above as the peroxygen bleach activator, in a ratio by weight of peroxygen bleach compound to peroxygen bleach activator of from about 1: 1 to about 100: 1, more preferably from about 1: 1 to about 50: 1, and more preferably from 1: 1 to about 10: 1.

The bleaching agents used in the present composition are inorganic peroxygen salts, organic peroxygen acids and their water soluble salts. Examples of inorganic peroxygen salts include water-soluble monopersulfates and water-soluble monoperoxyphosphates. Specific examples of such salts include sodium monopersulfate, potassium monopersulfate, disodium monoperphosphate and dipotassium monoperphosphate. Highly preferred peroxygen salts, such as those which are more highly activated by the activators used in the present invention are the sodium and potassium monopersulfates of the formulas NaHS03 and KHS05 respectively. Potassium monopersulfate is commercially available from E.l. duPont de Nemours and Company, Inc., under the trade designation "Oxone". The Oxone contains approximately 41.5% by weight, KHSOj the rest being KHS04 and K2S04 in almost equal proportions.

The peroxyacids which are suitable for use in the present invention have the general formula O II HO-0-C-R-Y wherein R is an alkylene group containing from 1 to about 16 carbon atoms or an arylene group containing from 6 to about 8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic group in aqueous solution. And includes, for example, -C-OH -C-0-OH, and -S-OH The organic peroxyacids or salts thereof suitable for use in the invention may contain either one or two peroxy groups and may be either aliphatic or aromatic. When the organic peroxyacid is aliphatic, the unsubstituted acid has the general formula HO-0-C- (CH2) n-Y where Y, for example, can be -CH3, -CH2C1, -C-OH, -C-O-OH, -S-OH and n can be an integer from 1 to 12, with the peracetic acids (n = 7) being the preferred compounds. The alkylene and / or Y group bond (if there is alkyl) may contain halogen or other non-interfering substituents. Examples of the preferred aliphatic peroxyacids include diperacetic acid and diperadipic acid.

When the organic peroxyacid is aromatic, the unsubstituted acid has the general formula HO-O-C-C ^ -Y where Y is hydrogen, halogen, alkyl, -C-OH -O-S-OH -C-O-OH for example -C-O-OH and the groups Y can be in any relative position around the aromatic ring. The ring and / or the Y group (if it is alkyl) may contain a non-interfering substituent such as the halogen groups. Examples of suitable aromatic peroxy acids or salts thereof include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid and the monosodium salt of diperoxideterphthalic acid. Preferred aromatic peroxyacids are m-chloroperoxybenzoic acid and p-nitroperoxybenzoic acid. A highly preferred aromatic peroxyacid is a diperoxyisophthalic acid. Mixtures of the peroxygen salt compounds and the peroxyacids can also be employed in the present invention.

The concentration of peroxygen bleach compound in the compositions of the invention is from about 1 to about 75% by weight, preferably from about 5 to about 60% by weight and more preferably from about 5 to about 50% by weight. The concentration of the peroxygen bleach compound is of a sufficient level in the composition to provide about 1 ppm to about 1000 ppm, when the composition is contacted and dissolved in water at the higher ambient temperature.

The peroxygen bleach activating compounds of the present invention have the formula selected from the group of: wherein R.sup.lf R.sup.2, R.sup.3 and R.sup.4 are each hydrogen, Cj-C, C6-C, 2-aryl, C6-C alkylaryl, halogen (fluoro, bromo or chloro) or nitrogen and may be in any ring-in any combination; is O, 1, 2 and 3 and n is 0, 1, 2 or 3. Preferably the alkyl has l to 6 carbon atoms, and the arylalkyl has from 7 to 10 carbon atoms. The functions Diketone can be in any position on the cyclic structure in any combination. Three examples of the preferred bicyclic and tricyclic diketones are decalin-1, 5-dione (formula 3), methyldecalin-1, 6-dione (formula 4) and tricyclic dione (formula 5). (See the form given below) The most preferred peroxygen bleach activators are those that have a melting point of at least 25 ° C at atmospheric pressure.

Unlike in the case of a bleach containing chlorine, for example, sodium hypochlorite, the reaction mechanism of the bleaching system is an oxygen donor mechanism giving rise to an intermediate dioxirane when the composite composition of the bleaching compound and the bleach activator they come in contact with water at room temperature or higher.

The mechanism can be generally shown as: 0 The peroxygen bleach compound reacts with the decayindione peroxygen bleach activator upon contact with water to form the dioxirane bleaching agent. It is believed that during the bleaching process the intermediate dioxirane reverts back to the original diketone, thus behaving as a catalyst.

The peroxygen bleach activators of the present invention as mentioned previously have a melting point of at least 25 ° C which allows dry solid peroxygen bleach activators, unlike liquid peroxygen bleach activators. , being dry mixed later and easily with the peroxygen bleaching compound. Additionally, the peroxygen bleach activators of the present invention they have the advantage that they are fully activated in the presence of water over a wide temperature range below room temperature to higher temperature conditions; they are stable solids resistant to hydrolysis; and they are biodegradable leaving no nitrogen residue and therefore are environmentally safe and acceptable. In addition, the decalindiones as described above exceed the operation of the bleach activators of the current state of the art including those described in the copending application Series No. 7 / 870,632.

The concentration of the dioxirane formed in the water in use is from about 1 to about 10,000 parts per million (ppm), more preferably from about 1 to about 5,000 ppm, and more preferably from about 1 to about 1,000. ppm.

The peroxygen bleach composition which can be used directly in water or as an additive in a fully formulated cleaning composition comprises the peroxygen bleach compound and the peroxygen bleach activator in a ratio by weight of bleach compound to bleach activator of about 100%. 1: 1 to about 100: 1, preferably from about 1: 1 to about 50: 1 and more preferably from about 1: 1 to about 10: 1. The peroxygen bleach composition can be used as a additive for a fully formulated composition at a concentration level of from about 1 to about 75% by weight, preferably from about 6 to about 60% by weight, and more preferably from about 5 to about 50% by weight , depending on the type of cleaning composition.

In order to improve the shelf life of the peroxygen bleach composition, either the peroxygen bleach compound, for example, the monopersulfate or the decalindione bleach activator can be encapsulated using any of the conventional encapsulating agents which are soluble in water at a preselected temperature. Conventional techniques can be used for encapsulation.

A typical automatic dishwashing composition in powder form of the present invention comprises: (a) from 20 to 70% of a detergent builder salt; (b) from 5 to 40% of an alkali metal silicate; (c) from 0 to 30% of an alkali metal carbonate; (d) from 0 to 6% of a nonionic anionic surfactant; (e) from 0 to 6% of a foam depressant; (f) from 0 to 4% of an anti-film agent selected from the group consisting of silica, alumina and titanium dioxide; (g) from 0 to 20% of a low molecular polyacrylic acid; (h) from 0 to 20% of at least one enzyme; (i) from 1 to 75% of a peroxygen bleach compound; Y (j) from 1 to 75% of a decalindione or derivative thereof as a bleach activator.

A typical non-aqueous liquid automatic dishwashing composition comprises approximately by weight: (a) from 3 to 20% of an alkali metal silicate; (b) from 0 to 15% of a clay gel thickener; (c) from 0 to 1% of a hydroxypropyl cellulose polymer; 5 (d) from 0 to 25% of a low molecular weight polyacrylate polymer; (e) from ~ 0 to 15% of a liquid non-ionic surfactant; (f) from 2 to 15% of an alkali metal carbonate; (g) from 0 to 7% of a stabilizing system; 15 (h) from 0 to 25% of an alkali metal citrate; (i) from 0 to 20% of at least one enzyme; (j) from 0 to 20% of a non-aqueous liquid carrier; (k) from 1 to 75% of a peroxygen bleach compound; Y (1) from 1 to 75% of a decalindione bleaching compound activator.

A typical detergent composition in powder form comprises approximately by weight: (a) from 0 to 25% of at least one nonionic surfactant; (b) from 0 to 25% of at least one anionic surfactant; (c) from 0 to 40% of a zeolite; (d) from 5 to 45% of at least one reinforcing salt; (e) from 0 to 5% of a polyethylene glycol; (f) from 0 to 10% of an alkali metal silicate; (g) from 0 to 10% of a low molecular weight polyacrylate polymer; (h) from 0 to 30% of an alkali metal sulfate; (i) from 1 to 75% of a peroxygen bleach compound; Y (j) from 1 to 75% of a decalindione bleaching compound activator.

A typical non-aqueous laundry detergent comprises approximately by weight: (a) from 20 to 70% of a nonionic surfactant; (b) from 0.5 to 20% of a non-aqueous solvent; (c) from 10 to 60% of at least one reinforcing salt; (d) 0.5 to 1.5% of a foam depressant; (e) from 1 to 75% of a peroxygen bleach compound; Y (f) from 1 to 75% of a decalindione bleach compound activator.

A typical scouring powder composition comprises approximately by weight: (a) Silex White 90.85 (b) Detergent 2.0 (c) Sodium Carbonate 6.0 (d) Decalindiona bleached system l.O (e) Perfume 0.15 A typical non-concentrated powder bleaching composition comprises approximately by weight: (a) from 1 to 75 Potassium Monopersulfate (b) from 1 to 75 Decalindiona (c) from 2 to 15% Sodium carbonate (d) 50-0% Silex A more detailed description and explanation of the ingredients used in the previously defined formulas is as follows: The bleaching activating process of the invention is carried out in the aqueous solution having a pH of from about 7 to about 12. Outside of this pH range, bleaching operation fails markedly. Since an aqueous solution of the persalts or peracids of the present invention is generally acrylic, it is necessary to maintain the pH conditions required by using standard buffering agents. A buffering agent is, of course, any non-interfering compound which can alter and / or maintain the pH such as any standard buffering agent or combination. For example, phosphates, carbonates or bicarbonates are useful which buffer the pH range 7-12. Examples of the buffering agents include sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate and sodium hydrogen phosphate. Other buffering agents for any desired pH can be obtained by a skilled artisan from any chemistry manual or standard chemistry text. Buffering agents generally comprise from about 1% to about 85% by weight of the concentrated bleaching compositions present.

The nonionic surfactants that can be used in the compositions are well known.

Nonionic synthetic organic detergents suitable for use herein include fatty alcohols propoxylated ethoxylated which are low foam surfactants and are possibly clogged. These detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an aromatic hydrophobic compound of organic alkyl or aliphatic with ethylene oxide and / or propylene oxide (hydrophilic in nature). Almost any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen subject to oxygen or nitrogen can be condensed with ethylene oxide or with propylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a non-ionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those described in U.S. Patent Nos. 4,316,812 and 3,630.92.

Preferably, the nonionic detergents are low foam polyalkoxylated lipophilic, wherein the desired hydrophilic-lipophilic balance is obtained by the addition of a hydrophilic poly-lower alkoxy group to a lipophilic group. A preferred class of the non-ionic detergents are the poly-lower alkoxylated higher alkanols, wherein the alkanol has from 9 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) it is from 3 to 15. It is preferred to employ the lower poly-lower alkoxylated alkanols, the alkanol being a fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and containing from 5 to 15 or from 5 to 16 groups of lower alkoxy per mol. Preferably, the lower alkoxy is ethoxy but in some cases, this may be desirably mixed with propoxy, the latter, if present, usually constituting more than 50% of the mixture. Examples of such compounds are those wherein the alkanol contains from 12 to 15 carbon atoms and about 7 ethylene oxide groups are present per mole.

The useful nonionics are represented by the low foam Plurafac series available from BASF Chemical Company which are the reaction product of the linear higher alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Product A (a C? 3-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Product B (a C13-C fatty alcohol, 5 fused with 7 moles of oxide) of propylene and 4 moles of ethylene oxide) and Product C (a C13-Cu fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide). The preferred surfactants are Plurafac LF132 and LF231 which are capped nonionic surfactants. Another nonionic surfactant Liquid suitable for use here is sold under the trade name Lutensol SC 9713.

The nonionic ionic surfactants available from ICI such as Synperonic LF / D25 are especially preferred for use in the formulation of automatic dishwashing detergent compositions of the present invention.

Other useful surfactants are Neodol 25-7 and Neodol 23-6.5, the products of Shell Chemical Company, Inc. The latter is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 13 carbon atoms, the number of ethylene oxide groups present averaging about 6.5. The higher alcohols are primary alkanols. Still other examples of suitable detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corporation. The first is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide.

Also useful in the present invention is a component of nonionic, higher molecular weight nonionic detergents, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are made by Shell Chemical Company In the lower poly-lower alkoxylated alkanols, in order to obtain the best balance of the hydrophilic and lipophilic groups, the number of lower alkoxy groups will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably from 40 to 60% thereof and the nonionic detergent will preferably contain at least 50% of such preferred higher poly-lower alkoxy-alkanol.

The alkylpolysaccharide surfactants which may be used alone or in combination with the aforementioned surfactants are those having a hydrophobic group containing from about 8 to 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, more preferably from 12 to 14 carbon atoms, and a polysaccharide hydrophilic group containing from 1.5 to about 10, preferably from about 1.5 to 4, and more preferably from 1.6 to 2.7 units removed (eg, galactoside, glucoside , fructoside, glucosyl, fructosil and / or galactosyl units). The mixtures of the groups Saccharides may be present in the alkyl polysaccharide surfactants. The alkyl polysaccharide surfactants correspond to the following formula: In the formula, x indicates the number of units removed in a particular alkyl polysaccharide surfactant. For a particular alkyl polysaccharide molecule, x can only represent an integral value. Any physical sample can be characterized by the average value of x and this average value can assume non-integral values. As used in this application, the value of x is to be understood as a designated average value. The hydrophobic group (R) can be attached to the 2-, 3- or 4-positions rather than the 1- position (resulting in, for example, a glucosyl or galactosyl as opposed to a glucoside or galactoside).

However, fastening in the 1- position is preferred, eg, glycosides, galactosides, fructosides, etc. In the preferred product, the extra saccharide units are predominantly attached to the unit of previous removal position 2-. The union through the 3-, 4- and 6- position can also occur. Optionally and less desirably, there can be a polyalkoxide chain linking the hydrophobic group (R) and the polysaccharide chain. The preferred alkoxide group is ethoxide.

Typical hydrophobic groups include alkyl groups, whether saturated or unsaturated, branched or unbranched, containing from about 8 to about 20, preferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group contains up to 3 hydroxy groups and / or a polyalkoxide chain containing up to about 30, preferably less than 10, more preferably 0 alkoxide groups.

Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosils, lactosils, glucosyl and / or glactosils and mixtures thereof.

The alkyl onosaccharides are relatively less soluble in water than the higher alkyl polysaccharides.

When used in combination with the alkylpolysaccharides, the alkyl monosaccharides are solubilized to some extent.

The use of alkyl monosaccharides in combination with the alkylpolysaccharides in a preferred way of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

Preferred alkyl polysaccharides are alkyl polyglucosides having the formula: (R20) C? HÁ0) t (Z) x wherein Z is derived from glucose, R is a hydrophobic group selected from alkyl, alkylphenyl, hydroxyalkylphenyl and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms. carbon; n is 2 or 3 preferably 2, r is from 0 to about 10, preferably 0; and x is from 1.5 to about 8, preferably from 1.5 to 4, more preferably from 1.6 to 2.7. These compounds are prepared by reacting a long chain alcohol (R20H) with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step process in which a short chain alcohol (Cj-6) is reacted with glucose or a polyglucoside (x = 2 to 4) to give a short chain alkyl glucoside (x = 4) which can in turn be reacted with a longer chain alcohol (R2OH) to displace the short chain alcohol and obtain the desired alkyl polyglucoside. If this two-step process is used, the short chain alkyl glucoside content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5% and more preferably 0% the alkyl polyglucoside.

The "amount of unreacted alcohol (the content of free fatty alcohol) in the desired alkyl polysaccharide surfactant is preferably less than 2%, more preferably less than about 0.5% by weight of the total alkyl polysaccharide. uses, it is desirable to have the monosaccharide alkyl content of less than about 10%.

As used herein, the "alkyl polysaccharide surfactant" is intended to represent both the preferred glucose and galactose-derived surfactants as well as the less preferred alkyl polysaccharide surfactants. As used in this application the term "alkyl polyglucoside" includes the alkyl polyglycosides because the stereochemistry of the saccharide group is changed during the preparation reaction.

An especially preferred glycoside surfactant APG is an APG 625 glycoside manufactured by Henkel Corporation of Ambler, PA. APG 25 is a nonionic alkyl polyglycoside characterized by the formula: where n = 10 (2%); n = 12 (65%); n = 14 (21-28%); n = 16) (4-8%) and n = 18 (0.5%) and x (degree of polymerization) = 1.6. The APG 625 has: a pH of 6-8 (10% of APG 625 in distilled water); a specific gravity of 25 ° C of 1.1 grams / ml; a density at 25 ° C of 9.1 kilograms / gallon; a calculated HLB of around 12.1 and a Brookfield viscosity at 35 ° C, a spindle 21, 5-10 RPM from around 3,000 to about 7,000 centipoises. Mixtures of two or more of the liquid nonionic surfactants can be used advantageously.

Other detergent active materials useful in the compositions are the water dispersible surfactants of betaine and sulfoxide, phosphine oxide, amine oxide, organic anionics, the first mentioned anionic being the most preferred, the particularly preferred surfactants here are the mono, and / or commercially available linear or branched alkali metal alkyl (C8-C) diphenyl mono- and / or di-oxide sulfates, for example as DOWFAX® 3B-2 and DOWFAX 2A-1. In addition, the surfactant must be compatible with other ingredients of the composition. Other suitable organic anionic non-soap surfactants include the primary alkyl sulphates, the alkylsulfonates, the alkylaryl sulfonates and the sec. alkyl sulfates. Examples include sodium C 0 -C 8 alkyl sulfates such as sodium dodecyl sulfate and sodium tallow alcohol sulfate; sodium C, 0-CIg alkenesulfonates such as solid hexadecyl-1-sulfonate and sodium C, 2-C, alkyl g, alkyl, benzenesulfonates, for example, sodium dodecylbenzenesulfonate. The corresponding potassium salts can also be used.

Other suitable surfactants or detergents, suitably for use in the invention include the amine oxide surfactants typically of the structure R2R, NO, in which Rj represents a lower alkyl group, eg, methyl, and Rt represents an alkyl group of long chain having from 8 to 22 carbon atoms, for example, a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a corresponding R ^ PO surfactant phosphine oxide or a sulfoxide RR, S0 can be used. Betaine surfactants are typically of the structure R2R1N + R "C00-, in which each R represents a lower alkylene group having from 1 to 5 carbon atoms.Specific examples of these surfactants include lauryl dimethylamine oxide, myristyl oxide dimethylamine, the corresponding phosphine oxides and sulfoxides, and the corresponding betaines, including dodecyldimethylammonium acetate, tetradecyldiethylmonium pentanoate, hexadecyldimethyl-lamonium hexanoate and the like. To ensure biodegradability, the alkyl groups in these surfactants must be linear and any compounds are preferred.

Surfactants of the above type, as well as known in the art, are described, for example, in U.S. Patent Nos. 3,985,668 and 4,271,030. If the chlorine bleach is not used, then any of the well-known low-foam nonionic surfactants such as the alkoxylated fatty alcohols, for example, the propylene oxide-ethylene oxide condensates mixed with fatty alcohols They can also be used.

Foam inhibition is important to increase the efficiency of the laundry machine and dishwasher and minimize the destabilizing effects that may occur due to the presence of excess foam inside the washing machine during use. The foam can be reduced by proper selection of the type and / or amount of the active detergent material, the main foam producing component. The degree of foam depends somewhat on the hardness of the washing water in the machine so that the proper adjustment of the proportions of the reinforcing salts such as NaTPP having a water softening effect can help to provide a degree of foam inhibition. . However, it is preferred generally including a stable foam inhibitor depressant chlorine bleach. Particularly effective are the alkyl phosphoric acid esters of the formula: HO-P-OR In the formula indicated above, one or both of the groups R independently represent an alkyl ethoxylated or alkyl group. The ethoxylated derivatives of the ester, for example, the condensation products of an ester mold with from 1 to 10 moles, preferably 2 to 6 moles, more preferably 3 or 4 moles of ethylene oxide may also be used. Some examples of the alkyl phosphoric acid esters that are commercially available include the SAP products from Hooker and LPKN-158 from Knapsack. Mixtures of esters or any other stable types of chlorine bleach, or mixtures of mono-, and di-esters of the same type may also be employed. Especially preferred is a mixture of C6-C18 alkyl acid phosphate mono- and di-esters such as the diatearyl / monostearyl phosphates 1.2 / 1 and the ethylene oxide condensates of 3 to 4 moles thereof . When used, the proportions of 0 to 1.5% by weight, preferably from 0.05 to 0.5% by weight of the foam suppressant in the composition are typical, the weight ratio of the active detergent component to the foam suppressant generally varying from about 10: 1 to 1: 1 and preferably from about 5: 1 to 1: 1 . Additional defoamers which may be used include, for example, known silicones, such as those available from Dow Chemical. In addition, it is an advantageous feature of this invention that many of the stabilizing salts, such as the stearate salts, for example, aluminum stearate when included, are also effective as foam inhibiting suppressors.

Some specific examples of the alkali metal detergent builder salts used in the composition include the polyphosphates, such as alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal metaphosphate and the like, for example, sodium or potassium tripolyphosphate. (hydrated or anhydrous), tetrasodium or tetrapotassium pyrophosphate, sodium or potassium hexa-metaphosphate, trisodium or tripotassium orthophosphate, and the like. Phosphate boosters, where they are not prohibited due to local regulations, are preferred and mixtures of tetrapotassium pyrophosphate (TKPP) and sodium tripolyphosphate (NaTPP) (especially hexa idrate) are especially preferred. Typical proportions of NaTPP to TKPP are from about 2: 1 to 1: 8, preferably from 1: 1.1 to 1: 6. The The total amount of detergent builder salts is preferably from about 5 to about 45% by weight, preferably from about 15 to 35%, more preferably from about 18 to 30% by weight of the composition.

In combination with the reinforcing salts, a low molecular weight unlinked polyacrylate is optionally used having a molecular weight of from about 1,000 to about 100,000, more preferably from about 2,000 to about 80,000. A preferred low molecular weight polyacrylate is Norasol LMW45ND manufactured by Norsohaas and having a molecular weight of about 4,500. These low molecular weight polyacrylates are used at a concentration of about 0 to 15% by weight, more preferably 0.1 to 10% by weight.

Other useful cross-linked low molecular weight polymers are Acusol "** 0 640D sold by Rohm &Haas and Norasol QR1014 sold by Norshohaas having a GPC molecular weight of 10,000.

The compositions may also contain a phosphate-free reinforcing system composed of a mixture of phosphate-free particles formed from a reinforcing salt and a low molecular weight polyacrylate. A solid reinforcing salt preferred is an alkali metal carbonate such as a sodium carbonate or sodium citrate or a mixture of sodium carbonate and sodium citrate. When a mixture of sodium carbonate and sodium citrate is used, a ratio by weight of sodium carbonate to sodium citrate of about 9: 1 to about 1: 9, preferably from about 3: 1 to about 1: 3.

Other reinforcing salts which can be mixed with sodium carbonate and / or sodium citrate are the gluconates, phosphonates and salts of nitriloacetic acid. In conjunction with the reinforcing salts, low molecular weight polyacrylates are optionally used having a molecular weight of from about 1,000 to about 100,000 and preferably from about 2,000 to about 80,000. Preferred low molecular weight polyacrylates include Sokalan * 1 ** 0 * CP45 and SokalanMARCA CP5 manufactured by BASF having a molecular weight of about 70,000. Another preferred low molecular weight polyacrylate is AcrysolMARCALMW45ND manufactured by Rohm and Haas having a molecular weight of about 4,500.

SokalanMARCA CP45 is a partially neutralized copolymer of methacrylic acid and maleic anhydride. For use herein, the copolymer must have a water absorption at 38 ° C and 78% relative humidity of less than about 40% and preferably less than about 30%. The Sokalan1 ** 0 * CP5 is a fully neutralized copolymer of methacrylic acid and maleic acid anhydride. Solan "** 0 * CP45 is classified as an agent against deposition and suspension, which has a low hydroscopicity as a result of decreased hydroxyl group content. Against the redeposition they exhibit a low hidrospicity The copolymerized polyacids have this property, and particularly when they are partially neutralized The Aucsol "** 0 * 640ND available from Rohm &; Haas is another agent against redeposition and useful suspension. Another example of a suitable reinforcer is SokalanMARCA 9786X which is a silicate copolymer and is described in British Patent No. 1,504,168, in United States Patent No. 4,409,136 and in Canadian Patent Nos. 1,072,835 and 1,087,477 . Illustrative of the amorphous zeolites useful herein are those described in Belgian Patent No. 835,351. Zeolites generally have the formula (MjO) x (A1203) and (Si02) zWH20 wherein x is 1, and is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably from 2 to 3 and w is from 0 to 9, preferably from 2.5 to 6 and M is preferably sodium . A typical zeolite is type A or a similar structure with type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange of about 200 milliequivalents per gram or greater, for example 400 meq / g.

The alkali metal silicates are anti-corrosion agents working to make the anti-corrosive composition for the eating utensils and for the parts of the automatic dishwashing machine. Sodium silicates of Na20 / SiO2 proportions of from 1: 1 to 1: 3.4 especially from about 1: 2 to 1: 3 are preferred. Potassium silicates of the same proportions can be used. The preferred silicates are sodium disilicate (hydrated or anhydrous) and sodium metasilicate.

The thickeners that can be used to ensure the physical stability of the suspension and to improve its viscosity are those that will swell and develop thixotropic properties in a non-aqueous environment. These include organic polymeric materials and modified organic and inorganic clays. Essentially any clay can be used as long as it is swollen in a non-aqueous medium and exhibits thixotropic properties. A preferred clay is bentonite. A swelling agent is used with the bentonite clay. The preferred swelling agent is a combination of a propylene carbonate and a tripropylene glycol methyl ether. However, any other substance that will make the bentonite Inflate in a non-aqueous environment and develop thixotropic properties can be employed.

The non-aqueous liquid carrier materials that can be used to formulate non-aqueous liquid compositions include the higher glycols, polyglycols, polyoxides and glycol ethers. Suitable substances are propylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, tripropylene glycol methyl ether, propylene glycol methyl (PM), dipropylene glycol methyl ether (DPM), propylene glycol methyl ether acetate (PMA), dipropylene glycol methyl ether acetate (DPMA), ethylene glycol n-butyl ether and ethylene glycol n-propyl ether. A preferred non-aqueous carrier of the present invention is polyethylene glycol 200 (PEG200) or polyethylene glycol 300 (PEG300).

Other useful solvents are ethylene oxide / propylene oxide, random liquid copolymers such as Synalox solvent series from Dow Chemical (eg Synalox 50-50B). Other suitable solvents include propylene glycol ethers such as PnB, DPnB and TPnB (propylene glycol mono n-butyl ether, dipropylene glycol and tripropylene glycol mono-n-butyl ethers). Sold by Dow Chemical under the Dowanol brand. Other tripropylene glycol monomethyl ether "TPM Dowanol" available from Dow Chemical are suitable. Other useful series of solvents are supplied by CCA Biochem of the Netherlands as, for example, Plurasolv® • • F LS (x), Plurasolv EL, Plurasolv IPL and Plurasolv BL.

Mixtures of solvent PEG with Synalox or PnB, DPnB, TPnB and TPM solvents are also useful. Preferred mixtures are PEG 300 / Synalox 50-50B and PEG 300 / TPnB in proportions by weight of about 95: 5 to 20:80, more preferably of about 90:10 to 50:50. EP / P0 capped nonionic surfactants can be used as a liquid solvent carrier and an example of such a nonionic surfactant is Plurafac LF / 132 sold by BASF.

The system used in the present compositions to ensure phase stability (stabilizing system) may comprise a finely divided silica such as Vab-0-Sil M5, Cab-0-Sil EH5, Cab-O-Sil TS720 or Aerosil 200. The Stabilizer is used at a concentrated level of around 0 to about 4.0% by weight, and preferably from about 0.5 to about 3.0% by weight. Also, finely divided silica mixtures such as Cab-O-Sil and associative non-ionic thickeners such as Dapñral T210, T212 (Akzo) which are dialkyl polyglycol ethers of low molecular weight with a structure of the type can be employed as a stabilizing system. Pluracol hood TH 916 and TH 922 (BASF) associative thickeners having star-like structures with a hydrophilic core and a hydrophobic tail. These thickeners are used at concentration levels around Or at about 5.0% by weight together with about 0 to about 2.0% by weight of finely divided silica. Other useful stabilizing systems are mixtures of organoclay gel and hydroxypropyl cellulose polymer (HPC). A suitable organoclay is Bentone NL27 sold by NL Chemical. A suitable cellulose polymer is Klucel M cellulose having a molecular weight of about 1,000 sold by Aqualon Company. The Bentone gene contains 9% Bentone NL27 powder (100% active), 88% TPM solvent (tripropylene glycol mono methyl ether) and 3% propylene carbonate (polar additive). Organic modified clay thickener gels are used at concentration levels of about 0.0% by weight to about 15% by weight in conjunction with Klucel M at concentration levels of from about 0 to about 0.6% by weight, preferably from about 0.2% by weight to about 0.4% by weight. Another useful thickener is a high molecular weight long chain alcohol such as Unilin **** 0 * 425 sold by Petrolite Corporation.

The detergent formula may also contain a mixture of a proteolytic enzyme and an ilolytic enzyme and optionally a lipolytic enzyme which serves to attack and remove organic waste on glasses, plates, pots, trays and eating utensils such as cutlery. The proteolytic enzymes attack the protein residues, the lipolytic enzymes the fatty residues and the amylolitic enzymes the starches Proteolytic enzymes include the protease enzymes subtilis, bromelin, papain, trypsin and pepsin. Amyololytic enzymes include the amylase enzymes. Lipolytic enzymes include lipase enzymes. The preferred amylase enzyme is available under the name Maxamyl, derived from Bacillus Licheniformis and is available from Gist-Brocades from the Netherlands in the form of a non-aqueous solution (18% by weight of enzyme) having an activity of about 40,000 TAU / g . The preferred protease enzyme is available under the name of Mexatasa derived from a strain of Bacillus designated "PB92", a culture of the bacillus is deposited in the Laboratory for Microbiology of the Technical University of Delft, has the number OR-60 and is supplied by Gist-Bricades, from Holland in a non-aqueous solution (22% by enzyme / activity weight of around 400,000 DU / g.) Preferred enzyme activities per wash are Mexatasa-100-800 KDU per wash and Maxamyl-1, 000 -8, 000 TAU per wash.

The ratio by weight of the solution of the proteolytic enzyme to the amylolytic in the non-aqueous liquid automatic dishwashing detergent compositions is from about 25: 1 to about 1: 1, and preferably about 15: 1 to 1.5 :1.

Other conventional ingredients may be included in these compositions in small amounts, generally less than about 3% by weight, such as perfume, hydrotropic agents, such as sodium benzene, toluene, xylene and eumeno sulfonates, preservatives, dyes and pigments and the like, all of course being stable in the bleaching compounds and the high alkalinity. Especially preferred for the colors are the chlorinated phthalocyanines and the aluminosilicate polysulfides which respectively provide pleasant blue and green tints. Ti02 can be used to whiten- or neutralize bleaching.

The invention can be practiced in various ways and a number of specific embodiments of the bleaching compositions of the present invention are set forth below to illustrate the invention.

In order to test the efficacy of the claimed compositions, the following compositions were prepared and the described procedures were carried out. A solution of 350 mg of potassium monopersulfate (Oxone) and 1.0 gram of Ultra Fab detergent in one liter of water were prepared as the solution of Oxone and Fab Ultra detergent were added 100 mg of 1,5-decalindione (solution A-composition of the invention). A solution of 350 mg of potassium monopersulfate, one gram of Ultra Fab in 1 liter of water, 100 mg of 1,4-cyclohexanedione monoethylene ketal added to the resulting solution was prepared. (Solution B) - Composition of the request for patent series No. 7 / 870,632. A solution of 1 gram of Ultra Fab and 350 milligrams of Oxone in 1 liter of water (Solution C) - Control was prepared.

The bleaching tests were carried out in a terg-o-tometro of 6 cuvettes (1 liter) at 80 ° F and 120 ° F. The tests were carried out with tap water. Solution C acted as a control.

The dioxiranes were generated in place by the addition of Oxone (0.35 grams) and diketone and decalindione (0.10 gms) to the terg-o-tmometer cuvette containing the Fab Ultra detergent. After 30 seconds of stirring the aforementioned solution, the stained samples were added to the solution and the stirring was continued for 15 minutes. The spots were rinsed in tap water, dried and their reflectances were measured on a reflectometer to determine the average percentage of dirt removal (percent ASR).

The following four stained samples were evaluated with respect to the bleaching in the test: o Grape Juice on dacron (65 / cotton (35) or Blueberry cake on cotton calico OR Red pine-114 on heavy cotton or Instant coffee on cotton calico .

* Commercial stain sold as EMPA-114 by Test Fabrics.

Determination of the Average Dirt Removal Rate: The average% dirt removal value (% ASR) was calculated by averaging the individual percentage values of soil removal (% SR) of the four evaluated spots. The percent removal of dirt (% SR) of the stained sample was determined by manipulating its reflectance values which are measured from the sample both before and after washing. A reflectance value is the amount of light that a surface (such as that of a sample) will reflect. The following example illustrates this protocol. The samples stained with red wine (EMPA-114) were bleached in the Dioxirane system (bicyclic Dicetone-Oxone A) or cyclohexyldione monoethylene ketal-B using the procedure given above. Table 1 provides the reflectance values measured on the samples without stain (without dirt, with the stain (soiled) and after washing (washing).) For each stain there were two samples evaluated so that there is a calculated average value.

Summary of Dioxin Bleaching Efficacy Comparisons in Tert-O-Tachometer at 80 and 120 ° F: Asua de la Llave: 15 minutes.

Table 1: Dirt Removal% values at T = 8Q ° F Activator Juice Red Wine Cake * Coffee / Tea Promedi Grape Cranberry Empa-114 (System f65D / 35C) (Cotton Percale) (Heavy Cotton) (Cotton Percale) 4-Spot Dicetone (A) Bicyclic 59 + 1 89 + 1 43 + 2 73 + 1 65 + Dione (B) Cyclohexyl 58 + 1 86 + 1 39 + 1 69 + 7 63 + Monoketal Sol. Pat. E.U.A. No. 7/870362 Oxone (C) 37 + 6 38 + 10 35 + 3 26 + 6 34 + (A) Decalin-1, 5-dione (100% active) (100 ppm or 100 mg / l), FAB Ultra (1000 ppm, or 1 gm / 1), Oxone (350 ppm, or 350 mg / l).

(B) 1,4-Cyclohexanedione, monoethylene ketal (100 ppm, 6 100 mg / l), FAB Ultra (1000 ppm, 6 1 gm / 1), Oxone (350 ppm, or 350 mg / l). (C) FAB Ultra (1000 ppm, or 1 gm / 1), Oxone (350 ppm, or 350 mg / l).

Ahem II The bleaching efficiency of the bicyclic diketone (A) was also evaluated in comparison to the cyclohexyldione monoethylene ketal (B) of the co-pending application at a temperature of 120 ° F. The results are set forth in Table 2. In all cases, the bicyclic diketone was more effective in the removal of the stain.

Table 2; Values of% Dirt Removal at T = 12Q ° F Activator Juice Red Wine Cake * Coffee / Tea Average Grape Empa-114 (System (65D / 35C) (Cotton Percale) (Heavy Cotton) (Cotton Percale) 4-stain Dicetone (A) Bicyclic 55 + 4 89 + 1 46 80 + 4 68 + 2 Dione (B) Cyclohexyl 27 + 2 75 + 2 40 + 2 51 + 1 48 + 1 Monocetal Sun. Pat. E.U.A. No. 7/870362 (A) Decalin-1, 5-dione (100% active) (100 ppm or 100 mg / l), FAB Ultra (1000 ppm, 61 gm / 1), Oxone (350 ppm, or 350 mg / l).(B) 1,4-Cyclohexanedione, monoethylene ketal (100 ppm, or 100 mg / l), FAB Ultra (1000 ppm, or 1 gm / 1), Oxone (350 ppm, or 350 mg / l).

Table 3: Values of% of Removal of Dirt to T * 80 «F Activator Juice Red Wine Cake * Coffee / Tea Average Grape Empa-114 (System (65D / 35C) (Cotton Percale) (Heavy Cotton) (Cotton Percale) 4-stain Dicetone (A) Bicyclic 54 + 2 74 + 2 33 + 1 86 + 5 62 + 2 Dione (B) Cyclohexyl 65 + 2 86 + 1 41 + 1 89 + 2 70 + 1 Monocetal Sun. Pat. E.U.A. No. 7/870362 SNOBS (C) 51 + 1 57 + 3 58 + 3 55 + 5 55 + 2 (A) Methyl decalin-l, 65-dione (100% active) (100 ppm or 100 mg / l), FAB Ultra (1000 ppm, or 1 «gm / 1), Oxone (350 ppm, or 350 mg / l) ).

(B) 1,4-Cyclohexanedione, monoethylene ketal (100 ppm, or 100 mg / l), FAB Ultra (1000 ppm, or 1 gm / 1), Oxone (350 ppm, or 350 mg / l).

(C) SNOBS (106 mg), 94.3% Active (100 mg, 0.297 mmol), Ultra FAB (1000 ppm or 1 gm / ml), Sodium Perborate (127 ppm, 4: 1).

Table 4: Values of% Dirt Removal at T - 120 ° F Activator Juice of Red Wine Cake * Coffee / Tea Average Grape Emulberry Em-a-114 (System (65D / 35C) (Cotton Percale) (Heavy Cotton) (Cotton Percale) 4-stains Dicetone (A) Bicyclic 63 + 2 82 + 2 51 + 1 91 + 3 72 + 1 Dione (B) Cyclohexyl 48 + 4 71 + 5 47 + 1 77 + 6 61 + 4 Monocetal Sun. Pat. E.U.A. No. 7/870362 SNOBS (C) 58 + 2 64 + 3 57 + 2 78 + 4 64 + 2 (A) Methyl decalin-1, 65-dione (100% active) (100 ppm or 100 mg / l), FAB Ultra (1000 ppm, or 1-gm / 1), Oxone (350 ppm, or 350 mg / l) ).

(B) 1,4-Cyclohexanedione, monoethylene ketal (100 ppm, or 100 mg / l), FAB Ultra (1000 ppm, or 1 gm / 1), Oxone (350 ppm, or 350 mg / l).

(C) SNOBS (106 mg), 94.3% Active (100 mg, 0.297 mmol), Ultra FAB (1000 ppm or 1 gm / ml), Sodium Perborate (127 ppm, 4: 1).

Claims (30)

R E I V I N D I C A C I O N S

1. A peroxygen bleaching composition which comprises approximately by weight a mixture of: (a) about 1 to about 75% of a peroxygen bleach compound; Y (b) about 1 to about 75% of a peroxygen bleach compound activator which is characterized by the formula: wherein R ,, R2, R3 and R4 are each a member selected from the group consisting of hydrogen, alkyl having from about 1 to about 8 carbon atoms, aryl having from about 6 to about 12 carbon atoms, alkylaryl having from 7 to 12 carbon atoms, fluorine, chlorine, bromine, and nitrogen, m is 0, 1, 2 or 3 and n is 0, 1, 2, 6, 3.

2. A peroxygen bleach composition, as claimed in clause 1, characterized in that said peroxygen bleach compound is an inorganic peroxygen bleach compound.

3. A peroxygen bleaching composition, as claimed in clause 2, characterized in that said inorganic peroxygen bleaching compound is a member selected from the group consisting of monopersulfates and monoperoxyphosphates.

4. A peroxygen bleaching composition, as claimed in clause 2, characterized in that said inorganic peroxygen bleaching compound is a monoperoxysulfate.

5. A peroxygen bleaching composition, as claimed in clause 2, characterized in that said inorganic peroxygen bleaching compound is potassium mono-peroxysulfate.

6. A peroxygen bleach composition, as claimed in clause 1, characterized in that each peroxygen bleach compound and said peroxygen bleach activator are present in an amount of from about 5 to about 60% by weight.

7. A peroxygen bleach composition, as claimed in clause 1, characterized in that each of said peroxygen bleach compounds and said peroxygen bleach activator are present in an amount of from about 5 to about 50% by weight. weight.

8. A peroxygen bleaching composition, as claimed in clause 1, characterized in that said mixture is dissolved in water at a concentration of about 0.050 to about 10 grams of said mixture per liter of water.

9. A peroxygen bleach composition, as claimed in clause 1, characterized in that it further includes at least one non-aqueous liquid carrier, said mixture of said inorganic peroxygen bleaching compound wherein said peroxygen bleach activator is present in a concentration of about 0.05 to about 10% by weight.

10. A peroxygen bleaching composition, as claimed in clause 1, characterized in that it also includes at least one member selected from the group consisting of anti-foam agents, thickening agents, surfactants, fabric softening agents, antistatic agents , stabilizers, buffering agents, salts inorganic reinforcers, agents against redeposition and suspension, alkali metal silicates, enzymes, anticorrosion agents, buffers, stabilizing agents, preservatives, dyes and pigments.

11. The bleaching composition, as claimed in clause 1, characterized in that said bleach compound activator has a cyclic structure selected from the group consisting of

12. A bleaching composition, as claimed in clause 11, characterized in that said bleached compound activator is decalin-1,5-dione.

13. A bleaching composition, as claimed in clause 11, characterized in that said bleach compound activator is methyl-decalin-1, 6-dione.

14. A bleaching composition, as claimed in clause 11, characterized in that said bleached compound activator is a tricyclic dione.

15. A bleaching composition, as claimed in clause 1, characterized in that it additionally includes a non-aqueous carrier.

16. A bleaching solution comprising water and about 10 to about 1,000 ppm of a composition according to clause 1.

17. A bleaching solution, as claimed in clause 16, characterized in that it includes at least one member selected from the group consisting of non-aqueous liquid carriers, surfactants, anti-foam agents, thickeners, fabric softening agents, agents antistatic, stabilizers, agents against redeposition and suspension, inorganic reinforcing salts, enzymes, buffers, anticorrosion agents, preservatives, dyes and pigments of alkali metal silicates.

18. A bleaching composition in powder form comprising by weight: (a) from 20 to 70% of an esterifying reinforcing salt; (b) from 5 to 40% of an alkali metal silicate; (c) from 0 to 30% of an alkali metal carbonate; (d) from 0 to 6% of a nonionic anionic surfactant; 10 (e) from 0 to 6% of a foam depressant; (f) from 0 to 4% of an anti-film agent selected from the group consisting of 15 silica, alumina and titanium dioxide; (g) from 0 to 20% of a low molecular polyacrylic acid; 20 (h) from 0 to 20% of at least one enzyme; (i) from 1 to 75% of a peroxygen bleach compound; Y 25 (j) from 1 to 75% of a decalindione or derivative thereof as a bleach activator.

19. A bleaching composition in a non-aqueous liquid automatic dishwashing form comprising by weight: (a) from 3 to 20% of an alkali metal silicate; (b) from 0 to 15% of a clay gel thickener; (c) from 0 to 1% of a hydroxypropyl cellulose polymer; (d) from 0 to 25% of a low molecular weight polyacrylate polymer; (e) from 0 to 15% of a liquid non-ionic surfactant; (f) from 2 to 15% of an alkali metal carbonate; (g) from 0 to 7% of a stabilizing system; (h) from 0 to 25% of an alkali metal citrate; (i) from 0 to 20% of at least one enzyme; (j) from 0 to 20% of a non-aqueous liquid carrier; (k) from 1 to 75% of a bleaching compound, peroxygen; Y (1) from 1 to 75% of a decalindione bleaching compound activator.

20. A bleaching detergent in powder form comprising by weight: (a) from 0 to 25% of at least one nonionic surfactant; (b) from 0 to 25% of at least one anionic surfactant; (c) from 0 to 40% of a zeolite; (d) from 5 to 45% of at least one reinforcing salt; (e) from 0 to 5% of a polyethylene glycol; (f) from 0 to 10% of an alkali metal silicate; (g) from 0 to 10% of a low molecular weight polyacrylate polymer; (h) from 0 to 30% of an alkali metal sulfate; (i) from 1 to 75% of a peroxygen bleaching compound; Y (j) from 1 to 75% of a decalindione bleaching compound activator.

21. A laundry detergent bleaching composition in a non-aqueous form comprising by weight: (a) from 20 to 70% of a nonionic surfactant; (b) from 0.5 to 20% of a non-aqueous solvent; (c) from 10 to 60% of at least one reinforcing salt; (d) 0.5 to 1.5% of a foam depressant; (e) from 1 to 75% of a peroxygen bleach compound; Y (f) from 1 to 75% of a decalindione bleach compound activator.

22. A bleaching composition in powder form for dry scrubbing comprising by weight: (a) Silex White 90.85 (b) Detergent 2.0 (c) Sodium Carbonate 6.0 (d) Decalindione bleaching system 1.0 comprising from 1 to 75% of a peroxygen bleaching compound; and from 1 to 75% of a decalindione bleaching compound activator; Y (e) Perfume 0.15

23. A bleaching composition in the form of non-concentrated powder comprising by weight: (a) from 1 to 75 Potassium Monopersulfate (b) from 1 to 75 Decalindiona (c) from 2 to 15 Sodium carbonate (d) 50-90 Silex

24. A method for cleaning fabrics soiled by bleaching comprising adding to an aqueous wash liquor the composition as claimed in clause 1 in an amount sufficient to clean soiled fabrics.

25. A method for removing stains on hard surfaces by bleaching comprising contacting said stained surface with an effective amount of a composition as claimed in clause 1.

26. A method, as claimed in clause 25, characterized in that said composition is present in an aqueous medium.

27. A method for inhibiting the occurrence of dye transfer from the aqueous medium in which the soiled fabrics are being cleaned by bleaching the fabrics comprising adding to the aqueous washing medium an amount of the composition of clause 1 in an amount sufficient to inhibit the transfer of dye.

28. A dioxirane selected from the group consisting of

29. A method for activating a peroxygen bleaching compound present in an aqueous solution which comprises adding an activator selected from the group consisting of to said aqueous solution containing said peroxygen bleach compound.

30. A method, as claimed in clause 29, characterized in that said peroxygen bleach compound is a monopersulfate salt. SUMMARY Bleaching compositions comprising an inorganic peroxygen compound and bicyclic and tricyclic diketone as an activator for the peroxygen compound. The composition preferably comprises about 1 to about 75% peroxygen bleach compound and about 1 to about 75% of a bicyclic or tricyclic diketone bleached compound activator. Conventional additives such as surfactants, antifoaming agents, fabric softeners, stabilizers, inorganic reinforcing salts, buffers, enzymes and the like may be present as indicated. The compositions can be formulated as dry concentrated aqueous solutions, aqueous solutions containing non-aqueous solvents, and so on. The compositions are safe for the environment, are effective bleaching agents below room temperature to higher temperatures, are biodegradable and are otherwise highly desirable.